Thesis Tgolnas

THIN-FILM THERMO-MECHANICAL SENSORS EMBEDDED IN METALLIC STRUCTURES
A DISSERTATION SUBMITTED TO THE DEPARTMENT OF MATERIALS SCIENCE AND ENGINEERING AND THE COMMITTEE ON GRADUATE STUDIES OF STANFORD UNIVERSITY IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
Anastasios Golnas December 1999
Copyright by Anastasios Golnas 2000 All Rights Reserved
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I certify that I have read this dissertation and that in my opinion it is fully adequate, in scope and quality, as a dissertation for the degree of Doctor of Philosophy.
Friedrich B. Prinz (Principal Adviser)
William D. Nix
David M. Barnett
Approved for the University Committee on Graduate Studies: _______________________________________________ Dean of Graduate Studies
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Abstract
The ability to monitor in real time the thermo-mechanical responses of tools, equipment, and structural components has been very appealing to the aerospace, automotive, drilling, and manufacturing industries. Such responses can be measured with the appropriate sensors: thermocouples for temperature and strain gages for deformation. So far, the challenge has been to instrument the tools, equipment, or structural components with a number of sensors in an economical way and also protect the sensors from the environment which the tools, etc. are exposed to. In this work, a sequence of manufacturing processes that can be used to build thin-lm temperature and strain sensors on internal surfaces of metallic structures is proposed and demonstrated. The use of thin-lm techniques allows the parallel fabrication of sensor arrays, whereas a layered manufacturing scheme, e.g.: Shape Deposition Manufacturing, permits the creation of sensors on the internal surfaces of metallic parts and their subsequent embedding as the parts are completed. Specically, thin-lm sensors are deposited on an insulating aluminum oxide lm, which is grown on a polished stainless steel substrate. The oxide is deposited by sputtering an aluminum target in a reactive atmosphere. The sensors are sputter-deposited from alloy targets, shaped via micromachining and
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partially covered with a passivation layer of aluminum oxide. The thin-lm structure is then partially covered by two protective layers of copper and nickel. Both layers are electroplated and their purpose is to protect the thin lms during the deposition of the embedding layers. Embedding is accomplished by using a high-power infrared laser to melt a powder bed on top of the protective layers. Invar, a Fe-Ni alloy with very small coefcient of thermal expansion, is used as embedding material in order to minimize the effect of residual thermal stresses on the structure. Among the issues that emerged during the denition of the fabrication sequence were: the long-term stability of reactive deposition, the presence of pinholes in the dielectric layers, the adhesion of the thin lms to their substrates, the reactions between the thin lms and the electroplating bath, the adhesion of the electroplated layers to the substrate, the optimal combination of materials and thickness of the protective layers, the bonding between the embedding and the protective layers, and the heat input and residual stresses resulting from the high-temperature embedding process. Last but not least, the calibration of the deposited thin-lm sensors and their splicing to measuring equipment had to be addressed. Finally, a nite element model was constructed in order to simulate the hightemperature embedding process. The heat transfer analysis performed on the model provides the temperature proles of all nodes and can be used as a tool for the optimization of the protective layer thickness. Its results can also be used for a stress analysis of the multilayered structure. In conclusion, an integration of technologies is offered to allow the instrumentation of metallic parts with embedded thermo-mechanical sensors during the manufacturing sequence, in an environment without stringent particle control, while making use of commonly available materials.
Acknowledgments
As the formal completion of my doctoral studies in the Department of Materials Science and Engineering is under way, I am very pleased to have the honor to express my gratitude from the pages of my dissertation to all those who were involved in this journey in research and applied knowledge. Initially, I would like to thank my thesis adviser, Professor Fritz Prinz, who gave me the opportunity to join his group in the spring of 1995. I am still grateful for having been offered a chance to gain direct engineering knowledge and apply my physical intuition by joining a research group where the focus is the fabrication of novel structures and devices. I also feel gratitude for his continuous support and encouragement that helped me overcome the disappointments that are so abundant in any experimental and engineering problem. Finally, I must thank him for our numerous discussions on a variety of scientic, engineering, cultural, and political subjects which augmented my vision and understanding. I am also indebted to Professor Robert Merz who was instrumental in the conception of the embedded sensors research project and the realization of the mesoscopic structures laboratory. Robert provided the early framework of the project, recruited me as the student in charge, and served as an excellent guide in the rst stages of the research.
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It is my honor to acknowledge the support of Professors David M. Barnett and William D. Nix who served in my Reading and Defense Committees, as well as Professor Martin Fischer who chaired my Defense Committee. I owe special thanks to Professor Michael Kelly, also a member of my Defense Committee, who was an excellent resource in my quest for the cause of pinholes in the dielectric thin lms, both through his class and his personal consulting. I would also like to thank the members of my Qualifying Examination Committees: Professors W.D. Nix, R. Sinclair, R.H. Dauskardt, and T. Huffnagel. Furthermore I am grateful to the Department, its faculty, students, and administration for providing a superb environment for learning, and for offering their help in every occasion I needed it. It has been an unmatched experience. I owe many thanks to my colleagues in the Rapid Prototyping Laboratory (RPL) for their help with my research and preparation for the Oral Examination, as well as for their support all these years. I am especially indebted to Tom Hasler, Dr. Jrgen Stamp, and Rudi Leitgeb, who helped with various aspects of the deposition chamber operation. Special thanks are due to my ofcemates, Dr. Alexander Cooper, Dr. Alex Nickel, and Dr. John Kietzman, with whom I engaged in vastly entertaining discussions. I also want to thank Sylvia Walters and Lynn Hoschek for their administrative help throughout my service in the RPL. All research on the embedded sensors project was funded by the Ofce of Naval Research through the contract N00014-96-1-0354-P00003, and it is my satisfaction to acknowledge their continuing support for a second three-year period. Concluding my expression of gratitude to the scientic community at Stanford, I would like to make a very special reference to my colleagues Xiaochun Li of the RPL, and Kevin Ohashi and Dr. Surya Iyer of the R.H. Dauskardt group. Their contribution to the work presented in the next pages cannot be overstated. Surya (now with Applied Materials, Inc.) did all the setup for the rst experimental
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strain measurements of the thin lm strain gages, in March of 98. Kevin contributed many hours helping me to repeat those experiments, twice, in the summer of 99. Without their input it would have been very difcult to test the sensors. Xiaochuns contributions were also of central importance to the project. Apart from his help with the sample preparation, he operated and troubleshot the laser deposition station for the embedding experiments, and offered excellent insight in many stages of the project and especially in the high-temperature aspects. I am also indebted to Professor Reinhold H. Dauskardt for his kind permission to use the testing equipment in his laboratory, Ali Farvid from SLAC for his help in establishing an electroplating facility, and Bob Jones from CMR for his help with the EPMA measurements. It would be an omission not to mention the people who inspired, encouraged, helped, and allowed me to come to one of the premier research institutions of this country. Namely, I want to thank my senior thesis adviser Professor Stergios Logothetidis, and Professors D. Gounaris, G. Theodorou, N. Economou, E. Paloura, K. Paraskevopoulos, and E. Hatzikraniotis, all from the Physics Department of the Aristotle University in Thessaloniki, Greece. I also want to thank the admissions committee of the Department of Materials Science and Engineering, Professor David M. Barnett who served as my academic advisor during my rst year at Stanford, and the School of Engineering for the Fellowship that supported me during the rst academic year. Last, but not least, I would like to express my gratitude to all those who made me feel at home with their love, friendship, and care, and especially to Athina Vassilakis, Dimitris Pantelidis, Constantinos Papadias, Stelios Diamantidis, Phaedon Kyriakidis, Raj Vaidyanathan, Joe Tringe, and Fr. Peter Salmas. Of course, I will always be indebted to my old friends at home and abroad. Finally, I would like to express my deep gratitude and love to my family and acknowledge their unconditional trust and multifaceted support through all these years.
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Table of Contents
Abstract Acknowledgments Table of Contents List of Tables List of Figures 1 Introduction iv vi ix xii xiv 1
1.1 Incentive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1.2 Thin-film Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1.2.1 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1.2.2 Manufacturing Issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 1.3 Basics of Sensor Physics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 1.3.1 Strain Sensors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 1.3.2 Thermocouple Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 1.4 Deposition Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 1.4.1 Sputtering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 1.4.2 Electroplating. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 1.4.3 Laser Assisted Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 1.5 Dissertation Outline. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
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2 Proposed Solution
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2.1 Cleanliness and Surface Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 2.2 Insulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 2.3 Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 2.4 Thermal Protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 2.5 Embedding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 3 Fabrication 28
3.1 Substrate preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 3.1.1 Cutting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 3.1.2 Grinding and polishing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 3.1.3 Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 3.1.4 Sputter-etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 3.1.5 Discussion of cleaning processes . . . . . . . . . . . . . . . . . . . . . . . . . . 33 3.2 Bottom insulation layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 3.2.1 Determination of transition oxygen flow . . . . . . . . . . . . . . . . . . . 36 3.2.2 Deposition sequence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 3.3 Sensor layer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53 3.3.1 Photolithography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53 3.3.2 Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 3.3.3 Lift-off . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56 3.4 Top Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 3.5 Protective Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58 3.5.1 Copper layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60 3.5.2 Nickel layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63 3.6 Embedding Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65 3.6.1 Thermal stress minimization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66 3.6.2 Fusion of the powder layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 3.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71 4 Characterization 73
4.1 Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
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4.1.1 Dielectric layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73 4.1.2 Sensor layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 4.2 Microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79 4.2.1 Dielectric layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79 4.2.2 Sensor films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81 4.2.3 Protective layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81 4.3 Electrical measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 4.3.1 Dielectric strength of dielectric layers . . . . . . . . . . . . . . . . . . . . . . 83 4.3.2 Resistivity of sensor materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 4.4 Strain-gage characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 4.4.1 Experimental setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 4.4.2 Experimental objective and results. . . . . . . . . . . . . . . . . . . . . . . . . 89 4.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98 5 Modeling 100
5.1 Model Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100 5.1.1 Geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100 5.1.2 Material Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 5.1.3 Simulation of a moving heat source . . . . . . . . . . . . . . . . . . . . . . . 106 5.1.4 Boundary and initial conditions . . . . . . . . . . . . . . . . . . . . . . . . . . 107 5.2 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 5.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114 6 Conclusions A The thin-film deposition system B Positive masks of strain sensors C Sample LabView file D ABAQUS heat transfer input file Bibliography 116 120 124 125 128 142
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List of Tables
Table 3.1: Table 3.2: Table 3.3: Table 3.4: Table 3.5: Table 3.6: Table 3.7: Table 3.8: Table 3.9: Nominal composition of 304L stainless steel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 Sputter-etching process parameters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 Surface composition of 304L substrates cleaned with different methods. . . . . . . . . . 33 Atomic content of O, Fe, and Cr in 304L surfaces after sputter-etching. . . . . . . . . . . 34 Material properties for insulating thin films. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 Linear fit parameters for high oxygen flows (Figure 3.1 and Figure 3.2). . . . . . . . . . 39 Characteristics of the voltage-flow hysteresis curves in Figure 3.1. . . . . . . . . . . . . . . 40 Process parameters for reactive deposition of aluminum oxide. . . . . . . . . . . . . . . . . 50 Deposition parameters for the sensor alloys and the adhesion interlayer. . . . . . . . . 56
Table 3.10: Deposition parameters for the seed copper film and the adhesion interlayer. . . . 61 Table 3.11: Chemical composition of copper electroplating solution. . . . . . . . . . . . . . . . . . . . . . . 63 Table 3.12: Electrodeposition parameters for the copper protective layer. . . . . . . . . . . . . . . . . . . 63 Table 3.13: Chemical composition of nickel strike electroplating solution. . . . . . . . . . . . . . . . 64 Table 3.14: Electrodeposition parameters for the seed nickel layer. . . . . . . . . . . . . . . . . . . . . . . 64 Table 3.15: Chemical composition of nickel sulfamate electroplating solution. . . . . . . . . . . . . . . 64
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Table 3.16: Electrodeposition parameters for the nickel protective layer. . . . . . . . . . . . . . . . . . . . 65 Table 4.1: Table 4.2: Table 4.3: Table 4.4: Table 4.5: Table 5.1: Table 5.2: Table 5.3: Nominal composition of constantan, measured values for deposit. . . . . . . . . . . . . . 78 Nominal composition of chromel, measured values for deposit. . . . . . . . . . . . . . . . . 78 Nominal composition of alumel, measured values for deposit. . . . . . . . . . . . . . . . . . 78 Resistivity and thickness of alumel, chromel, and constantan films. . . . . . . . . . . . . . 86 Dimensions and moment of inertia for beam substrate. . . . . . . . . . . . . . . . . . . . . . . . 87 Nodal density along the three axes. Initial model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103 Nodal density along the three axes. Final model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103 Density and thermal properties of materials in the FE model. . . . . . . . . . . . . . . . . . . 105
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List of Figures
Figure 1.1: Generic hysteresis curve in a reactive sputtering system.. . . . . . . . . . . . . . . . . . . . . 17 Figure 1.2: Asymmetric bipolar dc voltage as applied to a magnetron target. . . . . . . . . . . . . . 20 Figure 3.1: Discharge voltage and total pressure vs. oxygen ow for two Al targets. . . . . . . . 37 Figure 3.2: Variation of total pressure with oxygen ow. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38 Figure 3.3: Transition voltage and ow for two Al targets (Figure 3.1 & Table 3.7).. . . . . . . . . 40 Figure 3.4: a) Transition ow and power values for depositions from one Al target. b) Transition ow vs. corresponding power level (from graph a). . . . . . . . . . . . . . 41 Figure 3.5: Actual (markers) and predicted (line) transition ows for 4 depositions. . . . . . . . 43 Figure 3.6: a) Calculation of partial pressureoxygen ow relation. b) Total pressure vs. increasing oxygen ow with and without discharge. . . . . . . 46 Figure 3.7: Oxygen consumption rate vs. discharge power.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48 Figure 3.8: Shadow mask for shaping sputter-deposited Al2O3 layers. . . . . . . . . . . . . . . . . . . 49 Figure 3.9: Discharge voltage and oxygen ow variations during reactive deposition. . . . . . 52 Figure 3.10: Schematic of the photolithography steps preceding a lift-off process. . . . . . . . . . . 54 Figure 3.11: Jagged edge of deposited constantan lm after lift-off.. . . . . . . . . . . . . . . . . . . . . . . 57
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Figure 3.12: Cross-section showing an Al2O3 lm damaged during laser deposition. . . . . . . . 59 Figure 3.13: a) Clustered voids at the invar/copper interface. b) Distinct phases across the partially remelted invar/copper interface.. . . . . . . . 60 Figure 3.14: a) Schematic of substrate with sensor enclosed between two dielectric lms. b) Schematic showing the copper layer footprint. c) Schematic showing the nickel layer footprint. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60 Figure 3.15: Laser path during progressive attempts to improve embedding. . . . . . . . . . . . . . . 68 Figure 3.16: Invar-nickel interface from a cross-section of an embedded structure. . . . . . . . . . 69 Figure 3.17: Final laser path conguration.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70 Figure 4.1: Oxygen-to-aluminum ratio vs. sputter-etching time. . . . . . . . . . . . . . . . . . . . . . . . . 75 Figure 4.2: Aluminum content of deposited Al2O3 lm vs. sputter-etching time.. . . . . . . . . . 76 Figure 4.3: SEM image of amorphous Al2O3 lm on a stainless steel substrate. . . . . . . . . . . . 80 Figure 4.4: XRD spectra of Al2O3 on 304L, and uncoated 304L substrate. . . . . . . . . . . . . . . . . 81 Figure 4.5: Grain sizes in sputtered and electroplated copper layers. . . . . . . . . . . . . . . . . . . . . 82 Figure 4.6: Copper grains in electroplated layer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 Figure 4.7: Optical micrograph of damage caused by self-healing dielectric breakdown. . . . 84 Figure 4.8: SEM image of Al2O3 lm with pinholes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 Figure 4.9: Dimension details of the 4-point bend test setup. . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 Figure 4.10: Outer ber stress and of deposited strain gage output from 4-point bend test. . . 90 Figure 4.11: Displacement and calculated outer ber stress as functions of time. . . . . . . . . . . . 91 Figure 4.12: a) Experimental gage output and nominal strain vs. calculated strain and stress. b) Nominal strain vs. experimental gage output.. . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 Figure 4.13: a) Calculated outer ber stress and output of deposited strain gage.
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b) Calculated outer ber stress and strain measured by calibrated strain gage. . . 94 Figure 4.14: a) Outer ber stress vs. experimental gage output. b) Outer ber stress vs. nominal strain. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 Figure 4.15: Maximum stress and experimental gage response prior to plastic deformation. . 96 Figure 4.16: a) Stress-strain curves for the experimental sensor. b) Stress-strain curves for the commercial sensor. . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 Figure 4.17: Nominal strain vs. deposited sensor output. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97 Figure 5.1: Materials and dimensions of the 4 strata in the geometric model. . . . . . . . . . . . . 102 Figure 5.2: Quantization of the powder bed in elements, top view. . . . . . . . . . . . . . . . . . . . . . 107 Figure 5.3: Heat ux for element sets 1 and 2 in Figure 5.2 and total heat ux. . . . . . . . . . . . 108 Figure 5.4: Experimental and calculated temperature at a point on the Ni-invar interface. . 111 Figure 5.5: Calculated maximum temperatures at the Ni-invar interface.. . . . . . . . . . . . . . . . 112 Figure 5.6: Calculated temperature at the steel-copper interface. . . . . . . . . . . . . . . . . . . . . . . . 113 Figure B.1: The numbers denote the smallest linewidth in m.. . . . . . . . . . . . . . . . . . . . . . . . . 124
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Introduction
The goal of this chapter is to provide the necessary background for the development of the dissertation in the sections that follow. Particularly, an incentive for the embedding of thermo-mechanical sensors is presented, followed by a review of the recent progress on thin-lm sensors. In addition, a brief reference to the physics of thermo-mechanical sensing is made as well as a description of the processing techniques that are useful in making and embedding the sensors.
1.1 Incentive
The idea for embedded sensors came forth by the combination of a commercial need and the existence of an enabling manufacturing concept. It was understood that in various industrial practices it is useful to know in real time the basic operating conditions (i.e.: temperature and deformation or strain) of certain mechanical tools and components. Furthermore, it could be desirable to know these conditions over extended areas of those parts. Examples of cases in which such a concept is useful include the manufacturing industry (molds, dies, drilling bits, etc.), the aerospace industry (components of jet engines), the oil industry (drilling equipment), the power industry (vessels and pipes), the automotive
CHAPTER 1: INTRODUCTION
industry (components of motors), as well as the construction industry (structural components in buildings). Temperature and strain information can only be obtained by placing sensors in those tools, and information from extended areas can only be obtained from arrays of such sensors. Such a solution would call for the placement of the sensors near the points of interest, and therefore the issues of assembly and protection would have to be successfully addressed. The assembly of a large number of sensors is cumbersome, time-consuming, and costly, and this endeavor might become very difcult for tools operating in harsh environments. However, the layered manufacturing of components and tools could allow for the placement of sensors close to the points of interest and for their subsequent enclosure. Besides, the use of Large Scale Integration (LSI) thin-lm processes for the fabrication of the sensors, similar to the ones used in the Integrated Circuit industry, could allow for the simultaneous fabrication of sensor arrays. Thus, the combination of these methods would offer proximity to the desired places, protection from the environment during operation, and the large scale integration of units (i.e. sensors) without the need for extensive postmanufacturing assembly [merz97]. The obvious challenges for this idea result from the fact that most tools and components in the manufacturing, automotive, power, and oil industries, are metallic. Therefore, the sensors (which are essentially simple passive circuits) should be adequately insulated from the surrounding conductive matrix. Furthermore, any layered fabrication technique that is designed to produce functional metallic parts has to add the layers in a high-temperature state. This will achieve a high-quality interlayer bonding via either interdiffusion or partial remelting of the substrate surface. In this case, the sensors, and their insulation, will have to be protected during the high-temperature deposition steps.
Last, but not least, comes the problem of the successful integration of two manufacturing techniques that are fundamentally different in terms of scale and production environments. In most cases, in IC fabrication lines, only silicon and a small number of carefully selected elements are processed in order to produce exceedingly small structures. On the other hand, in large-scale manufacturing plants, where traditional engineering materials are heavily or exclusively used, the conditions are unsuitable for thin-lm processing, which needs a very controlled environment.
1.2 Thin-lm Sensors

1.2.1 Applications
Surface thermocouples have been produced by thin-lm techniques since the 1930s by vacuum evaporation [burg30], or sputtering [harr34]. In the more recent past, the aerospace industry has intensively explored the use of thin-lm thermocouples (TFTCs) as well as strain gages (TFSGs) and ux meters for measuring the conditions on jet-engine turbine blades. Such work was done at Pratt & Whitney Aircraft in the early 1970s, where TFTCs suitable for high temperatures (Type S: Pt/Pt0.9Rh0.1) were sputter-deposited on iron superalloy (FeCrAlY) substrates [gran85]. The substrates were oxidized in air to form an insulating layer of aluminum oxide prior to the deposition of the sensor lms. During the same period NASA began contracting research on thin-lm sensors, and researchers in United Technologies Corp. built TFTCs and TFSGs on typical turbine blade materials (MAR-M-200 with Hf, Hastelloy X, and B1900 with Hf). The substrates were rst coated with a nickel superalloy layer (NiCoCrAlY) that was thermally treated in a controlled atmosphere in order to grow a surface
aluminum oxide lm. In later experiments that were conducted mostly at the NASA Lewis Research Center, an additional alumina lm was deposited by evaporation or rf-sputtering from a compound target [mart94, lei97]. In yet another implementation of TFTC fabrication a seedcoat of aluminum oxide was sputtered on the superalloy layer before the substrate was oxidized in a vacuum furnace with 2% O2 using nitrogen and hydrogen as forming gases [nasa86]. The materials used to create the sensors were Pt and 90Pt-10Rh for the thermocouples (Type S) and NiCr or PdCr for the strain gages. Type S materials are traditionally used in high-temperature environments (up to ~1100C), while PdCr (13%wt. Cr) was selected as the best candidate for high-temperature strain measurements [huls87]. In order to further protect the sensors against corrosion, an aluminum oxide overcoat was deposited either by rf-sputtering or by evaporation onto the metal lms [mart94]. Researchers at the French National Institute for Aerospace Research and Studies (ONERA) have been building thin-lm thermocouples [gode87] and ux meters [gode90] since the 1980s, as well as strain gages [kays93]. The fabrication sequence has essentially the same components with the one developed by NASA and its contractors: Type-S TFTCs, NiCr or PdCr TFSGs, or platinel-type uxmeters were deposited on ~8m of Al2O3 which was also grown on substrates made of commercial nickel-base superalloys with a NiCoCrAlY coating (~30m). All lms and coatings were deposited by rf-sputtering of alloy or compound targets. Finally, the sensors were covered with a thin (0.5m) protective layer of Al2O3 or SiO2. A strong motivation behind efforts to detect the temperature pattern on the surface of turbine blades comes from the need to design blades that withstand ever higher combustion temperatures. As the operating temperatures are elevated, rst stage superalloy blades have to be cooled in order to survive. Film cooling through discreet holes or slots on the blade surface has been selected as a most effective method since the 1950s. However, it is very difcult to
theoretically predict the effectiveness of lm cooling, therefore it has to be determined experimentally [simo93, thak99]. Most research groups have employed stationary at or mildly curved plates to study the effect and data were obtained by wire thermocouples [sinh91, jump91]. It seems that arrays of TFTCs deposited on the surface of the turbine blade provide a more unobtrusive and efcient way to gather temperature data at a high spatial resolution [fess99]. Thin-lm sensors have also been used to monitor the performance of pressure transducers. The latter are widely used in a large variety of applications ranging from the chemical processing industry to the automobile engines. Researchers from the Indian Liquid Propulsion Systems Centre and the Indian Institute of Science deposited a manganese sensing lm on the steel diaphragm of a pressure transducer [naya90]. The diaphragm had previously been coated with an insulation multilayer consisting of alternating Al2O3 and SiO2 lms. The sensor was nally covered with a 0.2m SiO2 lm. All layers were deposited by evaporation and the insulating lms were deposited in a reactive environment.
1.2.2 Manufacturing Issues

Substrate preparation In almost all the examples referenced in Applications on page 3, substrate preparation was the rst key issue in the fabrication sequence. Its importance became apparent through its relation to the adhesion and quality of the insulating layer [naya90, garc93, stor96, nisk98]. The preparation techniques involved polishing of the metallic substrate to a mirror surface nish and subsequent cleaning with degreasing agents. Most of this processing was done in clean-room environments (class 1000-100). Some groups employed sputteretching of the substrates prior to the insulator deposition as a nal cleaning step. A more thorough investigation of the preparation process was carried out by a Spanish research team [garc93] on 17.4 PH stainless steel substrates. They
concluded that chloride particles attached to the surface were the main culprits for defects in the overdeposited dielectric layer as well as for corrosion-induced holes on the steel surface. They also observed that alkaline cleaners (dissolved NaOH) would remove such particles and that there is a denitive increase of the breakdown voltage of the dielectric layer for smoother substrate surfaces and thicker dielectric lms. Their suggested cleaning method takes place in a class 1000-100 clean room and consists of 12 distinct steps. Deposition of insulating lms The deposition of defect-free, adherent insulating lms has been the single greatest challenge for creating thin-lm sensor devices on metallic surfaces. Most groups employed radio frequency (13.56MHz) sputtering of a compound target as the deposition method of choice. The insulating lm was aluminum oxide for all the work done by the aerospace industry teams and a combination of aluminum oxide and silicon dioxide for the team from India. Radio frequency (rf) sputtering is a very slow deposition process and the reported growth rates were 0.03-0.04nm/s. Since a lm thickness of 6-8m was deemed necessary for adequate insulation, the total deposition time was on the order of 50 hours [gode87, lei97]. In many cases the substrate was heated (200-900C) during the aluminum oxide deposition, in order to aid the surface mobility of the adsorbed species, promote the formation of the metastable -phase (which is more corrosion resistant than the amorphous), and cause the development of residual compressive stresses in the ceramic lm upon cooling of the system to room temperature. The last effect would permit the oxide lm to remain below its tensile strength even at elevated temperatures (~1100C) [kays93]. Adhesion of sensor lms Since the sensors used in high-temperature applications contain noble elements such as platinum, it is generally difcult to achieve good adhesion to the
6
insulating lm. Deposition in a slightly reactive atmosphere [gode87], and a high energy sputter-deposition process [gran85] were proposed as solutions to this problem. Protective coatings The use of protective coatings has been advocated by all groups whose work is reviewed above. They are relatively thin (0.5-2.0m) lms of SiO2 or Al2O3 and their purpose is to prolong the usability of the underlying sensors, especially in the hot corrosive environments encountered in turbomachinery equipment. However, these coatings are impractical when there is mechanical contact between the tool or the component and the environment, as is the case in most manufacturing or drilling tools. It is evident that, in these situations, a far tougher coating is necessary and engineering alloys are the best candidate materials. The only drawback is that such coatings have to be grown by high temperature processes.
1.3 Basics of Sensor Physics

1.3.1 Strain Sensors
One-dimensional strain is the ratio of the incremental change of length to the length of an object: dl = --l (1.1)
Its usefulness lies with the fact that it can be used to infer the stress applied to an object and therefore indirectly dene its stress state. Of course, this can only be done accurately if there is a well known constitutive model that describes the relation between the two quantities (stress and strain). For the family of materials
that behave elastically below a stress level this is relatively simple as the uniaxial stress is related with the uniaxial strain with a linear formula: = E (1.2)
where E is the Youngs modulus of the material, a material property giving a measure of its stiffness and the strength of the interatomic bonding. The most common method to measure strain makes use of the piezoresistive effect, according to which the electrical resistance of a conductor changes when the conductor is mechanically deformed. For example, let us assume a cylindrical electrical conductor of length l, cross-sectional area a, and total volume V. The resistance of this conductor is simply given by: l l - = --R = -V a
2
(1.3)
where is the resistivity or specic resistance, a material property of the conductor and generally a polynomial function of temperature. When a uniaxial tensile stress is applied to the conductor, the latter will be elongated, but, if the stress is below the yield strength of the material, its volume will remain constant. Differentiating Eq.(1.3) with respect to the length and rearranging the terms with the aid of Eq.(1.1) yields a relation between the normalized incremental resistance and the strain of the conductor: dR ----- = Se R (1.4)
where Se is the gauge factor or sensitivity of the strain sensor, and for most metals ranges from 2 (ideal value) to 6 [frad93]. From Eq.(1.4) it is evident that the normalized change of the resistance of a conductor that is subjected to a uniaxial stress can give information about the
strain in the conductor. The resistance change can be very accurately monitored if the conductor is part of a balanced bridge circuit. Actually, this is the method employed by strain indicator devices to report a strain value based on the resistance change of the gauge [bray94]. The thin-lm strain gauge is usually grown on an insulating foil that is subsequently attached with a strong adhesive cement to the surface of the object whose strain state is of interest. There is a complication arising from the fact that the gage factor depends on the temperature of the conductor through its resistivity and for this reason a special alloy (constantan) has been produced that exhibits a very low temperature coefcient of resistivity (~10ppm/K) [buch91, frad93]. The theoretical value of the coefcient is derived from a linear t of the polynomial law that governs the resistivity dependence on temperature. Constantan is a copper-nickel alloy and its nominal composition is 50-65% Cu with Ni in the balance [blat76]. It is widely used as a strain gage material in order to minimize temperature effects on the resistance variation. The latter can be completely accounted for with the use of a dummy gage. The dummy gage should be on the same material and at the same temperature as the active gage but it should not be loaded. Compensation of the thermal strain of the active gage is achieved by connecting the two gages in adjacent arms of the bridge circuit [bray94].
1.3.2 Thermocouple Sensors

In 1821 T.J. Seebeck discovered the homonymous thermoelectric effect which manifests as a owing current in a loop made of two dissimilar conductors when the two junctions are at different temperatures. If one of the two junctions is open, an electric potential (Seebeck emf) will appear between the two free terminals. In this case the combination of the two conductors is referred to as a thermocouple and such a device, when properly calibrated, can be used to measure temperature.
The physical basis of this effect is the temperature dependence of the Fermi-Dirac function. Using purely quantum-mechanical principles, Mott and Jones [mott58] have derived expressions for the absolute thermoelectric power (or absolute Seebeck coefcient) of noble metals and transition elements (above their transition temperature). For reference purposes, the two expressions are presented in Eq.(1.5) and Eq.(1.6), respectively [bedf90]:
2 k B T - --------S = -------2 eE F 2
(V K )
(1.5)
2 kBT -------- -------------------------S = 6 e(E0 EF )
(V K )
(1.6)
where EF is the Fermi energy, E0 is the highest energy level in the (incompletely lled) d-band, kB is the Boltzmann constant and e is the electron charge. However, Eq.(1.6) is not useful below the Curie temperature of the transition elements or their magnetic alloys as the magnetic behavior of the electrons was not considered in its derivation. A thorough discussion of the thermoelectric transport properties of metals with reference to special problems in transition elements can be found in [blat76]. In the case of a thermocouple the resulting thermoelectric potential will depend on the difference of the absolute Seebeck coefcients of the conductors and the temperature difference between the hot junction and the terminals (cold junction) [poll85]: dV ab = [ S a ( T ) S b ( T ) ] dT = S ab ( T ) dT (1.7)
where Sab is the differential Seebeck coefcient of the thermocouple, also referred to as sensitivity of the thermocouple.
10
This coefcient is usually reported in VK-1 or mVK-1, is approximated by a linear function of temperature, and does not depend on the nature of the junction. The most common type of thermocouple (type K) is formed by joining a Ni0.9Cr0.1 conductor with a Ni0.94Mn0.3Al0.2Si conductor and has a sensitivity of 40.6 VK-1 at 298K when the cold junction is held at 273K. Its sensitivity remains reasonably constant for hot junction temperatures up to ~1300K. The alloys are referred to with their respective trade names: chromel (or chromel P) and alumel. Since the thermoelectric properties depend on the carrier transport mechanisms, it is expected that imperfections and/or surface and grain boundaries in thin lms will affect their magnitude due to increased carrier scattering. In particular, thin-lm thermoelectric materials exhibit a decrease in their Seebeck coefcient with decreasing thickness [balt94].
1.4 Deposition Processes

1.4.1 Sputtering
During the vapor deposition of a thin lm we can identify a sequence of distinct process phases: the generation of the species, its transport to the substrate surface, the adhesion of the particles to the substrate, the nucleation of the lm and its growth. The term sputtering refers to the species generation, a process that is described below. It is possible to ionize, in a sustainable fashion, a mass of gas that is between two electrodes by applying a voltage V across them. Then the free electrons, which exist in very small concentrations in the gas, will be accelerated towards the anode. In their trajectory they will interact with molecules of the gas or any other evaporants, unless the distance d between the electrodes is so small as to allow them to complete their travel uninterrupted. If the pressure P of the gas is low
11
enough, the electrons will have acquired enough kinetic energy as to ionize the gas molecules, thereby injecting more free electrons in the space between the electrodes. This cascading electron multiplication by gas-phase ionization is the mechanism of gas breakdown in an electric eld. Plasmas can be ignited and sustained via this mechanism. Apparently, the key parameters for this effect, for a certain gas species, are the applied voltage V, the pressure P of the gas, and the distance d between the electrodes. In fact, the pressure P is related to the mean free path le: l e = ( n n ) 1 (1.8)
where n is the molar density (analogous to P via the ideal gas law), and n is the collision cross-section, which depends on the type of collision and the electron energy. The generated gas cations are attracted electrostatically toward the cathode (or target) and impinge on its surface. The conservation of momentum and energy dictate that the kinetic energy Tm imparted to surface particles is: 4 mi mt - E = mEi T m = -----------------------( mi + mt ) 2 i where mi and mt are the masses of the impinging and the target particles respectively, and Ei is the energy of the impinging ion. For particles of roughly equal mass the transfer of energy is very efcient. Only a few tens of eV are enough to either displace a surface atom into the bulk of the target or dislodge a nearby atom to the vapor phase with a few eV of initial kinetic energy. The latter process, namely the erosion of the cathode surface due to impingement of cations produced in a glow-discharge, is called sputtering and
(1.9)
12
is used to produce vapor of a solid element, alloy, or compound that will condense on a substrate and form a thin lm. In its basic conguration, a sputter-deposition chamber contains a cathode to which the target is attached. The target is usually a disk or rectangular-shaped piece of the material to be deposited. If the target is conductive, the cathode is connected to a dc power supply. In the case of an insulator the cathode is capacitively coupled to a rf generator. Then, a high purity noble gas, generally Ar, is injected in the chamber, which must have been evacuated to a pressure that guarantees very low concentration of unwanted vapors. The substrate is usually positioned directly across from the target at a distance of 6-10cm. It can be at a oating potential, grounded, or biased at a dc or rf voltage. The application of a voltage to the cathode will instigate the breakdown of the gas and lead to the formation of plasma. This setup is described as diode sputtering. We can conne the plasma near the target and sustain the discharge at lower pressures and voltages by inserting magnets behind the target and thus effectively extending the path of the ionizing electrons. This technique is referred to as magnetron sputtering. Typical target voltages are in the few hundred Volts range, and by virtue of Eq.(1.9), the sputtered particles retain a good fraction of this energy. However, collisions with the noble gas atoms during their ight to the substrate will diminish their initial ejection energy. Microstructure As the sputtered species are ejected with an initial kinetic energy some of them are intercepted by the substrate. A fraction of them, dictated by the sticking coefcient, will be adsorbed to the surface and form nuclei. Species that arrive later will either form new nuclei or be added to pre-existing ones. When the nuclei cover the whole surface, then nucleation ceases and the newly arriving species contribute only to growth. The decisive factors for the nal
13
microstructure is the temperature of the surface and to a lesser extent the energy input to the substrate-lm system by other methods, such as the bombardment by neutralized species that bounce off the target surface, as well as the ux of the incoming species. Elevated substrate temperatures allow for the surface diffusion of the adsorbed particles and thus promote a denser lm. The diameter of the columnar grains generally scales with the temperature of the substrate. Low impinging uxes will promote strongly textured lms. When the substrate is at low temperatures, surface diffusion is limited or even quenched, and the lm grains have a ne columnar structure which may exhibit voids caused by the self-shadowing effect [smit95]. In general, sputtering at low working pressures (larger mean free paths, fewer energy-dissipating collisions for the impinging species, lower angular spread of incident angles) is thought to limit substantially the self shadowing effects and produce nely grained yet dense lms even at low temperatures. Stress state Sputtering can be responsible for what is called intrinsic or growth stress in the deposited lm. Of course, a sputter-deposited lm can have stresses that are caused by thermal strain mismatch (lm and substrate having different thermal expansion coefcients and elastic constants, and deposition occurring at high temperatures) or by lattice parameter mismatch (epitaxial stress). It can also exhibit a tensile stress due to atomic attraction between microclusters that are in close proximity. However, there can be a compressive stress component that arises due to the bombardment of the lm surface by energetic ions or neutrals. These projectiles can either be implanted into the lm and/or knock surface atoms into interstitial positions and bring them into closer proximity. At low temperatures, the displaced atoms can be frozen in the new positions and give rise to a compressive stress. The case of momentum transfer that builds compressive
14
stress is very analogous to the shot-peening process used to compressively stress the surfaces of bulk materials, so it is often called atomic-peening, or ionpeening. The peening effect is mostly visible at low working pressures, where the mean free path is large enough to allow the deposited particle to hit the substrate surface with a larger fraction of its initial momentum. Adhesion As explained before, the sputtered species are adsorbed to the substrate surface. Their adhesion depends on factors like the cleanliness of the substrate and the type of bonding that can be developed between the substrate and the incident particles. It is quite possible that an unclean surface, contaminated with monolayers of water or organic molecules, will not allow the chemisorption of the deposited particles. Instead, these particles will only be physisorbed to the substrate with weak dipolar bonds and the lm adhesion will be poor. Therefore, it is imperative that both the substrate is rendered atomically clean in vacuo immediately prior to the deposition, and the sealing of the vacuum chamber is very good. The top surface monolayers can be removed either by a physical process (sputter-etching, substrate heating), or by a chemical one (e.g.: oxidation of organic molecules in an oxygen plasma, reduction of oxides in a hydrogen plasma). With a clean surface the deposited particles can be chemisorbed to the underlying atoms via the formation of new molecular orbitals. The adhesion strength is then determined solely by the type of chemical bond that can exist between the two substances. Evidently, metal particles can bond very well to a substrate made of the same material. Also, some metals form strong oxides (Ti, Cr, Zr, Al) and they can strongly bond to oxidized surfaces. This property is used to promote adhesion between two otherwise weakly bonding materials (e.g.: Au on SiO2), by depositing an interlayer of a glue metal (e.g.: Ti). Furthermore, sputterdeposition, being an energy-enhanced process, provides the impinging species
15
with enough energy content to activate interfacial bonding, thereby resulting in better adhesion than evaporative deposition. Composition It is interesting that sputtered alloy targets will produce a deposit whose composition can be very close to that of the bulk alloy. The atomic ux leaving a target with two constituents a and b is:
k i Qk = SY
(1.10)
where SY is the sputtering yield, and i is the Ar-ion ux, whereas k denotes the element. It can be assumed that for a fresh target the fractional coverage of its surface by one of the constituents is k. However, due to the different sputtering yields, the ratio of the ejected fluxes (a Qa/bQb) will not be equal to a /fb. As the sputtering proceeds, the element with the higher sputtering yield will be depleted from a thin volume at the surface of the target (its depth being diffusion limited), and, consequently, the surface coverage of this element will decrease until the ratio of the ejected fluxes is a /fb. So, the composition of the ejected flux will be the same with that of the bulk target. If some further assumptions are met, (namely the equal sticking coefficients, the matrix independence of the atomic sputtering yields, and the absence of ejected dimers), then the deposited film will also have the same composition as the bulk target. Reactive sputtering The reactive sputtering technique is a variant of the sputter-deposition method used to produce either doped or compound lms by allowing an additional gas species (other than the noble gas) in the deposition chamber. The outcome of the deposition (doped lm or compound) is determined by the state of the target: in mode A, or metallic mode, the deposit is a metal lm doped with atoms from the reactive gas, while in mode B, or compound, or
16
poisoned mode, the deposit is a stoichiometric compound. The main parameter that places the system in one of the two states is the ow of the reactive gas (usually O2 or N2). The variation of the total system pressure with the particular ow follows a hysteresis curve and the existence of such a curve is indicative of a reactive system. A generic hysteresis curve is shown in Figure 1.1.
Pn P
Total pressure
PT PT PAr QT
Reactive gas flow
QT
FIGURE 1.1: Generic hysteresis curve in a reactive sputtering system.
Assuming that the sputtering gas (usually Ar) ow and the pumping speed remain constant, there is a history effect in the variation of the system pressure with the reactive gas ow. Initially, at zero reactive ow, the deposit is purely metallic (if the target is metallic) and the total pressure is equal to the argon pressure. If there were no discharge, the introduction of additional mass ow into the system would cause the system pressure to follow the diagonal dashed line (Pn(Q)). However, in the case of a discharge, and for small reactive gas ow values, the total pressure remains essentially constant. The reason for this phenomenon is the trapping or getter-pumping of the reactive gas in the deposited lm and the nal result is a doped metallic lm. The target is in the metallic mode A.
17
When the reactive gas ow exceeds a value QT, then the pressure rapidly increases to PT, which differs from Pn(QT) by an amount equal to P. Higher ow values will lead the system to higher pressures (P) but the difference
P(Q)=Pn(Q)-P(Q), for Q>QT, will be constant. This pressure difference

corresponds to the amount of the reactive gas that has been incorporated into the deposit, which is now a stoichiometric compound. The target forms a thin compound lm on its surface and transitions to the poisoned mode B. The target will remain in the poisoned state even for Q<QT and it will revert to the metallic mode for ows below a critical value QT. At this state the vast majority of the species ejected by sputtering of the target are compound molecules. The previously described hysteresis is explained by the difference in the sputtering yields between the metallic element(s) of the target and the compound formed in the presence of the reactive species. Generally, the compound will have a lower sputtering yield than the fresh, purely metallic surface and the deposition rate will drop. Consequently, the rate at which the reactive gas is getter-pumped in the deposit and consumed at free sites at the target surface will drop too, and there will be an excess amount of the reactive gas which will register as an increase in the total system pressure. The high transition ow QT represents the state where the rate of compound formation on the surface target (or target poisoning) becomes higher that the rate at which the target is sputter-cleaned of the compound. This trend, once the target becomes poisoned, is reversed only at the lower transition ow value QT. Due to the difference in the sputtering yields it is evident that the compound and the (doped) metal will have different deposition rates. This difference becomes dramatic when the compound is an insulator, e.g.: Al2O3. However, there is an operating window of reactive ow values that makes reactive deposition of insulators attractive from a deposition rate point of view. (It is obvious that reactive sputtering is more versatile than rf-sputtering as it is capable of
18
depositing different compounds from a single target, e.g.: AlN and Al2O3.) If the reactive gas ow is kept within a narrow range around QT, then it is possible to deposit a compound lm with good stoichiometry at a rate that is comparable to that of the metallic lm. The difculty associated with this procedure is keeping the total pressure at a level between PT and PAr, while the ow is kept at a value of QT. When the reactive gas ow is equal to the transition value QT, the system is in an inherently unstable equilibrium: a small perturbation of the ow towards higher values will increase the target poisoning rate, so less reactive gas will be consumed, thus the reactive gas partial pressure will increase and this will lead to a further increase of the poisoning rate until the equilibrium pressure of P1 is nally reached. At this pressure the target is fully poisoned and the deposition rate is very low. Alternatively, a perturbation towards lower ow values will result in faster sputter-cleaning of the target, faster consumption of the reactive gas, and lowering of the system pressure to the equilibrium value of PAr. At this stage the target is in the metallic mode, the deposition rate is high, but the deposit is a doped metallic lm and not a stoichiometric compound. From the discussion above it can be inferred that the most important parameter in reactive sputtering is the ow level of the reactive gas. Its control is essential for the high-rate deposition of stoichiometric compounds due to the unstable equilibrium that is characteristic of this state. Pulsed-dc sputtering In the case of reactive sputter-deposition of insulating lms from a metallic target (e.g.: Al2O3) the insulating species that form on the surface of the metallic target and get deposited over the anode-ground alter the electrical characteristics of the discharge, building effectively a capacitor between the plasma and the
19
electrodes. In particular, the growth of an insulating layer that covers gradually larger parts of the anode or ground (which is essentially the chamber walls) makes it more difcult for the plasma electrons to nd a conducting surface and close the circuit. The result of the disappearing anode is extensive arcing which damages the deposited lm , stray plasma, and long-term plasma instability [schi93]. The problem can be addressed for the mid-term with concealed or rotating anodes but it does not disappear altogether. Pulsed-dc sputtering is manifested by superimposing a low frequency square waveform on the dc signal that dives the magnetron target. The superimposed waveform can be unipolar or bipolar. In the latter case it can be symmetric or asymmetric. If a single target is used and the bipolar mode is selected in order to enhance the removal rate of the insulating species from the poisoned target surface, then the asymmetric waveform is preferred in order to avoid sputtering of the anode (chamber walls) and consequent contamination of the deposit. The operating principle behind bipolar asymmetric pulsed-dc sputtering lies with the enhanced momentum of the argon ions hitting the target when the voltage returns to its negative plateau (point A in Figure 1.2).
+100V time -300V
FIGURE 1.2: Asymmetric bipolar dc voltage as applied to a magnetron target.
At that point the parasitic capacitor, which has formed by the insulating lm grown on the target surface, has been fully charged and reached a potential equal
20
to -100V (as the metallic target was held at 100V). As the voltage reversal happens and the metallic target returns to -300V the effective voltage that accelerates the argon ions to the cathode is -400V, and therefore the sputtering yield increases, effectively cleaning the target from the insulating species [sell96]. The frequency of the pulse is generally in the 50-250kHz range and the pulse width, which governs the duty cycle, is in the 500-2000ns range. The use of pulsed-dc sources for reactive magnetron sputtering has allowed the stable and lengthy deposition of insulators at rates comparable (60%-70%) to those for the pure metals. The latter rates are signicantly higher (by at least an order of magnitude) than the rates for insulators from compound targets achieved with rf-sputtering.
1.4.2 Electroplating
Electroplating is the process of producing a coating by electrolysis. According to Faradays laws, when one Faraday of electricity (~96490As) is transmitted between two electrodes immersed in an electrolytic solution (bath), 1 g-equiv (gram-equivalent) of metal will be deposited on the cathode.The mechanism by which this happens is described below. When a piece of metal is immersed in a aqueous solution containing its ions some of the atoms will leave the lattice and dissolve into the solution, becoming hydrated. At the same time, some of the ions will leave the solution and attach to the electrode. The potential of an electrode at which the two opposite reactions have equal rates is called equilibrium potential E and depends on the metal, the solution and its temperature, per the Nernst equation [lyon74]: E = E M n + + RT ( nF ln a M n + )
0
(1.11)
21
where E0Mn+ is the standard potential for reduction of the simple metal ion Mn+ to the atom M, R is the gas constant, T is the absolute temperature and aMn+ is the activity of the metal ion in the solution. If we consider two copper rods dipped in a water solution of copper sulfate, and we connect them to an external direct current source, we will raise the potential of the rod connected to the anode and lower the potential of the rod connected to the cathode by supplying more electrons to the latter. The fact that the cathode assumes a potential lower than the equilibrium potential means that more copper ions will leave the solution and attach to that electrode, thereby closing the electric circuit and increasing the mass of the cathode. The reverse will happen in the anode. This is a very basic electroplating cell. Microstructure The electrodeposits are generally microcrystalline in nature. Crystal grains nucleate more easily at kinks, edges, or steps on the lattice of the substrate and, initially, grow laterally in a monolayer fashion as the ad-ions diffuse across the surface. When the grains encounter adsorbed impurities, or other growing grains, they start growing outward. At low currents and very low concentration of impurities it is possible to have epitaxially dictated crystallographic directions in the growing grains, assuming, of course, that the lattices of the basis metal and the coating are similar. It is also possible to affect the growth pattern by providing enhanced convection of fresh ionic species to the vicinity of the cathode, e.g.: by stirring. Stress state Stresses in the electrodeposits arise from lattice mismatch at the basis-coating interface, from coalescence of adjacent crystal grains and, more commonly, from incorporation of foreign substances in the lattice. Such inclusions as oxides, hydroxides, water, sulfur, carbon, hydrogen, and metallic impurities (foreign ions
22
in the bath) distort the lattice and produce stress elds around them which may manifest as macroscopic stresses [read74]. Adhesion As the rst monolayer of the elctrodeposit is grown on the surface of the basis metal, its atoms engage the lattice forces of the latter. In the absence of impurities from the basis-coating interface the bonding is very strong and approaches the strength of the bonds among the basis metal atoms. Only improper substrate preparation, or pronounced lattice mismatch between the basis and the coating materials, can be the cause for poor adhesion [lyon74].
1.4.3 Laser Assisted Deposition

A number of layered manufacturing techniques make use of a high-power laser beam to create fully dense metal parts by welding new layers onto substrates. The beam is focused on the surface of the substrate and thus creates a pool of molten material. Then, more material is injected into the pool in powder form and the beam is moved relative to the substrate. The powder feeder follows the laser motion and continuously supplies more material to the molten metal pool which in turn solidies and fuses to the substrate as the laser moves on its predened trajectory. An alternative method of supplying new material is to use a pre-deposited powder bed on the substrate. Particular incarnations of this additive welding-base technique include Laser Engineered Net Shaping (LENS) [beam97], Directed Light Fabrication (DLF) [beam97], Control Metal Build-Up (CMBU) [beam97], LaserCast [hous97], Laser Direct Casting [mcle97], and Laser Deposition in Shape Deposition Manufacturing (SDM) [nick99, link99]. In SDM, a sacricial support material is used in order to allow the realization of overhanging structures and pre-assembled mechanisms, and each layer is planarized and shaped after its deposition [merz94].
23
1.5 Dissertation Outline

The subject of the work presented in this dissertation is the embedding of thermo-mechanical sensors inside metallic components, tools, and structures. The main focus of the research has been the development of the processes necessary to achieve both the fabrication of the sensors and their subsequent enclosure (embedding). Chapter 2 describes the scheme we propose in order to produce the sensors and the layers necessary for their protection and embedding. The full details of the fabrication procedure are described in Chapter 3. The characterization results of the various components with respect to their most relevant properties are presented in Chapter 4. The results of a heat transfer nite element analysis, which was employed to predict the temperature at critical regions of the structure, are the subject of Chapter 5. The nal chapter contains the summarized conclusions for the research described in the dissertation and a few guidelines regarding the implementation of the technology developed at the Rapid Prototyping Laboratory at Stanford University towards the production of an instrumented tool.
24
Proposed Solution
In this chapter a solution to the embedding of thermo-mechanical sensors inside metallic components, tools, and structures is proposed vis-a-vis the challenges that were outlined in the previous chapter. The major obstacles towards the fabrication of a tool with embedded sensors can be identied as the electrical insulation of the sensors and their protection from the high temperature processes. The problem of compatibility between the various processes becomes more evident during a change of the production environments. Particularly, it is a matter of cleanliness and surface quality when a part is transferred from large-scale manufacturing to thin-lm processing and a matter of physical (mainly thermal) and chemical protection during the reverse procedure. Bearing the above in mind, our proposed solution can be outlined as follows:
2.1 Cleanliness and Surface Quality

Before entering the thin-lm processing stages the semi-completed part will have to be thoroughly de-greased, cleaned and dried. Its surface that will serve as a substrate for the thin-lm sensors will have to be polished and devoid of any residual chemicals. It is important that it is sputter-etched inside a vacuum
25
CHAPTER 2: PROPOSED SOLUTION
chamber to ensure that the contaminated top monolayers have been removed before any deposition takes place.
2.2 Insulation
The insulating material of choice should be easily deposited via a thin-lm method and be able to withstand elevated temperatures during subsequent processing and operation of the component. Possible candidates are the oxides of aluminum, silicon, and tantalum, and the nitride of silicon. All of them can be deposited by rf-sputtering of compound targets or reactive sputtering of the elemental targets in an atmosphere that contains oxygen or nitrogen. Obviously the insulating layers should fully enclose the sensors except for the contact pads which must remain exposed but insulated from the substrate. In the case of the temperature sensors it also makes sense to have the junction at direct contact with the surrounding matrix.
2.3 Sensors
The sensors can be deposited by sputtering targets of materials used for the fabrication of large-scale sensors, e.g.: constantan, copper, alumel, chromel, etc. Sputtering has the intrinsic advantage of achieving a deposited lm that has the same composition of the bulk target material assuming that all the molecules have roughly the same sticking coefcient. The patterning of the sensors can be achieved by means of photolithography and micromachining (e.g.: lift-off, etching, ion etching).
26
CHAPTER 2: PROPOSED SOLUTION
2.4 Thermal Protection

Our goal is to protect the thin lms of the insulation and the sensor during the completion of the component via high-temperature deposition or diffusion processes. This can be facilitated by providing an alternative fast path to the heat input during the high-temperature deposition so as to be conducted mainly to the thick metallic substrate (of higher heat capacity) than to the sensitive thinlm multilayer. This path can be produced by growing a thick layer of a material with high thermal diffusivity, such as copper. This layer, which has to be grown by a lowtemperature technique (e.g.: electroplating), will extend over and beyond the insulation layers as to have immediate contact with the metallic substrate. Of course, it will have to be insulated from the sensors by the top insulating lm.
2.5 Embedding
The embedding of the sensors and the protective layers in the metallic structures can be achieved by a high-temperature deposition technique akin to those used in layered manufacturing. For example, the fusion of a powder bed to the underlying structure can be achieved with a high-power laser. Alternatively, a more benign plasma-spraying process can be used if the full density and chemical bonding achieved by cast-like processes are not necessary. Diffusion bonding might also offer an additional option. However, a process that can lend itself to freeform fabrication is always preferable, as it can achieve the shaping of the added material into useful geometries.
27
Fabrication
The procedures and processes necessary to fabricate a thin-lm thermomechanical sensor and embed it in a metallic matrix are the focus of this chapter. Even though the processes described guarantee the successful production of such a device, it is expected that there can be optimizations which, when applied upon those processes, will result in a higher yield and/or faster production time.
3.1 Substrate preparation

Ideally, the thermo-mechanical sensors should be deposited upon an internal surface of a tool or other structure during its fabrication with a layered manufacturing technique of such a tool with the SDM process [Laser Assisted Deposition on page 23]. However, for practical reasons of availability, substrates that could simulate the part surface in terms of materials properties were used.
3.1.1 Cutting
The standard substrates used in the process are 3mm-thick stainless steel pieces with nominal lateral dimensions of 50x50 or 50x25mm. These pieces are cut from square 30x30cm plates using band saws and cutting wheels. As a result the exact dimensions of the substrates are systematically smaller than their nominal
28
CHAPTER 3: FABRICATION
values by up to 3mm.The stainless steel is of the 304L grade with a nominal composition [asm94] that is described in Table 3.1.
TABLE 3.1: Nominal composition of 304L stainless steel.
Cr 18-20%
Ni 8-12%
Mn 2%
C 0.03%
Fe bal.
The reasons behind the selection of the particular material were the wide availability, machinability, and mostly the corrosion-resistant character, which would allow its use in a variety of processing environments.
3.1.2 Grinding and polishing

The substrates need to be ground and polished for two reasons. First, a smooth surface can ensure easier and more efcient cleaning and provide little chance for large size particles to mechanically attach to it. Moreover, a smooth substrate is free of cusps which may function as stress concentration regions for the ceramic lm that will be deposited above them [stor96, nisk98]. The grinding process involves 5 grades of grinding paper with increasingly ner SiC particles denoted by grit numbers: #320, #400, #600, #800/2400, #1200/4000. Usually, 4 minutes of grinding over every sandpaper are sufcient for good results when the paper is fresh and the substrate orientation is rotated by 90 degrees after 2 minutes. A rotation speed of 180-220rpm seems to work best and the ushing of the substrate with water between successive sandpapers is absolutely necessary to avoid cross-contamination with lower grit particles. It is good practice to use latex gloves for handling the substrates throughout the whole preparation stage. The polishing process involves 3 different suspensions of alumina particles in distilled water. The sizes of the particles used are 1.0, 0.3, and 0.05m. The optimal time for polishing has not been established, however, the disappearance
29
of scratches that were left by the previous polishing (or grinding) step is adequate evidence that one may proceed with the next suspension. However, a bluish hue covering part of the substrate was observed after prolonged polishing. The rotation speed used is in the 300-500rpm range. It is always benecial to use fresh polishing cloth and it is mandatory to ush the substrate thoroughly with distilled water between polishing steps. The average roughness of the surface achieved by this method is always smaller than 20nm, as measured by a Tencor Alpha-Step stylus prolometer for scan distances in the 80-2000m range. In the quest for a polished surface, free of attached particles, the substrates were electropolished in a standard stainless steel polishing bath with a current of 5070A at a voltage setting of 8V dc. The results did not compare well with those achieved by mechanical polishing, as the surface revealed pits after 3 minutes of electropolishing.
3.1.3 Cleaning
The substrates have to be cleaned after the polishing process. The sequence of steps to that end is described in detail below and takes place inside a class-1000 clean room. In an effort to remove salts, oils and grease we rinse the substrates sequentially in borothene, acetone and isopropanol. Then the substrate is blown dry with dry nitrogen, rinsed with de-ionized water and dried again. The above steps are repeated once more and then the substrates are immersed in a 1:15 solution of micro-detergent in de-ionized water and are placed in an ultrasonic bath for 5 minutes. Finally the substrates are rinsed with copious amounts of deionized water and blown dry with dry nitrogen. It is expected that at least a monolayer of the surfactants in the micro-detergent will remain on the surface of the substrates [mbec98, also: Discussion of cleaning processes on page 33], as well as carbon from the organic solvents. In order to eliminate persistently adhered particles to the stainless steel surfaces and enhance their passivation it was suggested to immerse the substrates in a
30
1:10 solution of nitric acid (70%) in de-ionized water for a few minutes and then ush with de-ionized water [leve98]. The results of our attempts, in terms of insulation failures due to pinholes, were not conclusive as to the effectiveness of this method. Other researchers [nasa86] have employed exposure of the substrates in UV radiation in an ozone ow for 60 minutes to dissociate and remove organic substances from the surfaces. However, they did that in a clean room environment. This procedure was not replicated, as one of the goals of this work is to create a process sequence that can be carried out with successful results in a more traditional manufacturing environment. Since the thin-lm processing does not take place in a clean-room area, it is necessary to take precautions that minimize the exposure of the substrates to the environment outside the clean room during their transfer. For this reason it is recommended to mount the substrates onto the substrate holder in the clean room and transport the holder in a ziploc plastic bag lled with dry nitrogen.
3.1.4 Sputter-etching
The nal step of the substrate preparation takes place inside the vacuum chamber just prior to the deposition of the insulation layer. Its purpose is to remove any electrostatically attached particles or chemisorbed substances form the substrate surface by etching a thin layer off the top of the substrate material. This process uses accelerated argon ions to sputter material from the substrate instead of the target and is called sputter-etching, sputter-cleaning or backsputtering. The chamber is evacuated to a base pressure better than 10-4 Pa, then argon is injected and the pump is throttled to maintain a pressure of 6Pa. A pulsed-dc signal is applied to the substrate holder at a constant power setting of 100 W. The full details of this process are listed in Table 3.2.
31
TABLE 3.2: Sputter-etching process parameters.
Base pressure Argon ow Argon pressure Power (controlled) Pulse frequency/width Discharge voltage Etching time
<10-4 Pa 1503sccm 6.00.2Pa 100 W 201kHz/1056 ns 325-330V 600s
Since there is no magnet behind the substrate stage, it is necessary to use a high pressure of argon to ensure there are enough ionization events and consequently a self-sustaining electric discharge through the rareed gas. We also have to use a shutter between the substrate and any facing targets to avoid contamination of the target with material sputtered from the substrates. A measurement for the sputter-etching rate of the 304L stainless steel substrate was taken by step prolometry: a piece of silicon wafer was placed on top of the steel surface and after 600s of sputter-etching the height of the created step was measured. The resulting rate was estimated at 3nm/min. However, this rate results in just 30nm of height difference. Bearing in mind that the average roughness of the polished steel surface is of similar magnitude (10-20nm) and that the step was not very sharply dened, it might be necessary to create such a step with different methods and longer etching times. In the pulsed-dc mode, the rate of 3nm/min is achieved by sputter-etching during only 79% of the duty cycle. During the rest 21% the substrate assumes a positive voltage and no sputter-etching occurs. Ideally, a purely dc signal of the same power level would result in a rate of 3.8nm/min. The reason for using pulsed-dc mode is that it can be successfully used for conducting and insulating substrates alike and, more importantly, it can sustain a discharge for longer times
32
at lower pressures than the pure dc mode, which is very prone to arcing [cf. Pulsed-dc sputtering on page 19].
3.1.5 Discussion of cleaning processes

In order to evaluate the relative effectiveness of the different cleaning steps, three polished 304L stainless steel substrates were prepared, referenced as CLD, CLS, and CLN, and were cleaned in three different manners. Substrate CLD was cleaned in a micro-detergent and de-ionized water solution (1:15) inside an ultrasonic bath for 5 minutes. Substrate CLS was cleaned repeatedly with the organic solvents mentioned in Cleaning on page 30, and substrate CLN was immersed in a 7% v/v nitric acid solution. All of them were subsequently thoroughly rinsed with de-ionized water and blown dry with nitrogen. All substrates were scanned in a XPS system for a rough compositional analysis. Then, all samples were sputter-etched for 90s and re-scanned to gather compositional data. The surfaces were sputter-etched for another 210s before the nal scan. The rationale of this process sequence was to observe any changes in the surface composition and particularly carbon, oxygen, and iron contents with depth. The results are summarized in Table 3.3 and Table 3.4 .
TABLE 3.3: Surface composition of 304L substrates cleaned with different methods.
Substrate CLD CLS CLN
Carbon (at%) 23.4 21.0 28.7
Oxygen (at%) 57.3 60.5 53.0
Iron (at%) 8.1 9.5 8.2
Chromium (at%) 8.5 6.3 8.2
It can be seen than in all cases, oxygen and carbon constitute 81-82% of the as-prepared surface layers, irrespective of the cleaning process that was followed. The origin of the oxygen is mainly the water molecules that are attached to the substrate surface by Wan der Waals forces. We believe that this contamination is
33
TABLE 3.4: Atomic content of O, Fe, and Cr in 304L surfaces after sputter-etching.
Substrate
Etching time (s) 90 300 90 300 90 300
Oxygen (at%) 13.5 9.9 14.8 11.3 10.1 8.4
Iron (at%) 51.7 56.1 59.2 59.5 60.7 64.2
Chromium (at%) 13.8 14.3 10.1 10.2 11.2 16.1
CLD
CLS
CLN
due to the exposure of the samples to the atmospheric humidity during transport and/or storage. The carbon most probably originates from the organic solvents residue, and the organic agents in the micro-detergent or the atmosphere. In any case, it is remarkable that the treatment with organic solvents leaves the least carbon contamination on the surface.After 90s of etching there is no detectable carbon in the substrates and this is evidence that the carbon contamination is strictly a surface phenomenon and can be completely removed even by minimal sputter etching. The signicant oxygen content in the rst few nanometers beneath the topmost surface layers is probably due to diffusion of atomic oxygen and bonding with active elements such as iron.
3.2 Bottom insulation layer

The rst layer to be deposited will have to provide the sensors, and especially the strain gages, with adequate electrical insulation from the stainless steel substrate. Typical candidates for this function are the oxides of silicon and aluminum as well as silicon nitride and tantalum pentoxide. In principle, and practice, all of the above can be deposited in thin lm form via rf-sputtering from a compound target or reactive sputtering from a metallic target in an atmosphere that contains oxygen or nitrogen. In our case, reactive sputtering was the only available solution due to the lack of a rf generator and matching system and also due to
34
the high rates that can be achieved with reactive deposition. The high rates are necessary in cases with poor particle control, since thicker lms will be less likely to suffer from pinhole problems caused by particle contamination.The price to be paid for choosing a reactive system is the difculty in the control of the deposition process. We chose aluminum oxide as the preferred insulating lm for reasons based on thermal expansion coefcient compatibility, and target cost. These parameters are listed for the aforementioned insulating lms in Table 3.5 below:
TABLE 3.5: Material properties for insulating thin lms.a
Material
Dielectric strength (kV/mm) 9.9-15.8 15-25 >200c 15.8-19.8
Thermal expansion coefcientb ( K-1) 8.0 0.3-0.4
Cost of metallic target (US $cm-3) ~12 ~20 ~40
Al2O3 SiO2 Ta2O5 Si3N4
2.5-3.5
~20
a. [buch91], unless noted otherwise b. Mean thermal expansion coefcient of 304L stainless steel, in the 20-400C range: 18 K-1 [asm94]. c. [chen97]
The concept of reactive sputtering has been presented in Reactive sputtering on page 16. Hereafter, the focus is turned on the issues of the process as appeared in our system. Our goal was to produce an aluminum oxide lm that did not suffer from pinhole problems, was as close to the ideal stoichiometry as possible, and could be deposited in a reasonable time (1-2hr). The solution to these issues would entail certain compromises, since in order to guarantee perfect stoichiometry the deposition rates would have to be minimized and a thick lm (in the order of a few m) would take several hours to grow. The key to the solution is the
35
determination of the transition oxygen ow (or oxygen content) that would permit the metallic target to remain partially poisoned, therefore allowing high rates of deposition with a stoichiometry very close to the ideal.
3.2.1 Determination of transition oxygen ow

In order to establish this optimum concentration of oxygen in the sputtering gas mixture, the levels of the discharge voltage and the total pressure during the sputtering of an aluminum target were recorded versus a gradually varying oxygen ow. The argon ow was kept constant at 80sccm and the discharge current was preset at 0.80A. The power supply was switched to the pulse mode with a frequency of 181kHz and a pulse width of 1056ns. The goal was to reconstruc of the hysteresis curves for both the voltage and the pressure and thus determine the optimum oxygen ow. Two experiments (Figure 3.1) were conducted with targets in different stages of their useful life. The rst one, referenced as 980425, was a a relatively fresh target which had been previously sputtered in an argon-oxygen atmosphere for a total of 3 hours. The second target, referenced as 990416, had been used for 16 hours prior to the experiment and was approaching the end of its life. For both experiments the base pressure was less than 3.5x10-4 mPa and the argon ow was kept constant at 80sccm. The turbomolecular pump was throttled so as to maintain a pressure of 0.80Pa at 0.80A and zero oxygen ow (total pressure equal to argon partial pressure). In the case of target 980425 oxygen was introduced in the chamber in steps of 2sccm every 200 seconds, allowing for the stabilization of the voltage. The stabilized voltage and the total pressure were then recorded. It must be noted that the voltage is changing rapidly when the ow is close to the transition point. Furthermore, the measured mass ow was consistently smaller than the set ow.
36
This discrepancy reached a maximum of 0.7sccm at the maximum set ow level of 12sccm. For target 990416 the oxygen ow was increased in steps of 0.2sccm every 150 seconds and the voltage and pressure were recorded in 50 second intervals. The range of the set ow values was from 0 to 11.1sccm, which corresponds to a measured range of 0-10sccm. Thus, the maximum discrepancy between set and measured mass ow was 1.1sccm and occurred at the maximum set ow of 11.1sccm.
980425: fresh target

Voltage (increasing flow) Voltage (decreasing flow)
990416: old target
0.95
280
Voltage (increasing flow) Voltage (decreasing flow)
0.92
300
0.90
Pressure (Pa)
Pressure (Pa)
Voltage (V)
Voltage (V)
240
P = m1 + m2 * Qox m1 m2 R 0.7830 0.0137 0.9921
0.88
250
P = m1 + m2 * Qox m1 m2 R 0.7778 0.0137 0.9995
0.85
200
200 0.80
Pressure (increasing flow) Pressure (decreasing flow) Linear fit for pressure
Pressure (increasing flow) Pressure (decreasing flow) Linear fit for pressure
0.84
160 0 2 4 6 8 10 12
0.8
150 0 2 4 6
10
0.75 12
Oxygen Flow (sccm)
Oxygen flow (sccm)
FIGURE 3.1: Discharge voltage and total pressure vs. oxygen ow for two Al targets. Argon ow: 80sccm. Current: 0.80 A. Partial pressure of argon: 0.80Pa
The marked reduction of the discharge voltage at high oxygen ows is caused by the difference in the coefcients for emission of secondary electrons by ion bombardment between the metallic and the oxidized aluminum. The Al2O3 thin lm, which is formed on the surface of the target at high oxygen ows, has a much higher emission coefcient than metallic Al [mani80a]. Discussion of the high oxygen ow regime One common observation for both cases is the linear dependence of the total pressure on the oxygen ow at high ow values. The slope coefcient of the linear t for oxygen ows higher than 7sccm is 0.0137Pa/sccm. If we plot the
37
total pressure as a function of the oxygen ow when there is no plasma discharge (Figure 3.2), and do a linear t for ows higher than 7sccm, we get a slope coefcient equal to 0.01380.0004Pa/sccm. This fact is in accordance with the literature results [mani80b] where the pressure varies linearly with the ow of the reactive gas when the target is fully oxidized, an effect that manifests itself at high reactive gas ows.
0.95
Pressure (Pa)
0.90
0.85
P = m1 + m2 * Qox Value m1 m2 Chisq R 0.7856 0.0138 0 0.9975 Error 0.0038 0.0004 NA NA
0.80 0 1 2 3 4 5 6 7 8
10
11
12
Oxygen flow (sccm)
FIGURE 3.2: Variation of total pressure with oxygen ow. Argon ow: 80sccm. Current: 0 A. Partial pressure of argon: 0.80Pa. The linear t is calculated for the ow values used in the linear ts in Figure 3.1.
In these cases the extra amount of oxygen introduced is not getter-pumped at active aluminum surfaces in order to create more aluminum oxide. It only adds to the total pressure. Similarly, when there is no discharge at all, any amount of oxygen introduced to the chamber increases the total pressure. The vertical offset of the linear t curves is an indication of the amount of oxygen being consumed while the target is in the fully poisoned state. Assuming constant argon ow, discharge current, and pumping speed, the vertical offset should scale inversely with the amount of oxygen that is consumed in the process. The slope should remain the same since, in the fully poisoned state, it only depends on the pumping speed.
38
Ideally, a constant pumping speed over the range of total ow values (sum of oxygen and argon ow) would result in a vertical offset of 0.80Pa for the nodischarge case. However, the pumping speed is not constant at this pressure range [leyb94]. It decreases as the total ow and pressure are increased, leading to steeper slopes for the pressure-ow curves at high ow values. Consequently, when the linear ts for high values of oxygen ow are extrapolated to zero oxygen ow, the resulting offset is less than the actual pressure of 0.80Pa (see Figure 3.2). In Table 3.6 we summarize the results of the linear t curves and juxtapose them to the discharge voltage in order to show that our results are in agreement with the expected behavior of the process. In particular, the offset without discharge has indeed the highest value and decreases with increasing voltage (and power) levels. The reason is that at higher power levels the target is being eroded at higher rates which result in higher consumption rates of the available oxygen and, therefore, in a lower partial pressure for oxygen.
TABLE 3.6: Linear t parameters for high oxygen ows (Figure 3.1 and Figure 3.2).
Target 980425 990416 N/A
Offset (Pa) 0.77780.0022 0.78300.0037 0.78560.0038
Slope (Pa/sccm) 0.01370.0002 0.01370.0005 0.01380.0004
Voltage (V) 194 164 0
Discussion of the history dependence of the transition point Another interesting fact is the dependence of the voltage-ow curves on the history of the targets. In Table 3.7 we summarize the most important attributes of the two curves which are depicted overlaid in Figure 3.3. It is evident that as the a target is used for repeated depositions, the hysteresis loop becomes shorter, wider and more square and is displaced to the lower ow
39
TABLE 3.7: Characteristics of the voltage-ow hysteresis curves in Figure 3.1.
Target
Hours of use 3 16
Vmax-Vmin (Volts) 100 77
Vinita (Volts) 286 240
"Q at
(Vinit-Vn)/2b (sccm) 0.9 1.2
Qc (sccm) 9.4 4.8
QTd (sccm) 6.6, 5.8 4.6, 3.4
980425 990416 a. b. c. d.
Initial voltage at zero oxygen ow. Width of hysteresis loop halfway between the initial and nal voltage values. Highest oxygen ow at which hysteresis is still observed. Transition ow: value at which the voltage is Vinit-30 V.
350 16 hr target (incr. flow) 16 hr target (decr. flow) 3 hr target (incr. flow) 3 hr target (decr.flow)
300
Voltage (V)
250
Transition point
200
Transition point
150
10
12
Oxygen flow (sccm)
FIGURE 3.3: Transition voltage and ow for two Al targets (Figure 3.1 & Table 3.7).
values. The ow value Q is essentially the ow required to bring the target to the fully poisoned state. The most important parameters are the initial voltage Vinit and the transition ow QT. Prior to every deposition the target is sputtered for 200-300 seconds in a pure argon atmosphere (zero oxygen ow) and the measured voltage of the discharge is Vinit. The transition ow QT, and particularly the rst value which corresponds to an increasing ow, has been selected as the operating oxygen ow level. It results in a partially poisoned target and the associated voltage drop
40
can be maintained at that level over prolonged times with minor adjustments in the ow. Experience has shown that higher oxygen ows will result in more dramatic and even unstable voltage drops, while lower ow values are also prone to unstable voltage changes, albeit in the opposite direction. Furthermore, with oxygen ow at the QT level, the deposit has a stoichiometry close to the ideal and the deposition rates (0.4-0.7nm/s) are comparable to the ones observed for metals. An interesting result of the above is the drift of the transition point towards lower oxygen ows and lower voltage and power values as the targets get older. We have tracked the QT and power values for a series of deposition sequences for one target and we present the results in Figure 3.4. The most likely cause for this drift is the oxidized condition of the target at the end of each deposition sequence. It can be speculated that after every reactive sputtering process the target becomes more heavily poisoned, and therefore less oxygen is needed in order to bring the target in the transition state.
(a) 8.0
Power
(b) 240 220 6.0 200 6.5
7.5
Transition O2 flow (sccm)
7.0 6.5 6.0 5.5 5.0 4.5

O flow
O 2 flow (sccm)
Power (W)
5.5
180 160 140

2
5.0
Q = a + b*S
T
Value
Error 0.5210 0.0027 NA NA
4.5
a b Chisq R
-2.2602 0.0383 0.13146 0.98545
4.0
120 10
4.0 160
170
180
190
200
210
220
230
Deposition #
Power (W)
FIGURE 3.4: a) Transition ow and power values for depositions from one Al target. b) Transition ow vs. corresponding power level (from graph a). Argon ow: 80sccm. Current: 0.80 A. Each deposition lasts approximately two hours. The controlled variable is the transition oxygen ow, QT.
41
This speculation is supported by the drift in the initial voltage values Vinit, as the target is used repeatedly for reactive deposition of aluminum oxide lms. In effect, we observed a dependence which can be described as: Vinit = f (n) = Vinit (n)
where n is the number of depositions performed by a single target. To avoid any effects caused by the exposure of the target to the atmosphere, we compared the discharge voltage values before (i.e.: Vinit) and after each deposition sequence. Vinit was 2-10 Volts higher than the voltage measured in a pure argon plasma immediately after the process. Also, in the following reactive deposition sequence, Vinit(n+1) was lower than Vinit(n). Consequently, the new transition voltage, empirically dened as Vinit-30, decreased too. The most useful conclusion from Figure 3.4 is the linear relation between the average power of the discharge and the oxygen ow when the target is at the transition state. This relation has been used to predict the transition ow for reactive depositions with different aluminum targets with just the knowledge of the discharge voltage Vinit in a pure argon atmosphere(Figure 3.5). In particular, the desired level of the average power during the reactive deposition is calculated as: S
avg
= 0.8 ( V init 30 )
(3.1)
and then the predicted transition ow (based on the linear regression analysis on the data in Figure 3.4.b) is given by: Q T = ( 2.26 0.52 ) + ( 0.0383 0.0027 ) S
avg
(3.2)
42
Of course, this is just a guide for the correct range of the oxygen ow. The actual value, which will keep the voltage and power at the desired levels, will have to be dynamically re-adjusted during the deposition.
6.5
Transition O2 flow (sccm)
6.0
5.5
5.0
Q = m1 + m2 * S
T
4.5
Value m1 m2 -2.2602 0.038283
Error 0.52098 0.0026958
4.0 160
170
180
190
200
210
220
230
240
Power (W)
FIGURE 3.5: Actual (markers) and predicted (line) transition ows for 4 depositions. Predicted transition ow values are derived from Eq.(3.2).
The variance in the deposition rates is a direct result of the transition point drift, which depends on the history of target. The power of the discharge is directly related above a threshold and below a saturation value to the deposition rate. Another change that occurs with repeated and prolonged usage is in the shape of the target. As the target is sputtered, a circular erosion track forms on its surface, along the eld lines created by the permanent magnets in the magnetron gun. This track has grown as deep as 2mm in our targets, which have a total thickness of 3mm. It may be argued that the increased effective surface of the target causes a decrease in the current density and the voltage required to supply the constant current of 0.80 A. It has been suggested that prolonged pre-sputtering of the poisoned target in a pure argon plasma with a dc voltage might ultimately clean the target and restore Vinit to its value for a fresh target (~310V, at 0.80Pa, 0.80A, 181kHz).
43
However, it was not possible to achieve such results after 30 minutes of dc-sputtering in pure argon. In fact, when the target was driven with the standard pulsed dc signal, the discharge voltage remained the same as before pre-sputtering. The uctuation of the oxygen ow and the discharge power (or voltage) during a single deposition sequence, as depicted by the error bars in Figure 3.4 is attributed to two causes. First, there is a drift in the measured ow level with time. The measured ow value will be decreased by up to 0.4sccm in the course of a 2 hour long deposition, even though the set point in the mass ow controller has remained at the same value. This drift can cause the subsequent increase of the discharge voltage towards values higher than the transition point. Then, the operator may adjust generally, increase the oxygen ow so as to maintain the voltage at the transition level. Furthermore, due to the inherent instability of the process, a momentary perturbation in the ow may send the voltage irreversibly up or down the curves shown in Figure 3.3. At that point the operator has to adjust the ow in order to return the voltage to the transition value. In the case where the voltage has reached its lower limit, the deposition has to be interrupted and the target must be sputtered in a pure argon plasma so that the discharge voltage reaches, or at least approaches, Vinit. From the discussion above it may have become obvious that it is difcult to predict the transition oxygen ow for each deposition. The linear t from Figure 3.4 can be used to estimate the transition ow QT with relative accuracy in only half of the cases that were used to derive it. It can certainly be employed to obtain a rough estimate but the ne-tuning of the process must be performed either by the operator or by an expert system which would actively control the oxygen ow using the power values as a feedback.
44
Discussion of the relation between discharge power and deposition rate As has been discussed earlier, the discharge power for each deposition sequence is determined by the voltage Vinit of the target in a pure argon plasma. This initial voltage is decreased as the target is used repeatedly. Consequently, the oxygen ow that is necessary to bring the target to its transition state, empirically dened as the state where V = VT = Vinit-30, decreases also. It is expected that as the power of the discharge is decreased from one deposition to the next, the deposition rate will also suffer a similar decline. In order to substantiate this the rate at which the oxygen was consumed in each deposition was estimated. This estimate is based on the schematic in Figure 3.6.b, where the change of total pressure with oxygen ow is depicted with and without plasma discharge. A model with a nite transition range of ows is used in order to better approximate the experimental reality. If an average transition ow of oxygen QT is assigned for the total duration of a deposition sequence then, in principle, it is possible to estimate the partial pressure of oxygen corresponding to that ow, if the former is calibrated against the latter. This calibration was done by measuring the partial pressure of oxygen for various ow values in the 4-6.5sccm range. The particular interval was selected because in almost all depositions we selected a transition ow within that range. During all measurements a constant argon ow of 80sccm was kept and the main pump was throttled to maintain an argon partial pressure of 0.80Pa. Unfortunately, the stability of the latter cannot be guaranteed during the measurements since the pumping speed drifts with time generally decreases even when the ow remains constant. Moreover, the pumping speed is not constant at the pressure levels resulting from mass ows of tens of sccm. The exact values of our measurements and the result of a linear regression analysis are presented in Figure 3.6.a. The continuous pressure curve in
45
Figure 3.6.b is essentially the linear t curve derived from the pressure measurements.
(a)
0.1
P=P
(b)
0.9
No discharge Discharge with increasing flow
0.08
00
+a*Q Error 0.0021 0.0004 NA
Value P00 -0.0017
0.88
Partial pressure (Pa)
Total pressure (Pa)
0.06 0.04 0.02 0 -0.02
0.86 0.84 0.82 P0 0.8 0.78
0.9850
Total pressure
0.0123
Metallic mode Mode A Pn PT PAr Q

T
Insulator mode Mode B
P00 0 1 2 3 4 5 6
Oxygen flow (sccm)
Oxygen flow
FIGURE 3.6: a) Calculation of partial pressureoxygen ow relation. b) Total pressure vs. increasing oxygen ow with and without discharge. Graph (a): Argon ow: 80sccm. Argon partial pressure: 0.80Pa. No discharge. Graph (b): A realistic case with a nite transition range of ows is depicted. Constant argon ow and partial pressure. Constant pumping speed.
From Figure 3.6.b it is evident that at a ow equal to QT only the surplus oxygen contributes to the total pressure and its partial pressure is just PT-PAr, where PT is measured directly with a capacitance manometer, and PAr is measured in a pure argon plasma with 80sccm of argon, just after the deposition sequence, at the same throttling of the pump. Naturally, the consumed oxygen is responsible for the missing pressure which, if added to PT, would bring the total pressure to Pn. Then, the fraction of the supplied oxygen that is consumed is given by: ( P n P Ar ) ( P T P Ar ) f = -------------------------------------------------------------P n P Ar
(3.3)
46
However, Pn cannot be measured at the same conditions as PT. It can only be calculated from the linear t from Figure 3.6.a: P n = P 0 0.0017 + 0.0123 Q T (3.4)
where P0 was adjusted to be 0.8Pa and represents a constant pumping speed. It has to be noted that P00 (see Figure 3.6.a) should be equal to zero (0.00000.0025Pa) if the pumping speed was constant in the pressure range encountered during calibration. Its calculated value (-0.00170.0021Pa) comes close enough, yet its slightly negative value is evidence that the pumping speed at 0.84-0.88Pa is lower than that at 0.80Pa, and therefore the pressure-ow curve at 0.84-0.88Pa is steeper. PAr and P0 are measured in different conditions with and without discharge, respectively and therefore there is a leap of faith in accepting the partial pressure of oxygen without discharge as the difference Pn - PAr. To the extent that P0 can be approximated with PAr and inasmuch the pumping speed is constant during calibration and deposition, we can use Eq.(3.3) with relative condence, keeping always in mind the uncertainties in pressure readings and mainly the drift in the apparent pumping speed. As stated before, of interest is the consumption rate of oxygen, which is just the product of the supplied rate with the fraction that is consumed: Pn PT C r = Q T f = Q T ---------------------P n P Ar
(3.5)
The variation of Cr for two targets as a function of the average discharge power utilized in each deposition is presented in Figure 3.7. It is observed that during the useful life of a particular target, which is always sputtered at the transition voltage VT = Vinit-30, the estimated consumption rate of oxygen suffers a gradual
47
decrease of 45%, even though the supplied transition ow of oxygen is reduced by less than 35% (Figure 3.4.b). This difference implies that the consumed fraction of the supplied oxygen decreases throughout the life of a target, even when the discharge voltage is adjusted to the empirically determined transition value. Another signicant observation is that the decrease in the estimated consumption rate of oxygen explains the measured reduction in the deposition rate of the aluminum oxide. The latter falls from 0.7nm/s for a fresh target to 0.4nm/s towards the end of the target life. This agreement substantiates the preceding analysis since a high consumption rate of oxygen, in the transition state, will result to a high production rate of aluminum oxide and consequently to a high deposition rate.
Average power (% of maximum)

0 20 40
init
60
80
100
100
V =V -15...85
T
1.2 10 1 1018 8 10
17
18
Oxygen consumption rate
mc/s)
VT=V init-30 80 60
(100 = 1.15 x 10
18
6 1017 40 20 0 4 10 2 10 0 250
17
17
50
100
150
200
Average power (W)
FIGURE 3.7: Oxygen consumption rate vs. discharge power. Closed circles: depositions from one target. Open circles correspond to depositions from different target, carried out in different conditions (see legend).
Finally, the aberrant value in Figure 3.7 which corresponds to a power of 150W represents a deposition sequence where the target was fully oxidized (due to a high oxygen ow rate). In this case the fraction of the oxygen that is consumed is
48
so low that reduces dramatically the consumption rate despite the high supplied ow.
3.2.2 Deposition sequence

Ordinarily, it is necessary to deposit an insulating layer over a part of the substrate only, the goal being to minimize the area occupied by an insulator at the interface between the protective layers and the substrate. Thus, an increased mechanical integrity is achieved as the metallic protective layer is being grown on top of a metallic body. The minimization of the obstacle to the heat diffusion and conduction that is imposed by the insulating lm is also achieved. Currently, a simple shadow masking technique is employed. In particular, a piece of thin 304L stainless steel sheet, having the overall dimensions of the substrate, is mounted on top of the substrate on the substrate holder. The piece of sheet has a machined slot so as to leave part of the substrate exposed to the impinging molecules. In Figure 3.8 such a piece, used for 50x50mm substrates, is depicted.
FIGURE 3.8: Shadow mask for shaping sputter-deposited Al2O3 layers.
The deposition of the bottom insulation layer is preceded by the deposition of an adhesion-promoting titanium lm. The latter takes place immediately after the completion of the sputter-etching process which has been described in Sputteretching on page 31. It is important to note that sputter-etching, titanium and aluminum oxide deposition, all occur in the same vacuum in order to minimize contamination of the surfaces. The parameters used for the deposition of the two lms are described in Table 3.8.
49
TABLE 3.8: Process parameters for reactive deposition of aluminum oxide.
Target material Base pressure Argon ow Argon partial pressure Oxygen owa Oxygen partial pressure Power or Current (controlled) Pulse frequency/width Discharge voltage Deposition time Film thickness
Titanium <1E-4Pa 802sccm 0.800.01Pa N/A N/A 150W dc N/A 310-320V 20-30s 10-20nm
Aluminum N/A 802sccm 0.80000.0025Pa 4-6.5sccm 0.3-0.6Pa 0.80Ab 181 kHz/1056nsc 210-280V 5000-7000s 3-5m
a. Following the Discussion of the history dependence of the transition point on page 39, it is evident that, for each particular deposition sequence, the oxygen ow has to be adjusted in order to achieve a discharge voltage close to VT which is dened as the voltage 30 Volts below the discharge voltage in a pure argon atmosphere (Vinit). b. Value set at 80% of maximum. c. Lower frequency and pulse width values lead to long-term plasma instabilities, while higher values reduce the apparent deposition rate.
The substrate is mounted on the holder so as to be directly across the target during the deposition. However, due to the small target size (diameter of 50mm) it is impossible to get very uniform deposits with stationary substrates. Usually, the thickness prole of thick lms (2-3m) has a slope of 200-300nm across a radial distance of 1cm. The deposition of the titanium lm is quite straightforward. There is a 300s presputtering period in order to remove the oxide and adsorbed water molecules from the target surface and to achieve a stabilized discharge voltage. During this stage, the substrate is shielded with a shutter. The removal of the shutter marks the start of deposition.
50
Before every reactive deposition the aluminum target is also pre-sputtered for 300-600s in a pure argon atmosphere in order to remove surface contamination (region 1 in Figure 3.9). During this step, the shutter is placed between the substrate holder and the target. At the nal stage (60-100s) of pre-sputtering, the substrate holder and the shutter are moved away from the target in order to simulate better the conditions during actual deposition. The reason is the inuence of the target-shutter distance (3cm) to the discharge voltage. By removing the shutter and, of course, the substrate holder behind it the distance from the target to the nearest obstacle (15cm) is signicantly increased and therefore more ionization events are allowed to occur, which in turn decrease the discharge voltage necessary to sustain the pre-set current level of 0.80A. In this way a more reliable value for the initial voltage Vinit can be obtained and will be used to dene the transition voltage VT. During this stage, the turbomolecular pump is throttled so as to achieve a pressure of 0.8Pa. In order to enhance the atomic peening effect [cf. Stress state on page 14], a number of deposition experiments were carried out at partial argon pressures of 0.4-0.5Pa. However, it was impossible to sustain the discharge over a few minutes without extensive arcing. Therefore, the partial pressure of argon was kept at 0.8Pa for all subsequent experiments. The next step is to introduce oxygen at a level that will cause the discharge voltage to drop by 30 Volts (region 2 in Figure 3.9). An estimate for the necessary oxygen ow can be made using the linear t from Figure 3.4.b. which relates the discharge power to the average oxygen ow. However, it is necessary to netune the ow in order to get a stable voltage before the return of the substrate holder at the appropriate position for deposition (facing the target). This replacement of the substrate holder marks the start of the deposition sequence (region 3 in Figure 3.9).
51
During the entire deposition the discharge voltage should be monitored and any drifts from the desired value (VT) should be compensated by adjusting the ow (circled ow markers in Figure 3.9). In particular, when the voltage drifts to higher values, the oxygen ow should be increased in order to bring the target to a more poisoned state and counter the voltage hike. The reverse action is taken in the case of a voltage decrease.
(1) 260 250 240
(2)
Flow adjustments
(3) O2 Flow (sccm)
5.2 5.0
O Flow (sccm) 2
Voltage (V)
Flow drifts
230 220 210

Voltage drifts
4.8
4.6 4.4 4.2
200 190
90
Voltage (V)
1780 1870 2000 2180 2720 6400 6640 6740 6900 7200 7300 190 280 420 460 510 560 650 750 930
Time (s)
FIGURE 3.9: Discharge voltage and oxygen ow variations during reactive deposition. Region 1: pre-sputtering; region 2: initial oxygen injection; region 3: reactive deposition of aluminum oxide. Notice the drifts in the discharge voltage and the ow adjustments employed to counteract them.
It might happen that the voltage has drifted to its low limit before the operator takes notice of the change. In such a case an incremental ow decrease will force the discharge voltage to trace the lower (dashed) curve of the hysteresis loops in Figure 3.3, and the transition point will be reached at a lower ow. This is what happened in the case of Figure 3.9: initially QT was 5.1sccm. After the voltage had drifted to its low limit we decreased incrementally the ow until we raised
52
the discharge voltage to VT. However, the new QT was only 4.5sccm. In order to perform the deposition at the initial conditions we would have to shield the substrate with the shutter, interrupt the oxygen ow, wait until the discharge voltage returns to within 2-3 Volts from Vinit, and then re-inject oxygen at the original ow level and resume deposition.
3.3 Sensor layer

The materials used for the sensor circuits were selected with respect to their thermo-electric properties. In particular, strain gages are sputter-deposited from a constantan target because this alloy has a very low temperature coefcient of resistivity (30ppm @ 25-105C). Also, the standard thermocouple alloys or metals (alumel, chromel, constantan, copper) were used to build temperature sensors by sputtering the respective targets. The obvious reason for this selection is the ease in calibrating the deposited sensors using standard thermocouple reference tables.
3.3.1 Photolithography
The sensors are in essence electrical circuits and therefore they have to be shaped out of the blanket metallic lm that is deposited via sputtering. The shaping is achieved with micromachining which combines photolithography (steps (a)-(d) in Figure 3.10) and a removal sequence known as lift-off (step (f) in Figure 3.10). The main goal of this work has been to establish the feasibility of embedding sensors in metallic structures and therefore there was not put much of an emphasis on the geometry of the circuits. The designs (positive masks) for the strain gages are included in the Appendices (Positive masks of strain sensors on page 124). The line width varied from 420 to 50m and the size of the longest line varied from 30 to 8mm. The line width for the thermocouple was generally 176m and the length of the sensor itself was 30mm.
53
a) Photoresist is deposited on substrate
b) Patterned mask is placed on substrate and exposed
c) Mask is removed
d) Exposed photoresist is developed, leaving a patterned window
e) Metal thin film is deposited over the substrate
f) Photoresist layer is removed by acetone, carrying away overlying metal film (Lift-off)
FIGURE 3.10: Schematic of the photolithography steps preceding a lift-off process.
The masks were designed with the aid of a commercial drawing application, usually Adobe Illustrator, and after their transfer to a Postcript le the negative of the image was printed on a transparency by a high-resolution laser printer. Then, the mask pattern was transferred on the substrate surface in the following manner: a few drops of positive photoresist (Shipley 1813) were dropped on the substrate which was spinning at 2000-3000rpm for 30-40s. The rapid spin resulted in a thin (1.5-2.0m) layer of photoresist. The substrate was subsequently baked in an isothermal furnace at 90C for 20 min. After baking, the part of the mask with the desired sensor was positioned manually on top of the substrate and was held in place by a glass plate. The glass plate was pressed
54
against the substrate by a simple spring-loaded assembly. The assembly was then placed under an UV light source and was exposed for 40 seconds. Exposure of a positive photoresist to UV radiation causes a change in the chemical structure of the photoactive agent of the resist. This change makes the exposed volume soluble to developer solutions. After exposure the substrate was removed from the assembly and was immersed for 15-20 seconds in a bath containing concentrated developer from Shipley and de-ionized water in a 1:1 ratio. The developing time is enough to remove the photoresist from the exposed regions which correspond to the sensor pattern. Developing is stopped by rinsing in de-ionized water. Stylus prolometry of the developed region near the sidewalls has shown that the thickness of the photoresist is reduced from its maximum value (1.5-2.0m) to zero in a distance roughly equal to 8m. This corresponds to a rather shallow slope, suboptimal for the lift-off process which requires ideally negative slopes or at least vertical ones. Nevertheless, the lift-off results for the particular line widths have been quite successful.
3.3.2 Deposition
The substrate is mounted on the substrate holder and transferred to the sputtering chamber. After the pump-down the deposition sequence begins with the growth of a thin (10-20nm) adhesion layer out of titanium. Then the substrate is transported over the magnetron gun with the sensor alloy target and the deposition of the sensor layer commences. The parameters for the deposition of each particular lm are summarized in Table 3.9. The sputter-etching of the substrate is generally not recommended in order to prevent damage on the dielectric layer and the extreme hard-baking of the photoresist. The substrate is bombarded with high energy (~300eV) ions and electrons (since a pulsed-dc signal is used to drive the substrate holder) during
55
the sputter-etching process, and its temperature is raised to ~100C, thereby any S1813 photoresist layer would be unintentionally hard-baked and the lift-off procedure would be considerably hampered.
TABLE 3.9: Deposition parameters for the sensor alloys and the adhesion interlayer.
Target material Base pressure Argon ow Argon partial pressure Power (controlled) Discharge voltage
Titanium <1E-4Pa 802sccm 0.800.01Pa 150W dc 310-320V
Constantan <1E-4Pa 802sccm 0.800.01Pa 150W dc 390V
Alumel N/A 802sccm 0.800.01Pa 150W dc 410-420V
Chromel N/A 802sccm 0.800.01Pa 150W dc 408V
3.3.3 Lift-off
As soon as the sensor layer is deposited, the substrate is removed from the chamber and immersed in acetone. It is left to soak for 4-5 hours, a period which is usually adequate for the photoresist be dissolved. As the photoresist is removed, the metallic lms that have been deposited on top of it lose their base and can be washed by the acetone. Only the region of the lms that was deposited on top of the dielectric, through the window in the patterned photoresist, remains bonded to the substrate and forms the sensor. Ideally, in the case of vertical or negative photoresist sidewalls, the lm deposited on top of the photoresist would be fully detached from the part which is bonded to the substrate. However, in the case of positive slopes, the lm remains attached to the bonded region along its edges. The unwanted lm is removed by tearing these edges with the aid of pressurized dry nitrogen. The result is a relatively jagged edge on the sensor lm as shown in Figure 3.11. This undesired effect can be eliminated by using either negative photoresist (where
56
FIGURE 3.11: Jagged edge of deposited constantan lm after lift-off.
the exposed part stays, while the unexposed is dissolved), or a combination of chemical treatment and exposure that reverses the slope of the positive photoresist walls.
3.4 Top Oxide

The deposition sequence for the passivation layer that partly covers the sensor is almost identical to that for the base insulation layer. The only differences are relevant to masking and sputter-etching. Since it is necessary to leave parts of the sensor exposed for splicing purposes (splicing is the connection of wiring to the sensor to enable signal acquisition and processing) it is apparent that the mask in Figure 3.8 cannot be used as is. Usually, a piece of aluminum foil is used to cover the connection pads of the sensor during deposition. The rest of the substrate is covered with the shadow mask used in the deposition sequence of the rst oxide layer.
57
Sputter-etching is critical in achieving a pinhole-free oxide layer by removing the top few monolayers of the substrate where dust particles or organic molecules may be attached. However, in this case the sensor lm itself would be thinned by the sputter-etching action and its resistance would change. This is not an issue for the thermocouples where the output is only dependent on the difference of the thermoelectric coefcients of the two materials. Nevertheless, the generalization of a strain sensor calibration for a batch of similar devices would only be valid if the sputter-etching process altered the thickness and the resistance of the sensor in a well-dened and predictable manner.
3.5 Protective Layers

The purpose of these layers is to protect the thin lm structure (insulation and sensor) from the high-temperature embedding process. In particular, the protective layers are necessary to reduce the temperature experienced by the thin lms as an intense and localized heat ux is imparted by the laser during the formation of the embedding layer. The results of an attempt to form such a layer directly over the oxide lms can be seen in Figure 3.12. Initially, it was thought that a relatively thick (2-3mm) layer of copper (a metal with a thermal conductivity second only to silver) could be used to rapidly transfer the heat generated during the embedding step to the metal substrate. A necessary provision for this layer would be to directly contact the substrate over a large area, compared to the surface occupied by the dielectric lms that were sandwiched between the substrate and the protective layer (Figure 3.14.b). The thick copper layer could be grown by electrodeposition on top of a seed copper lm which would be sputter-deposited on the substrate, partially covering the top dielectric layer. Embedding experiments showed that the copper layer could not function as the sole protective coating for a number of reasons. First, its high thermal
58
Laser deposited invar Al2O3
2 mm
304L stainless steel substrate
FIGURE 3.12: Cross-section showing an Al2O3 lm damaged during laser deposition. Notice the discontinuity in the thin lm and the remelted invar/304L interface between the oxide fragments.
conductivity would not allow partial remelting near its surface, thereby causing the formation of void clusters at the interface with the embedding layer as shown in Figure 3.13.a. Such a condition would severely compromise the mechanical integrity and the fatigue resistance of the structure. In addition, even in the cases where partial remelting was achieved, the copper and the invar layer would retain their distinct phases, as can be seen in Figure 3.13.b, thereby falling short of a strong metallurgical bond. So, it became evident that a second protective layer could be essential for the successful embedding. Bearing in mind that electrodeposition would be the process of choice, we focused on a small number of elements and selected nickel for its lower thermal conductivity and the fact that it is one of the two constituents of the embedding alloy (invar). In the new conguration, the nickel layer would cover the copper layer and it would extend over the edges of the latter in three sides, as shown in Figure 3.14.c.
59
Laser deposited invar
Laser deposited invar
10 m
Electroplated Cu
50 m
(a)
Electroplated Cu
(b)
FIGURE 3.13: a) Clustered voids at the invar/copper interface. b) Distinct phases across the partially remelted invar/copper interface.
(a)
(b)
(c)
Top dielectric film Sensor film (contact pads)

FIGURE 3.14: a) Schematic of substrate with sensor enclosed between two dielectric lms. b) Schematic showing the copper layer footprint. c) Schematic showing the nickel layer footprint.
3.5.1 Copper layer

Since an electroplated layer can only be grown on a conductive substrate, it was necessary to cover the top dielectric lm with a metallic layer which would serve as a seed for the electrodeposited copper. Sputter-deposition is a relatively simple process that can deposit metallic lms on a great variety of substrates and was selected to grow a thin lm of copper on the substrate. A titanium interlayer was deposited in order to enhance the adhesion of copper to both the aluminum oxide and stainless steel areas. The deposition of the two lms was sequential
60
and was carried out in the same vacuum. The process parameters for the sputterdeposition are described in detail in Table 3.10.
TABLE 3.10: Deposition parameters for the seed copper lm and the adhesion interlayer.
Target material Base pressure Argon ow Argon partial pressure Power (controlled) Discharge voltage Film thickness
Titanium <1E-4Pa 802sccm 0.800.01Pa 150W dc 310-320V 10-20nm
Copper N/A 802sccm 0.800.01Pa 150W dc 400-410V 1-1.2m
To simplify the process, the shaping of the seed lm was achieved by simple shadow masking. Obviously, a more exact, photolithographic procedure can be used if necessary. After the growth of the seed layer, the area of the substrate that would not be covered by electroplated copper was masked with a relatively thick (3-4m) layer of photoresist. The back side of the substrate was fully covered with kapton (polyimide) tape or a thick resin, except for a small area that would be used for electrical contact. Finally, a die-like wall structure was placed around the area that would be electroplated. Generally, specially shaped kapton tape or teon was used in order to create a 4-6mm tall wall to contain the deposit up to its total thickness of 1-2mm. Special care was taken during the handling of the substrate so that the sputterdeposited seed lm of copper would not come in contact with anything but deionized water and that the whole preparation sequence, from the time the substrate was exposed to air until the time of its immersion in the electroplating
61
bath, did not take more than 1 hour. The reason for this precaution was to minimize the oxidation of the sputter-deposited copper surface, as this would affect in an adverse manner the adhesion of the electroplated layer to the seed lm. In the few cases of mishandling that caused the formation of a surface oxide on the copper lm, the substrate was immersed for a few seconds in a solution containing 10% v/v HCl. The acid would remove the oxide without attacking the metallic copper. However, such processing involved the risk of acid reaching the buried top oxide lm through pinholes in the copper lm. Since the aluminum oxide was deposited at a very low homologous temperature (Tsub /Tm<0.2), it was purely amorphous [cf. Microstructure on page 79] and therefore susceptible to etching by the acid. Therefore by allowing the dielectric lm to be attacked, there was a risk of exposing the encapsulated sensor lines (through tiny pinholes) to the electroplating bath and causing them to short-circuit to the protective layer. Such an event would severely harm the functionality of the sensor. Since it was observed that in samples treated with HCl for the removal of possible surface oxides the insulation of the sensors was compromised after only minutes of electroplating, this procedure was actively avoided. As soon as the substrate was ready, it was connected to the live cathode of the power supply in the electroplating system and then it was lowered into the bath which was generally agitated by air ow. Copper can be electrodeposited either in a cyanide or an acid bath. For reasons of operation safety the more benign acid method was chosen and its chemical composition is described in Table 3.11.
62
TABLE 3.11: Chemical composition of copper electroplating solution.
Copper sulfate pentahydrate Sulfuric acid Chlorine ions Aluminum potassium sulfate dodecahydrate
220-240g/l 55-65g/l 30ppm 2g/l
The exact parameters used during the electrodeposition process are presented in detail in Table 3.12.
TABLE 3.12: Electrodeposition parameters for the copper protective layer.
Initial current density Final current density Total thickness Temperature
21mA/cm2 31.5mA/cm2 ~1mm 27C
Time Time
1hr 30hr
At the end of the deposition the substrate was removed from the bath, rinsed with distilled water and blown dry after the removal of the die-like wall structure.
3.5.2 Nickel layer

Initially, the exposed polished stainless steel surface was mechanically roughened via grinding in order to improve the mechanical interlocking factor with the nickel layer. Subsequently, part of the surface was covered with a die structure surrounding the area to be electroplated, dened by the outer dashed line in Figure 3.14.c, in order to contain the thick nickel deposit. The deposition of the nickel layer was performed in two steps also. This time the seed layer was grown in a nickel strike bath, on top of the copper layer and part of the exposed stainless steel substrate. Prior to the seed layer deposition the substrate was subjected to electropolishing by the application of a reverse voltage (substrate connected to the anode) for 2 minutes. Then the voltage was
63
reinstated to its forward direction and the deposition commenced. The composition of the strike bath and the process parameters are presented in Table 3.13 and Table 3.14 respectively.
TABLE 3.13: Chemical composition of nickel strike electroplating solution.
Nickel chloride hexahydrate Hydrochloric acid

TABLE 3.14: Electrodeposition parameters for the seed nickel layer.
60g/l 125ml/l
Reverse current density Forward current density Total thickness Temperature
21mA/cm2 21mA/cm2 ~1m 27C
Time Time
2min 2min
The seed layer could also be deposited via sputter-deposition. However, that would involve an additional pump-down sequence and increased exposure to the air during the transfer between the chamber and the electroplating bath. Using a strike solution instead, the process time was minimized and the substrate is transferred immediately to the next bath while it is still wet. Following the strike deposition, the substrate was transferred immediately to the nickel sulfamate bath for the growth of the nickel layer. That bath was acidic in nature and its chemical composition is listed in Table 3.15, while the deposition process parameters are presented in Table 3.16.
TABLE 3.15: Chemical composition of nickel sulfamate electroplating solution.
Nickel sulfamate Boric acid Barrett additive-A Barrett SNAP A/M
265ml/l 38.6g/l 3.8g/l 0.3% by vol.
64
TABLE 3.16: Electrodeposition parameters for the nickel protective layer.
Initial current density Final current density Total thickness Temperature
21mA/cm2 42mA/cm2 1-1.5mm 48C
Time Time
2-3hr 40-50hr
At the end of the deposition sequence, the substrate was retracted from the solution and all the protective insulating layers (photoresist, resin, kapton tape) were removed. Finally, the substrate was rinsed in distilled water and blown dry.
3.6 Embedding Layers

The nal embedding of the sensor is accomplished with a high-temperature process. In the Rapid Prototyping Laboratory, there are two options available for producing fully dense metal layers: a) plasma microcasting, and b) laser deposition. The former uses a plasma arc to superheat the tip of a metallic wire in order to produce a droplet that subsequently falls onto the substrate, where it solidies upon impact. By moving the wire relative to the substrate (or vice versa) these solidied droplets can form a dense layer of material. The latter method (cf. Laser Assisted Deposition on page 23) uses a high power (2.4kW) infrared Nd:YAG laser beam to create a molten pool on a metal powder bed which is pre- (or concurrently) deposited on the substrate. The beam is created in the optical cavity and transferred via an optical ber whose end is attached to a computer-controlled robotic arm. The material in the spot of the laser beam is heated beyond its melting point and forms a molten pool. By moving the beam relative to the substrate the molten powder cools rapidly and is fused to the underlying material, thereby producing a bead of dense material.
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The laser deposition technique was chosen over plasma microcasting due to superior positioning control of the deposit. Indeed, plasma microcasting suffered from poor control in the landing position of the droplet and its deposit was rather shapeless due to the splattering of the droplet upon its collision with the substrate.
3.6.1 Thermal stress minimization

Initially, all embedding experiments were conducted with the substrate lying on top of a large aluminum mass, acting as a heat sink. The results were rather discouraging as a large percentage of the samples suffered from delamination between the embedding layers and the underlying structure. The delamination was caused by the large thermal stresses developed during the process. Since the thermal stresses originate from thermal strains, the minimization of the latter will lead to the minimization of the former (for the same materials). In layered multimaterial structures the thermal strains are caused by differences in the thermal expansion coefcients () as well as temperature differences among the constituting layers. The resulting thermal stresses will be accentuated by the elastic moduli of those layers. For a given set of substrate materials the only degrees of freedom lie in the selection of the last (topmost) layer and the temperature range of the processing. Therefore, the selected material for the embedding layer should have the smallest possible thermal expansion coefcient, elastic modulus and melting temperature in order to ensure minimal thermal stress generation. However, since the goal of the process is to produce a structure that can withstand high temperatures, it is obvious that the melting point and, consequently, the elastic modulus, must have high values. This reasoning leaves as the sole variable that can be minimized by material selection. The only high-meting point metal that offers a distinctly small is invar (Fe0.64-Ni0.36).
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With respect to the temperature gradient experienced by the structure the lower bound of the temperature at the topmost layer is the melting point of the embedding layer. It was assumed that the laser beam would raster the powder layer at an optimal speed, sufcient to produce a melting pool as deep as the powder bed itself. Lower speeds would unnecessarily increase the heat ux to the structure, whereas higher speeds would leave unfused powder behind the laser path. Therefore, the only way to decrease the temperature gradient would be to increase the initial temperature of the substrate. Such a move would also decrease, by a little, the necessary heat input to achieve fusion of the powder layer. So, the 50mm square stainless steel substrates were placed on top of a copper slab (20 x 20 x 1cm), which in turn was sitting on top of a temperature-controlled hot plate. The latter was set at 450C and the copper slab would reach thermal equilibrium at ~350C. In order to provide a consistent thermal interface between the stainless steel substrate and the copper plate, irrespective of the surface nish and the powder particles that might be attached to the contacting surfaces, a thin layer of silicone paste was applied to the bottom the stainless substrate. The equilibrium temperature of the substrate prior to deposition was 300-350C.
3.6.2 Fusion of the powder layer

The powder was placed was placed either automatically via a feed tube which was scanned above the substrate by a robotic arm or manually by the operator. The thickness of the powder layer was adjusted to 30.5mm. A supporting mass of powder was also arranged around the substrate in order to allow constant thickness of the powder layer all over the substrate surface. The attributes of the laser path, i.e.:cordinates, scanning speed, intervals between passes, were gradually determined by making educated guesses based on observation of attempts which succeeded only partially or failed catastrophically. Another decision which was inuenced by the observation of
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such attempts concerned the addition of an extra protective layer. The progressive attempts to arrive at nal and successful embedding procedure are depicted in Figure 3.15 and Figure 3.17. During the initial attempts the laser beam was scanned in a zig-zag fashion over the powder bed, with a constant linear speed of 20mm/s and without a stop between successive passes (which would be traced in opposite directions). The power was held constant at ~1.8kW and the diameter of the beam spot was 2.5mm, yielding a power ux of ~360MW/m2. The result of this conguration when used on a non-pre-heated sample with just one protective copper layer was inadequate bonding of the invar at the beginning of the path and through-thethickness remelting of the copper near the end of the path.
1 2
10
10
(a)
(b)
(c)
FIGURE 3.15: Laser path during progressive attempts to improve embedding. a) Original, continuous path; circle signals the end of the path; b) 20 second intervals introduced between passes; numbers signify pass order; c) Last four passes carried out at higher speeds.
This clearly indicated a problem with the amount and rate of heat that was injected to the sample. A rst response was to introduce 20 second intervals at the end of each path, allowing for the substrate to cool down. When this strategy was used in conjunction with pre-heating the substrate to a temperature of ~350C, the sample was cooling during those intervals to within a few degrees from its equilibrium temperature. In addition to switching off the laser power, another measure was to reduce the total amount of heat injected to the sample by
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accelerating the scanning speed towards the end of the path. So, during the last 4 passes of the path the laser was moved at a linear speed of 20-25mm/s, instead of 15mm/s. All these improvements did away with the remelting of the copper layer through its thickness near the end of the path. However, two other issues remained unresolved; namely, the inadequate bonding of the fused invar layer to the copper (Figure 3.13.a) and the delamination of the copper layer from the substrate at the edge near the end of the path (dotted edge in Figure 3.15.c). The former issue was attacked successfully only with the introduction of a nickel protective layer. The improvement in the quality of the interface can be seen in Figure 3.16 below.
Laser deposited invar 50 m
Electroplated nickel
FIGURE 3.16: Invar-nickel interface from a cross-section of an embedded structure.
The localized delamination of the copper layer was addressed by a modication in the path of the laser beam and the introduction of substrate pre-heating. The latter increased the temperature of the stainless steel substrate, thereby decreasing the magnitude of the product for the copper-stainless bilayer. The laser path was altered so as to fuse the powder initially over the two edges of the protective layers (passes #1 and #2 in Figure 3.17) and subsequently scan the
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rest of the powder bed in a zig-zag fashion.The actual LabView code that produces the path in Figure 3.17 is included in page 125, along with comments for the various commands.
11
FIGURE 3.17: Final laser path conguration. The numbers in the arrowheads signify the pass order. The dashed lines stand for higher scan speeds (20 instead of 15mm/s). During the last two (10,11) passes the laser is moved with a linear speed of 25mm/s.
At the end of the embedding step, which can be repeated in order to produce thicker embedding layers, the sample was left to cool down to ambient temperature and then the silicone paste was removed from the substrate base with acetone. Subsequently, the sensor was tested to ensure functionality. In the case of a strain gage, we measured the resistance from the sensor to the substrate and the resistance between the contact pads of the sensor. If the resistance to the substrate was greater than 1 MOhms and the gage resistance was close to its value before the embedding, then there would be strong reasons to believe that the strain gage survived the embedding process. Of course, only a full-edged mechanical test would give an unambiguous answer. In the case of a thermocouple, the calibration procedure would prove the functionality of the sensor.
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3.7 Summary
In this chapter, the fabrication process for embedded thermo-mechanical sensors was described. Since the purpose of this work is the proof-of-feasibility, the sensors were fabricated on sample 50mm-square substrates made out of 304L stainless steel. We presented in detail the substrate preparation sequence from the cutting of the material to polishing and cleaning, especially with respect to the particle-ridden environment of a manufacturing facility. We concluded that sputter-etching the substrate prior to the deposition of the dielectric thin lm would remove the topmost contaminated layers and most of the particles which were causing the formation of pinholes. Then, we presented reactive pulsed-dc magnetron sputtering of aluminum oxide as the selected method to produce thick dielectric layers at a high deposition rate. We covered the issues that surfaced during the implementation of the technique, especially the migration of the transition voltage and ow for an aluminum target to lower values during its useful life, and the subsequent effects, such as the decrease of the oxygen consumption and the deposition rate. We also presented a guiding linear law, based on empirical results, that could be used to predict the transition values for the oxygen ow prior to the deposition. We described the photolithography, deposition and micro-machining processes that were employed to produce the strain gages and thermocouples from blanket metal lms and we stressed the importance of an adhesion-promoting interlayer between the sensor and the dielectric substrate. Then we exhibited the necessity of protective layers that would shield the thin-lm structure from the hightemperature embedding process, and presented the deposition technique (electroplating) for producing those layers. In the nal discussion which concerned the embedding stage, we explained the need for an additional protective layer to the original copper one, and showed how nickel served adequately as such a layer. We also described the attempts to
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tune the embedding process so that the sensors could be embedded successfully. The corrections that proved most critical where the aforementioned introduction of an additional protective layer, the pre-heated substrate, and the reduction of the heat input and heat input rate to the substrates during embedding.
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Characterization
In the following section we present data with respect to properties, characteristics, and responses of individual components of the embedded structure.
4.1 Composition
Compositional analysis of dielectric and sensor layers is important because their electrical behavior depends strongly on the stoichiometry. Such analysis is not critical for the protective and embedding layers at this stage and it will be assumed that elemental copper and nickel are deposited during the electroplating process, and that the composition of the fused invar powder bed is the same as the composition of the powder particles.
4.1.1 Dielectric layers

The stoichiometry of the deposited aluminum oxide lms was investigated with X-ray Photo-electron Spectroscopy (XPS) and Electron Probe Micro-Analysis (EPMA). The lms used in both techniques had a thickness in the 3m range.
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CHAPTER 4: CHARACTERIZATION
XPS measurements Even though XPS is not suitable for the exact quantitative determination of the composition, it can be used to compare the unknown composition of a sample with that of a standard sample. For example, in our case a sapphire piece (stoichiometric, crystalline Al2O3) was used as a reference sample. Furthermore, since XPS is a surface analysis technique (most of the signal is generated from the top monolayers of the sample, or within 1.5nm from the surface), it was necessary to create a compositional depth-prole of the sample by taking measurements at the bottom of a well created by sputter-etching. Initially, the sapphire crystal was examined by measuring the aluminum and oxygen atomic contents at the surface and at the end of each of 3 sputter-etching intervals. Each interval lasted for 300s and the sputter-etching rate was estimated at ~0.13.04nm/s (cf. Determination of the sputter-etching rate for aluminum oxide on page 75). Then, 3 lms, which were grown by reactive sputtering of an aluminum target in different conditions, were scanned. In particular, one (F1) was deposited with the target at the transition state, achieved by an average oxygen ow equal to 5.7sccm, while the other two (F2 and F3) were deposited with the target at the fully poisoned state, caused by a high oxygen ow, equal to 9.8sccm. The rst lm (F1) was a thick deposit (in the order of 3m) and a depth-proling of its composition was performed in the same manner with the sapphire sample: 4 measurements of the oxygen and aluminum atomic content, with a 300s sputter-etching interval between successive measurements. Films F2 and F3 were relatively thin (in the order of 50nm) and the sputter-etching intervals were much sorter in duration (10, 30, and 80s). All results, in the form of oxygen-toaluminum atomic ratios are depicted in Figure 4.1. The immediate observation is the initial sharp decrease of the oxygen content with depth for all samples. Film F3 was analyzed in order to provide a minimum
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scale for the observation of the reduction. Indeed, a mere 10s of sputter-etching is sufcient to remove the layers responsible for the increased oxygen content which is measured at the surface. In such a short interval only a small number of monolayers can be removed and thus the excess oxygen can be attributed to the water molecules attached to the surface after its exposure to atmospheric humidity. Following the removal of these molecules the oxygen content remains relatively constant for the rest of the depth-proling analysis. Another observation is that all sputter-deposited lms show a lower O/Al ratio than the sapphire sample. The deviation from the mean sapphire value ranges from ~13% for lm F1 to ~3% for lm F3. Therefore, deposition from a fully oxidized target surface results in a composition that is closer to the correct stoichiometry, at the expense, of course, of the deposition rate.
3.0 2.5 2.0
Sapphire F1 (Q Ox=5.7 sccm) F2 (Q Ox=9.8 sccm) F3 (Q Ox=9.8 sccm)
O/Al
1.5 1.0 0.5 0.0
200
400
600
800
1000
Etching time (s)
FIGURE 4.1: Oxygen-to-aluminum ratio vs. sputter-etching time. XPS data from three samples of reactively sputter-deposited Al2O3 and one sample of sapphire.
Determination of the sputter-etching rate for aluminum oxide In order to determine the erosion rate of the deposited aluminum oxide by the sputter-etching action of argon anions we used lm F2 which had a measured thickness equal to 4515nm, as measured by stylus prolometry. The particular
75
lm was grown on a polished 304L stainless steel surface with an average roughness equal to 10 nm. Our goal was to create the compositional depth-prole of the lm by monitoring its aluminum content after short sputter-etching intervals. The results are presented in Figure 4.2, where it can be seen that after 350s of sputter-etching the aluminum content has fallen to 37% (e-1) of its maximum value. It is reasonable to argue that at this time the lm/substrate interface has been reached and therefore to calculate the sputter-etching rate by dividing the known lm thickness with the total sputter-etching time up to the critical point. This calculation yields a rate equal to 0.130.04nm/s. Alternatively, if the interface is assumed to be reached at about 300s, where the last plateau value of atomic content is obtained, the calculated rate is 0.150.05nm/s.
100
80
Al (at. %)
60
40
20 Cmax/e 0 0 100 200 300 400
Etching time (s)
FIGURE 4.2: Aluminum content of deposited Al2O3 lm vs. sputter-etching time. Film F2 from Figure 4.1. Film thickness: 4515nm. Highlighted time corresponds to atomic content equal to 37% of maximum value.
EPMA measurements As opposed to XPS, EPMA can give very accurate results for lms of adequate thickness (larger than 1m). This technique gave measurements of a near-perfect stoichiometry with an oxygen-to-aluminum ratio of 1.499 0.005.
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Perfect stoichiometry is guaranteed at high oxygen ows (QQ, cf. Table 3.7 on page 40). Then, the target is fully covered by an aluminum oxide lm, thin enough to be sputtered even in the pure-dc mode. This lm is stoichiometric and therefore the deposit is stoichiometric, too. Arguably, there can be inclusion of free oxygen ions or atoms in the growing lm, even at the absence of active aluminum atoms. However, judging from the relative abundance of argon (~5:1 for a fully poisoned target, if all the oxygen molecules are dissociated) and the fact that its content in the lm never exceeds 4%, it is difcult to get deposits that are signicantly oxygen-rich, unless the sticking coefcient of oxygen on aluminum oxide surfaces is considerably higher than that of argon. Of course, it is very easy to get aluminum-rich lms when the oxygen ow is lower than QT. The target surface is only partially oxidized and the sputtered species include both aluminum and aluminum oxide particles. Studies have shown that it is only at conditions of a fully poisoned target that Al2O3 does form on the surface of the substrate [stir71, gora78]. Oxygen-decient lms will have a dark brown, or even black, color instead of being transparent, as the extra aluminum atoms provide energy states within the energy gap of the awed insulator which absorb in the visible spectrum and colorize the lm.
4.1.2 Sensor layers

Compositional information for the sensor layers is very signicant for their adequate characterization. The sensor layers for this work are always metal alloys and their electrical response to strain and temperature is dependent on the relative atomic contents of the various constituent elements. As explained before (cf. Deposition on page 55), the sensing lms are sputterdeposited from alloy targets. These targets were machined from bulk blanks which were supplied by manufacturers of commercially available sensors. Due to
77
the different sputtering rates of the constituent elements, the alloyed targets form a thin surface layer whose composition is such that the sputtered species get ejected in direct proportion to their concentrations in the bulk material. This results in a deposited lm that has the same composition with the bulk target (cf. Composition on page 16.) Our goal was to determine the composition of the deposited lms, and compare the results with the nominal values available in the literature. The latter are summarized in Table 4.1 for constantan, in Table 4.2 for chromel, and in Table 4.3 for alumel.
TABLE 4.1: Nominal composition of constantan, measured values for deposit.
Element Cu Ni
Nominal (at. %) 50 50
Deposit (at. %) 50.4 49.6
TABLE 4.2: Nominal composition of chromel, measured values for deposit.
Element Cr Ni
Nominal (at. %) 10 90
Deposit (at. %) 12 88
TABLE 4.3: Nominal composition of alumel, measured values for deposit.
Element Al Mn Ni Si
Nominal (at. %) 2 3 94 1
Deposit (at. %) 2.5 1.8 95.7
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All measurements were performed with EPMA. The lms were grown on single crystal Si wafers, thus the inability to provide reliable data for the Si content in the alumel lm.
4.2 Microstructure
The microstructural characteristics of the thin lms are dening to a large extent their chemical and transport properties. However, the scope of this work is focused more on the development of a working prototype and less on the thorough characterization or specic property enhancement of the constituent layers. Therefore, only simple measurements and educated estimates were performed.
4.2.1 Dielectric layers

The decisive factors for the microstructure of sputter-deposited thin lms are the working pressure and the homologous temperature (the ratio of the substrate temperature and the melting point of the deposit, in K) [ohri92, smit95]. The substrate was never externally heated during sputter-deposition. The temperature at the back side of the substrate (facing away from the magnetron gun) was reaching 80-90C during deposition. Considering that it was supported only by teon spacers, it may be reasonable to assign a temperature of ~100C (~373K) at the front of the substrate1. Such a temperature is typical of magnetron sputtering systems, were substrates are relatively cooler than in simple diode sputtering chambers [wasa92].
1. A rough, steady-state heat transfer calculation, where all the heat ux to a 100cm2, 3mm-thick, stainless steel substrate comes from the impingement of electrons accelerated to ~300eV assuming no energy loss due to collisions making up an electric current of 0.8A, yields a ~15C difference between the front and the back sides.
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The melting point of aluminum oxide is 2323K [incr90], and therefore the ratio Tsub /Tm is ~0.16. Such a ratio, according to the well-known Zone Structure for sputter-deposited coatings [thor77], can only facilitate small brous grains with voided boundaries at pressures of ~1Pa. However, the substrate temperature is far below the crystallization temperature of Al2O3, which is 1003K (730C), and therefore the deposit will have to be amorphous [wasa92]. Images of the deposited lm, produced by Scanning Electron Microscopy (SEM), show a glassy phase. A representative picture is shown in Figure 4.3. The domeshaped structures at the surface of the lm may be either evidence of columnar grains or features due to the surface topography of the substrate surface.
FIGURE 4.3: SEM image of amorphous Al2O3 lm on a stainless steel substrate.
In order to substantiate the SEM evidence of the microscopy, Al2O3 lms deposited on 304L stainless steel were examined in an X-Ray Diffractometer. The XRD spectra of the lm and the uncoated substrate were superimposed (Figure 4.4) so that any crystalline alumina peaks be immediately recognized. As it is easily seen from Figure 4.4, the peaks of the aluminum oxide lm coincide with the (111), (200), and (220) peaks of the austenitic 304L stainless steel [iccd90] and only the amorphous peak is pertinent to the lm. These results are at complete agreement with previously published work on the effect of the substrate temperature on the microstructure of reactively sputter-deposited
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10000 Al2O 3 304L 1000
Amorphous 'peak'
Counts
100
111 200
10
220
20
40
60
80
FIGURE 4.4: XRD spectra of Al2O3 on 304L, and uncoated 304L substrate.
alumina lms. In particular, no -Al2O3 or -Al2O3 was detected at substrate temperatures below 330C [zywi96]. The microcrystalline lms, especially the thermodynamically stable -Al2O3 form, have very low thermal conductivity, high wear resistance, high hardness, and excellent acid resistance. However, they require substrate temperatures above 1000C, thereby excluding stainless and tool steels as possible substrates. There is an ongoing effort to produce microcrystalline alumina lms at lower substrate temperatures (500-700C), using high-power (26W/cm2) pulse magnetron reactive sputtering [schi93].
4.2.2 Sensor lms

The sensor lms are expected to have the characteristic columnar structure of lms which are sputter-deposited at low substrate temperatures (Tsub/Tm<0.3 for the nickel based alloys). A limiting factor for the grain size is the very small thickness of the lms (~600nm).
4.2.3 Protective layers

The grain size of the protective layers depends solely on the method of deposition. The sputter-deposited 2m-thick seed copper layer has a ne-grain
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structure, while the electroplated nickel layer has grains in the order of 30-50m. The two optical micrographs in Figure 4.5 attempt to show the dramatic difference between the two layers.
FIGURE 4.5: Grain sizes in sputtered and electroplated copper layers.
The electroplated layer develops a distinctive elongated grain texture through its thickness. An example of the texture can be seen in Figure 4.6.
FIGURE 4.6: Copper grains in electroplated layer.
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4.3 Electrical measurements

The electrical characteristics of the thin-lm components in the embedded structure offer a measure for the effectiveness of these components as dielectric layers or sensor devices. The measured quantities will be compared with the bulk values as well as published thin-lm data.
4.3.1 Dielectric strength of dielectric layers

The successful deposition of adequately insulating aluminum oxide lms on stainless steel substrate has been the most difcult step throughout the development of the technology outlined in the Fabrication chapter. A large number of sensors deposited on the Al2O3 layers was exhibiting a very small resistance to the substrate. Since the compositional measurements ruled out the possibility of non-stoichiometric aluminum oxide as the cause of the low resistance paths, our attention was turned to pinholes. Pinholes were a severe problem in the IC industry in the 60s and 70s and this pronlem was only resolved by enforcing strict particle control in the fabrication facilities. The concept of clean rooms is the result of that strategy. Pinholes are thought to be caused by particles which are electrostatically attached to the substrate and are incompletely covered by a blanket layer. During subsequent processing (e.g.: rinsing) those particles might be removed, leaving a tiny hole in their place. Therefore, any over-deposited layer will make contact with the original substrate, and, if that layer is conductive, the contact will lead to shorting. In order to verify the existence of pinholes two simple methods were employed. Initially, a small voltage (~5-10V) was applied between a shorted sensor and the stainless steel substrate. After the application of the voltage, the sensor was rendered insulated from the substrate, the resistance between them becoming higher that 20M. This method is referred to as self-healing dielectric breakdown
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[kern73]. The surface of the sensor was then examined by an optical microscope to reveal any damage.Figure 4.7 shows an optical micrograph of the region were a crater was created at a pinhole site. As the voltage is applied across the constantan/304L contact in the pinhole, a high current has to pass through a small volume of material and generates a large amount of heat which explosively evaporates the surrounding materials. This action eliminates the short-circuit between the conducting layer and the metallic substrate which was caused by the pinhole. It has to be noted that 5-10V could cause no dielectric breakdown between a well insulated conducting lm and the substrate, with a dielectric lm of the usual 3-4m thickness.
FIGURE 4.7: Optical micrograph of damage caused by self-healing dielectric breakdown.
A direct observation of pinholes was possible with the large depth-of-eld of an SEM. An image of two pinholes, and possibly a speck of dust which is semiburied in the sputter-deposited Al2O3 layer is shown in Figure 4.8. below. In order to develop a measure of the dielectric strength of the deposited aluminum oxide lms, metal conductors (aluminum and constantan) were deposited on a 3m-thick oxide which was sputter-deposited on polished
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FIGURE 4.8: SEM image of Al2O3 lm with pinholes.
stainless steel substrate. The conductors were photolithographically shaped in 200m squares. The thickness of the dielectric was measured by a step prolometer. Then, using a dc power supply, a voltage was applied between the conducting patches and the substrate with the aid of copper electrodes. The voltage varied continuously from 5 to 32V. In all cases, the dielectric broke down at 301V, thereby exhibiting a dielectric strength of ~10V/m, which is near the low end of the reported values [chen97]. Yet, that value was adequate for the purposes of this work. It is expected that microcrystalline aluminum oxide, and especially the stable -phase, would show higher dielectric strength values [drr84].
4.3.2 Resistivity of sensor materials

The resistivity of the sensor lms was measured with a standard 4-point probe station. In its simplest incarnation the probe consists of four equidistant tips which are pressed on to the lm surface. The four tips lie on a straight line and the outer two supply a known constant current I while the inner two measure voltage V. As long as the lm thickness is a lot smaller that the distance between the tips the sheet resistance RS (in /")of the lm can be calculated by Eq.(4.1)
85
[smit95].The resistivity of the material is given by multiplying the sheet resistance with the thickness of the lm. V - --R S = ------ln 2 I (4.1)
We prepared three lms, one for each of the three sensor materials, and present the results along with data from the literature inTable 4.4.
TABLE 4.4: Resistivity and thickness of alumel, chromel, and constantan lms.
Material Alumel Chromel Constantan
Published (.nm) 260a 594a 490b
Measured (.nm) 440 819 840
Thickness (nm) 630 630 1050
a. Measured for wires with 50.8m diameter [alda84]. b. Bulk value at 25C [crc85].
The considerably higher resistivity of the deposited lms (70% higher than the reported bulk values for alumel and constantan) can be explained by the nature of the lms grown by sputtering at low homologous temperatures. Indeed, all the experimental sensors were deposited without any thermal activation of the substrate so that the surface mobility of the physisorbed species on the substrate was rather low. In such a case, the resulting microstructure is strongly microcrystalline and at best columnar, in which case the largest dimension of the grains is equal to the lm thickness (a few hundred nm in our case). The small grain size results in a large number of grain boundaries which act as scattering centers for the electrons and therefore increase resistivity.
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4.4 Strain-gage characterization

The investigation of a strain-gage response to applied loads is of central importance to the characterization of the embedded system. It is true that a sensor mounted on the surface of a component will bear higher strains than in any other position, therefore we chose to test the strain gages in their most vulnerable state. This method would also be revealing for the mechanical integrity of the dielectric lms under strain.
4.4.1 Experimental setup

The simplest conguration for such a test is the four-point bend test (4PBT) of a beam with a strain gage deposited on its surface. This setup allows an exact comparison of the strain gage output with a calibrated commercial gage and beam-theory calculations as well. The latter comparison is possible because the bending moment is constant between the two inner pins (cf. Figure 4.9), and therefore the resulting outer-ber strain is constant in the same region. The beam substrate was of a rectangular cross-section and its dimensions are given in Table 4.5.
TABLE 4.5: Dimensions and moment of inertia for beam substrate.
Length (10-3 m) 50
Width (10-3 m) 23.4
Height (10-3 m) 2.96
Moment of inertia (10-12 m4) 50.55
The substrate was cut out from a 304L stainless steel plate. The nominal Youngs modulus and yield strength for this material are 193GPa and 170MPa [asm94] respectively, at room temperature. Following the procedures described in Substrate preparation on page 28, a 3m-thick aluminum oxide layer was sputter-deposited on the polished surface of the substrate. No shadow mask was used and the layer covered the surface in
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its entirety. Then, a strain gage was deposited from a constantan target according to the processes described in Sensor layer on page 53. Its longest dimension, along the longest substrate dimension, was 8mm and the line-width was 75m. The strain-gage resistance was measured equal to 225 . A calibrated constantan gage was attached next to the experimental one. The commercial gage was a thin-lm sensor deposited on a polyimide foil carrier. This carrier was bonded to the aluminum oxide lm on the substrate surface by means of a fast curing adhesion agent. The commercial gage resistance was 120 . Both strain gages were connected to bridge circuits prior to the mounting of the substrate on the 4PBT apparatus. Connections to the sensor leads were made by using regular solder. The commercial gage was connected to a specialized strain indicator box (Model P-3500 from the Measurements Group) with the ability to provide both a digital readout of the strain as measured by the gage and an output signal to be processed by external Data Acquisition Systems (DAqS). The experimental gage was connected to a bridge circuit which was built in the laboratory and was controlled by the testing equipment. The testing equipment was manufactured by MTS and could be equipped with a 2240N load cell. The accompanying control electronics could be used to operate the system in displacement-control or load-control mode. The substrate was mounted on a 4PBT rig in such a way that, when load was applied, the sensors would be in tension. The dimensional details of the setup are depicted in Figure 4.9. Also, the substrate had to be fully insulated from the testing equipment. In order to achieve this, the back surface (upper side in Figure 4.9) was covered by Kapton tape and all wire connections were wrapped with insulating tape. Inadequate electrical insulation would often result in erratic sensor behavior, especially for sensors that featured a nite (~1M) shunt resistance to the substrate.
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Strain gages
10 mm
20 mm 40 mm
FIGURE 4.9: Dimension details of the 4-point bend test setup.
Data processing was facilitated by a PC equipped with data acquisition equipment controlled by a LabView application. The 4 voltage signals read by the DAqS were generated by the applied load from the load cell, the cross-head displacement from the ram, the bridge circuit with the experimental sensor, and the bridge circuit with the commercial sensor, as amplied by the strain indicator box. Finally, a common ground was used for all testing and control equipment.
4.4.2 Experimental objective and results

Clearly, one of the most important requirements for a strain sensor is the absence of any hysteresis effects when the tested structure is experiencing elastic strains only. Furthermore, for the particular implementation of our design it is important that the aluminum oxide lms that encapsulate the sensor are not strained to fracture while the substrate is still behaving elastically. These two requirements, no history effects and no carrier failure in the elastic regime of the metal matrix, dictated the form of the load curves that were imposed on the tested substrate.
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All experiments were performed in the displacement-control mode so that timedependent localized deformation could be easily detected, and extended yielding could be prevented. In the load-control mode the machine moves the ramp until the pre-dened load level is achieved. Apparently, if the applied load causes the stress to exceed the yield limit, the resulting deformation will be rather extensive. During the experiments the ram displacement was increased or decreased until a pre-dened load level was reached. The system was kept at that displacement for a short period of time (one or two minutes) and then the displacement was readjusted so that the next load level would be reached. Elastic regime In the initial experiments the maximum applied stress was kept below the nominal yield strength of the stainless steel substrate (170 MPa). In Figure 4.10 we present the stress at the outer bers of the test sample during the 4PBT, as calculated by beam theory based on the applied load, and the voltage output of the bridge that contained the experimental deposited sensor. Both quantities are plotted against time.
250 Experimental gage 200
-10 -15
Experimental gage output (Volts)
Outer fiber stress (MPa)
150
-5
100 stress (MPa) 50
200
400
600
800
1000
10
Time (s)
FIGURE 4.10: Outer ber stress and of deposited strain gage output from 4-point bend test. Test run in displacement control mode. Strain gage in tension. 10% of total data shown for clarity.
90
The form of the loading and unloading curve permits the comparison of the gage output for load levels of the same magnitude which were reached in different manners (i.e. after increasing and after decreasing the load). This comparison for loads resulting to stresses of ~25, ~50, ~80, and ~100 MPa, shows that the gage output levels remain constant irrespective of the loading history. This is a rst evidence that, in the purely elastic regime, there are no history effects in the behavior of the deposited sensor. It can also be observed that while the displacement was kept at a constant level, the load (and the resulting stress and strain at the outer bers) would relax with time, even though the maximum stress was below the yield strength of the material. This time-dependent behavior was attributed to the local deformation of the polymer tape that had been attached to the back of the substrate (top surface in Figure 4.9), as the hardened-steel pins would cause the underlying tape to ow. A supporting argument for this conclusion is the much smaller scale of the effect when the displacement has been reduced from a higher value (cf. Figure 4.11.b), rather than increased from a lower one (cf. Figure 4.11.a).
(a)
-20 Displacement 85
(b)
-20 Displacement 85
Displacement (x10 m)
80 -15 75
Displacement (x10 m)
80 -15 75 Stress
Stress -10 480 520 560 70 600
-10 720
740
760
70 780
Time (s)
Time (s)
FIGURE 4.11: Displacement and calculated outer ber stress as functions of time. a) Measurement after displacement (absolute value) increase, b) Measurement after displacement (absolute value) reduction. The time scale is the same as in Figure 4.10. 10% of total data shown for clarity.
91
However, the litmus test for the correct functionality of the experimental gage is the direct comparison of its output with that of the calibrated commercial strain sensor. The graphs in Figure 4.12 depict the experimental gage output as a function of the commercial gage reading, and the output of both sensors as functions of the calculated outer ber strain. The latter was obtained by applying beam-theory calculations to the sample, using the measured load values as input.
(a)
Outer fiber stress (MPa) -10
0 50 100 150
(b)
800
800
(x10 ) = a + b * V
-6
-8 -6 -4 -2 0 0
Nominal strain (x10-6 )
Experimental gage 600
-6 Nominal strain (x10 )
600
a b
Value -9.315 -69.065
Error 0.28121 0.050369
400 Calibrated gage 200 Nominal fracture strain for aluminum oxide 200 400 600 0 800
400
200
0 0.0
-2.5
-5.0
-7.5
-10.0
Calculated strain (x10-6)
FIGURE 4.12: a) Experimental gage output and nominal strain vs. calculated strain and stress. b) Nominal strain vs. experimental gage output. Nominal strain as measured by calibrated gage. All other values from Figure 4.10. 10% of total data shown for clarity.
From Figure 4.12.a it is understood that the experimental gage output is perfectly linear with the applied load and the calculated resulting stress and strain. Moreover, there is no visible history effect even though the loading was far from monotonic (cf. Figure 4.10). The spread of strain values measured by the calibrated gage at a particular stress level is attributed to both the resolutionlimited method of acquisition and the electrical noise generated during the amplication and transport of the signal.
92
Another interesting conclusion from the rst graph is the agreement between the calibrated gage readout and the calculated strain values. The linear t of the calibrated gage output values is given by:
fit
calibr
= 8.98 10
+ 0.98 calc
(4.2)
The intercept is exceedingly small in absolute numbers and one to two orders of magnitude smaller than the elastic strains measured on the sample (50-600). Also, the slope of the curve is very close to unity, even though the elastic modulus value used in the calculations was taken from the literature. This agreement provides condence in the validity of the theory-based calculations. Furthermore, the relation of linearity between the measured and calculated values is solid evidence that the proportional elastic limit was not exceeded during this portion of the 4PBT, as the calculated values were based on linear elasticity theory. The second graph (Figure 4.12.b) provides a calibration curve for the deposited strain sensor, for the particular signal acquisition and amplication system. This curve is also a linear t where the relation between the measured voltage and the corresponding strain is given by: calibr = 9.31 10
6
69.07 10
(4.3)
whereas the voltage output range is 0-(-10)Volts. The maximum uncertainty in Eq.(4.3) (as expressed by the combined errors for the intercept and the slope coefcient) is realized at very small signals (<-0.1V) and can be as large as 1.8-3%. At high output values (~-10V) the error can be as small as ~0.11%. The sources of this uncertainty are again the electrical noise generated by the strain indicator device that was attached to the calibrated gage, and the low resolution of the acquisition equipment.
93
Inelastic regime In the second set of experiments, the sample was subjected to loads that resulted in an outer ber stress greater than the nominal yield stress (170MPa) of 304L stainless steel. All equipment remained the same except for the data acquisition card attached to the bridge containing the experimental gage. The previous acquisition system reached its maximum output during loading in the elastic regime and was replaced by a card with lower amplication. In Figure 4.13.a we present the voltage output of the bridge with experimental gage and the calculated outer ber stress as functions of time. In graph (b) of the same gure we present the nominal strain as measured by the calibrated strain sensor.
(a)
500 Experimental gage
-4
(b)
500 Nominal strain 1400
-6 Calibrated gage (x10 )
Outer fiber stress (Mpa)
400
-3
400 700 300 0
300
-2
200
-1
200
100 stress (Mpa) 0 1200 1400 1600
100 stress (Mpa) 1200 1400 1600
-700
Time (s)
Time (s)
FIGURE 4.13: a) Calculated outer ber stress and output of deposited strain gage. b) Calculated outer ber stress and strain measured by calibrated strain gage. From 4-point bend test in displacement control mode. Strain gages in tension. Inelastic regime.
The dashed lines in the graphs have been included to emphasize the fact that while the applied stress returns to the same level, the strain (as measured by both sensors) does not. Such behavior is strong evidence of plastic deformation. A better visualization of the permanent deformation can be given by the stressstrain curves based on the data enclosed in the rectangles in Figure 4.13. In the two graphs of Figure 4.14 the outer ber stress is plotted against the output of the strain gages. The direction of loading is indicated by different
94
markers and the stress values lower than the yield strength of the substrate (170MPa) are linearly t.
(a)
inc
(b)
=a+b*V -142.01 -114.53
150
Increasing load Decreasing load "Plastic" load
200
a b
inc
=a+b* -4.2549 0.20066
200
a b
150 Increasing load Decreasing load 100
100
"Plastic" load
dec
dec
=a+b*V -161.53 -114.07
a b
=a+b* -21.69 0.19757
50 -1.5 -2.0 -2.5 -3.0 -3.5
50 300 600 900
a b
1200
-6
Nominal strain (x10 )
FIGURE 4.14: a) Outer ber stress vs. experimental gage output. b) Outer ber stress vs. nominal strain. Linear t parameters for elastic stress values (<170MPa). Data from Figure 4.13 (within rectangles).
Both strain gages register a permanent strain, roughly equal to 0.01% (as measured by the calibrated sensor). Also, the loading and unloading curves have almost identical slope coefcients (within 0.4% for the experimental sensor and within 1.5% for the calibrated sensor). Since the slope coefcient is the apparent elastic modulus of the system this agreement further enhances the credibility of the results. The data corresponding to the rst loading-unloading sequence in Figure 4.13 were not included in the calculation of the slope coefcients due to the presence of a small history effect. During that sequence, the maximum applied stress is just below (~165MPa) the nominal yield strength of the stainless steel substrate. It is noted that during testing in the elastic regime the outer ber stress did not exceed 135MPa and no history effects were observed.
95
A closer look at the response of the sensors prior to the subjection of the substrate to plastic loads is attempted in Figure 4.16. For reference, the actual loading history is shown in Figure 4.15 with identiers for the segments of interest.
800
-4
Experimental gage 600
-3
-2
400
-1
200
1
Stress 0 1100 1200 1300 1400 1500 1600

2
Time (s)
FIGURE 4.15: Maximum stress and experimental gage response prior to plastic deformation. Data from Figure 4.13.a, during elastic loading and unloading (segments
, , ).
180 160
(a)
) = a + b * V
180
(b)
) = a + b *
) = a + b * V
a b
-122.96 -107.79
160 140 120 100 80 60
a b a b a b
5.1923 0.18978 -4.1686 0.19931 -4.2525 0.20066
140 120 100 80 60 40

-1.6
) = a + b *
a b
-143.85 -115.35
) = a + b * V
a b
-142.03 -114.53
) = a + b *
-1.8
-2.0
-2.2
-2.4
-2.6
-2.8
40 200
300
400
500
600
700
800
900
Experimental gage
Nominal strain
FIGURE 4.16: a) Stress-strain curves for the experimental sensor. b) Stress-strain curves for the commercial sensor. All data from segments , , and in Figure 4.15. Notice that segment is the increasing load segment in Figure 4.14
96
Again, the calibrated sensor response is juxtaposed to that of the deposited strain gage in order to show that the history effect detected by the latter is not an artifact of the sensor. This history effect manifests itself not so much as a permanent strain after a premature plastic deformation, as a change in the apparent stiffness of the system (4.8-5.4% as indicated by the calibrated sensor). Since it was observed that higher loads, which did result in plastic deformation, did not alter the systems elastic response, it can be assumed that the particular change in Figure 4.16 was due to a re-alignment effect which was triggered by the particular load. Finally, in analogy to the elastic regime case, we can attempt a calibration of the sensor with respect to the acquisition system used in this case with the higher loads. Indeed, tting the nominal strain, as measured by the calibrated sensor, to the output of the deposited strain gage yields a straight line (see Figure 4.17) which is described by: calibr = 680.27 10
6
567.66 10
(4.4)
1400 1200
Nominal strain (x10 )
-6
1000 800 600

(x10 ) = a + b * V
-6
400 200 0 -1.0

a b R
Value -680.27 -567.66 0.9987
Error 0.90623 0.39461 NA
-1.5
-2.0
-2.5
-3.0
-3.5
FIGURE 4.17: Nominal strain vs. deposited sensor output. Calibration curve based on all data from Figure 4.13. 10% of total data shown for clarity.
97
The voltage output range from the bridge containing the experimental sensor is 0-(-10) Volts. It must be noted that the signal data from the two sensors remain in very good agreement through the elastic and plastic sections of the experiment, but the intercept is quite large (-680.27) and corresponds to a compressive strain. The explanation of this discrepancy lies with the lack of data from the deposited gage with the lower amplication system near the zero-load region, before the onset of plastic deformation in the substrate.
4.5 Summary
In this chapter the measurements regarding the chemical composition of the dielectric and sensor lms, as well as resistivity measurements for the latter were presented. Also, the experimental results from 4-Point Bend Tests (4PBT) of a deposited sensor are included and commented in their correlation with stress and strain values acquired with calibrated media. The aluminum oxide dielectric lms were found to be almost perfectly stoichiometric (O/Al=1.4990.005) when measured by the more accurate Electron Micro-Probe, and slightly aluminum rich when measured by X-ray Photoelectron Spectroscopy (XPS). XPS measurements revealed a dependence of the composition on the oxidation degree of the aluminum target during reactive sputtering. In particular, high oxygen ows that bring the target to the fully poisoned state will result in compositions closer to the stoichiometry, at the expense of the deposition rate. The measured resistivity of the deposited sensor lms was signicantly (up to 70%) higher than the bulk values reported in the literature. This deviation was attributed to the increased electron scattering from the proliferation of grain boundaries in thin lms which were sputter-deposited at room temperature.
98
A 304L stainless steel substrate was subjected to two tests in the 4-Point Bend geometry. We deposited a constantan strain sensor on the surface where tensile stress would be observed, and next to it we attached a calibrated strain gage. In the rst test the stress at the outer bers of the substrate did not exceed the nominal yield strength of the 304L stainless steel. The response of both sensors was linear with respect to the stress and strain values that were obtained from beam theory calculations. The measured dimensions of the substrate as well as the load values from the testing equipment were used in the stress calculations. The calculated strain was obtained using a nominal elastic modulus for stainless steel. The correlation between measured outputs and calculated values was very good. The ratio between the calibrated strain gage values and the calculated strain was 0.98. By plotting the calibrated gage output against the voltage measured by a bridge circuit which contained the deposited sensor, we were able to obtain a linear calibration curve for the experimental sensor. The curve is specic to the amplication system attached to the experimental gage. In the next 4PBT the applied loads were raised in order to cause stresses that would exceed the yield stress of the substrate. Plastic deformation was registered by both sensors upon unloading. The stress-strain slopes of the loading and unloading curves (corresponding to elastic applied stresses) were equal to within 0.4% and 1.5% for the experimental and the commercial gage respectively. The resulting permanent strain was ~0.01% as measured by the calibrated gage. Finally, throughout both the elastic and plastic stages of the second test the correlation between the commercial and the experimental gage remained very good, thus enabling the calculation of new calibration curve for the experimental sensor. The linear curve was specic to the low-resolution signal amplication system used in this test.
99
Modeling
The subject of this chapter is the effort to model the embedding process employing a nite element analysis software package (Abaqus). The rst goal of this model is to predict the temperature at the copper/stainless steel interface by simulating the heat transfer during the laser deposition process. The primary purpose is to predict the optimum thickness of the protective layers in order to minimize their deposition time while still adequately shielding the thin lms from the high temperatures produced during embedding. Ultimately, a rened model can be used to predict the mechanical behavior of the substrate during and after the laser deposition process.
5.1 Model Description

5.1.1 Geometry
The model attempts to replicate the geometry and the dimensions of the actual substrate, the protective, and the embedding layers. For simplicity the model is comprised of 4 strata. The rst stratum is the stainless steel substrate and is a 50x50x3mm rectangular slab. The second stratum contains the protective copper layer as well as parts of the nickel layer and the powder bed. The third stratum contains the rest of the nickel layer (whatever is deposited on top of the copper
100
CHAPTER 5: MODELING
layer) and part of the powder bed, while the fourth stratum contains only powder. Each of strata 2-4 have a thickness of 1mm and their origins are offset by 20mm from the origin of the rst stratum, along the Y-axis, in order to account for the part of the stainless steel surface that is left uncovered to provide access to the sensor leads. The structure is depicted in Figure 5.1 on page 102. Mesh Selection Since the main goal was to calculate the temperature at the interface between the copper and the stainless steel layer, a high nodal density along the Z-axis was deemed necessary. The nodal densities along the two principal axes in the horizontal plane were selected in order to facilitate the simulation of the moving laser beam. The diameter of the laser beam spot on the part is 2.5mm with a cross-sectional area of 4.91mm2. The initial nodal densities along the three axes are mentioned in Table 5.1. The particular values lead to the construction of brick-like, 3D elements with a top face area equal to 5mm2 (2mm x 2.5mm). This value is only 1.8% larger than the actual cross-sectional area of the laser beam spot. This approximation allows the assignment of a maximum heat input value to an element face which results into a heat ux equal to the actual value imparted by the laser beam. The immediate benet is the simplication of the simulation of the moving heat source. Unfortunately, the elements that are generated by the mesh according to Table 5.1 are quite attened, and the result is a non-physical uctuation of the temperature at certain nodes during the heat transfer calculations. The uctuations usually prompted the analysis to be aborted. In order to determine the cause of the problem two simple models were built (each with 4 strata of equal dimensions), using a single material for each stratum to avoid geometry effects. The rst model used the nodal densities in Table 5.1.
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CHAPTER 5: MODELING
30 mm
30 mm
Invar
45 mm 24 mm Invar 30 mm
Nickel
50 mm 40 mm Invar 30 mm Nickel Copper 20 mm 50 mm
Invar powder 50 mm
304L stainless steel
55 mm
FIGURE 5.1: Materials and dimensions of the 4 strata in the geometric model.
102
CHAPTER 5: MODELING
TABLE 5.1: Nodal density along the three axes. Initial model.
X-axis Nodal density (nodes/mm) 0.4
Y-axis 0.5
Z-axis 2
The second model used values increased by 5-fold along the horizontal axes. In this model the horizontal dimensions were reduced by a factor of ve so that the elements were nearly cubic, but the heat ux remained at the same level. The behavior of the second model showed no evidence of temperature uctuations and its analysis completed succesffuly. Therefore, it was deduced that the densication of the mesh would be necessary for the successful completion of the analysis In order to retain a relatively small number of nodes and the approximation of the laser beam spot with a superset of element faces, the mesh was densied by increasing 2-fold the horizontal nodal densities (Table 5.2).
TABLE 5.2: Nodal density along the three axes. Final model.
X-axis Nodal density (nodes/mm) 0.8
Y-axis 1
Z-axis 2
This quadrupled the total number of nodes in the model to 21,443, without including the nodes in the surrounding material which provides for more realistic boundary conditions (cf. Boundary and initial conditions on page 107, and Invar powder regions in Figure 5.1). At the same time, the elements at the top-most layer were grouped in element sets. Each new element set consists of four 1mm x 1.25mm elements which share an edge along the Z-axis, and has a top surface area of 5mm2. Therefore, it is identical in size to the elements produced by the mesh in Table 5.1
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CHAPTER 5: MODELING
Simplications This simple model does not take into account the thin-lm multilayer which is located between the stainless steel substrate and the copper protective layer. The multilayer consists of a 10-20nm titanium adhesion layer, two 3-4 m-thick aluminum oxide lms and a second 10-20nm titanium adhesion layer (on top of which a copper seed layer is sputter-deposited in order to permit the growth of the copper protective layer by electroplating), thus its total thickness is roughly 6-8m. The sensor circuit which is enclosed in the dielectric envelope has a very small area compared to the envelope itself (6-7%) and its thermal properties do not affect signicantly the thermal behavior of the multilayer.
5.1.2 Material Properties

Calculation of the temperature prole in a heat transfer problem requires the knowledge of the thermal properties for all the materials involved. In the actual object the constituent materials are: solid 304L stainless steel, solid copper, solid nickel, invar (Fe-36Ni) in both solid and powder form, and nally the titanium and aluminum oxide thin lms. As explained before, the thin lms are not included in this heat transfer calculation. The thermal properties required by the FE model include specic heat, thermal conductivity, latent heat, and liquidus and solidus temperatures. Finally, the density of each material is also required. The arithmetic values for the aforementioned properties are reported in Table 5.3. Latent Heat The inclusion of the latent heat effect in the analysis makes the problem nonlinear and requires the use of rst-order 3D elements [hks97]. Such elements have 8 nodes and 6 faces instead of the 20 nodes and 6 faces in second-order elements. In rst-order elements the temperature is linearly interpolated between adjacent nodes.
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CHAPTER 5: MODELING
TABLE 5.3: Density and thermal properties of materials in the FE model.
Material 304L Copper Nickel Invar a. b. c. d. e. f.
Density (kgm-3) 7900a 8933b 8900b 8000c
Specic heat (JK-1) 477a 385b 444b 515d
Thermal conductivity (Wm-1 K-1) 14.9a 401b 90.7b 11
Latent heat (JK-1)
Solidus/ Liquidus (C)
282290e
1440/1450f
Room temperature [frad93]. Room temperature [incr90]. Full theoretical density. Room temperature [toul70]. Interpolated value from Fe and Ni data [crc85], for 64Fe-36Ni. [asm73]
Simplications In reality, invar is rst deposited in powder form and its volume is gradually solidied as the laser beams scans the surface. The solidication results in a density increase, accompanied by an increase in the apparent thermal conductivity, which cannot be modeled with the tools available. The reason is that the model properties cannot be altered in real time while maintaining the temperature values achieved by the preceding analysis steps. Therefore, the density and the thermal conductivity of the invar layers have to be dened at constant values throughout the whole analysis. Since it is rather difcult to estimate the apparent thermal conductivity of the powder, and the densication to full density is instant upon the melting caused by the laser beam, it was deemed both practical and realistic to assume a fully solid invar layer, which is, in effect, being remelted by the laser beam. The disadvantage of this assumption is the incorrect calculation of the lateral heat conduction in the plane of the invar layer. Furthermore, all thermal properties were considered as temperature independent, which does not reect reality accurately. In particular, the thermal
105
CHAPTER 5: MODELING
conductivity of copper decreases with increasing temperature, while its specic heat increases. Invar and nickel, as magnetic materials, exhibit a non-monotonic variation of their thermal conductivities and specic heats in the vicinity of their Curie temperatures (invar: TC=279C; nickel: TC=358C). As temperature decreases from the melting point (or solidus), thermal conductivity and specic heat values decrease for both materials. Thermal conductivity exhibits a cuspshaped minimum at the Curie temperature, while specic heat reaches a minimum above TC and then rises to a discontinuity at the magnetic transition temperature. Below TC both properties decrease in a monotonic fashion [toul70]. Also, the specic heat at room temperature is lower than that at high temperatures for all materials. The opposite is true for the thermal conductivity with the exception of invar, whose thermal conductivity increases with temperature, at least up to 540C [toul70].
5.1.3 Simulation of a moving heat source

The actual laser beam is scanning the part surface with a speed pre-dened in the LabView code [Sample LabView le on page 125] that controls the robotic arm which carries the end of the optical ber connected to the lasing cavity [Embedding Layers on page 65]. By quantizing the powder surface in 2x2.5mm rectangles we can modulate the heat ux input in the model in a way so that a moving heat source is simulated. This technique is outlined below. Lets assume a strip of the powder bed along the X-axis of length a and width b. The strip is exactly divided in m element sets, each one of length a and width b, so that a=ma. Lets also assume that the spot size of the beam is axb and the speed of the laser beam along the same axis is ua. All these quantities are depicted in Figure 5.2
106
CHAPTER 5: MODELING
ua element set 1 laser spot at t=t1
element set 2
a element set m b
FIGURE 5.2: Quantization of the powder bed in elements, top view.
In fact, the laser is already on when its spot gradually enters the powder bed, therefore, some heat will be input to the element during a time interval of 2a/ua (see also Figure 5.3). The power ux to an element increases linearly from zero to maximum (where the spot coincides with the element) during the rst half of that interval and then decreases to zero during the second half, as the laser beam moves to the adjacent element. Due to the adjacency condition, the heat ux increases in the second element while it decreases in the previous one, but the total heat ux remains constant as in the actual experiment. Also, due to this overlap the total time during which power is input to the strip is (m+1)a/ua. Therefore, selecting the top face size of the element set to be equal to the spot size of the laser beam allows a simulation of the moving heat ux as it becomes possible to prescribe a time-varying heat ux to a face of an element set and address the overlapping heat input intervals through a universal timing system. The heat ux for each of the rst two element sets in Figure 5.2 as well as the total ux are shown in Figure 5.3.
5.1.4 Boundary and initial conditions

It may be helpful to note at this point that, in the context of embedding, the notion of the substrate includes the stainless steel base and the two protective layers. During the actual embedding process the substrate is pre-heated by contact with a copper slab sitting on hot plate (cf. page 67). The equilibrium temperature of the copper piece is ~350C. Our assumption is that the
107
CHAPTER 5: MODELING
heat flux element set 1 heat flux element set 2 heat flux all element sets 0 t1 2a ------ua a ( m + 1 ) ---ua t
t t
FIGURE 5.3: Heat ux for element sets 1 and 2 in Figure 5.2 and total heat ux.
temperature at the bottom face of the substrate remains constant and equal to 350C during the embedding process, the copper-hot plate system effectively being a heat sink. Furthermore, the entire substrate and the powder bed are assumed to have an initial temperature equal to 320C. The top surface of the powder bed (considered as fully dense solid in the model) as well as the uncovered surface of the substrate are all considered thermally insulated, except for the portion of the powder bed where heat ux is imparted from the top. The heat ux value is calculated by dividing the laser power as measured at the exit of the laser source with the cross-sectional area of the laser beam. The latter has been measured equal to 4.91mm2. In all embedding experiments the output power of the laser was equal to ~1.8kW, and therefore the heat ux was ~360MWm-2. Allowing for a reectivity coefcient equal to 0.1, the value used in the calculations was 330MWm-2. Even though invar has a very high reectivity in the infrared, the surface of the powder bed is very rough and inhomogenous, thus, a low reectivity coefcient was chosen. Prior to embedding, the deposited powder bed extends around the substrate in order to provide lateral support to the powder placed on top of the nickel layer.
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CHAPTER 5: MODELING
This surrounding mass of invar powder has been included in the model as a wall with a height equal to 6mm and thickness equal to 2.5mm. The nodes that reside on the outer boundary of the wall (Invar powder in Figure 5.1 on page 102) are assumed at contact with an innite heat reservoir held at a constant temperature of 320C. The thermal properties of the invar powder are taken from Table 5.3, with two exceptions: the density is assumed to be 50% of the theoretical value (i.e.: 4000kgm-3), and the latent heat is assumed to be zero in order to simplify calculations. Simplications Film (convection) cooling effects or radiation effects are not taken into account. The simulation of convective cooling is beyond the scope of this simple model as it would require the experimental determination of the convective lm coefcients for the stainless steel and the solidied invar layer. In reality, convective cooling is enhanced by the ow of dry nitrogen towards the substrate. The nitrogen is introduced to minimize oxidation of the powders and the surfaces, but provides non-uniform cooling as it is injected by a permeable shroud which is attached to the robotic arm that moves the laser over the substrate. Radiation effects are not taken into consideration as they become important only at very high temperatures. The total net radiation ux emanating from an object at an absolute temperature T can be calculated by the Stefan-Boltzmann law [hks97]:
4 4 W (T ) = T (T 0)
(5.1)
where is the emissivity of the object (with a value in the 0-1 range, 1 being the emissivity of a black body), is the Stefan-Boltzmann constant, equal to 56.70nWm-2 K-4 [crc99], and T0 is the ambient temperature.
109
CHAPTER 5: MODELING
The emissivity of invar near its solidus temperature (1440C) is close to 0.33 [wahl52]. As the output power ux of the laser used in the embedding process is ~360MWm-2, we realize from Eq.(5.1) that the temperature necessary for radiation uxes equal to 5% of the incident power ux is above 5200C. This is well above the vaporization temperatures of both iron (2861C) and nickel (2913C) [crc85], and it can be assumed that only an exceedingly small amount of the illuminated mass is evaporated.
5.2 Results
An actual heat transfer calculation involves a single pass of the laser beam across the substrate, which is completed in 3.5s, and a natural cooling of the substrate for another 16.5s (3.5s less than the 20s cooling time used in reality). The calculation is completed in 77 hours with the software running on a 333MHz UltraSPARC-IIi system. The complete heat transfer calculation for the 11 laser passes would scale accordingly in time and data-space, and it was not attempted due to practical limitations. The rst priority was to check the calculated results with previously recorded experimental data. The latter, in Figure 5.4, were obtained with a type-K thermocouple connected to a Data Acquisition system, polling the sensor at a frequency of 10Hz. The thermocouple was held in contact with the nickel layer surface while the laser was scanning the invar powder bed. The calculated values correspond to the temperature of a node in the nickel-invar interface, positioned at the same location with the thermocouple in the embedding experiment. The simulated laser beam was also moved with the speed used in the experiment (15mm/s). It can be seen that the calculation describes adequately well the process. However, there are four points that deserve closer attention. First, the calculation
110
CHAPTER 5: MODELING
1400 1200
Experim. Calculated
Temperature (C)
1000 800 600 400 200 0 85 90 95 100
Time (s)
FIGURE 5.4: Experimental and calculated temperature at a point on the Ni-invar interface.
predicts a lower heating rate than the experiment. This can be attributed to the fact that in reality the invar layer is initially in powder form and therefore exhibits an apparent thermal conductivity much lower than the bulk value which was used in the calculations. Next, the calculated cooling rate is higher than the observed one. This disagreement is most likely caused by the variation of the material properties with temperature. As mentioned in page 106, the specic heat values at high temperatures are larger than the room-temperature values used in the calculations, and therefore the actual cooling rate could have been overestimated. The temperature values which lie below the measured initial steady state temperature of ~350C can be ignore as they were caused by temporary loss of contact with the substrate. During the deposition of subsequent invar layers the thermocouple was fused to the substrate and no such cooling effects were observed. Finally, the calculations overestimate the temperature at the end of the cooling cycle by as much as 20C. A possible explanation for this is the disregard of the cooling effect imparted by the nitrogen ow.
111
CHAPTER 5: MODELING
Another concern regarding the validity of the model was the maximum temperature at the invar-nickel interface. As experiments have shown, the interface is completely remelted (cf. Figure 3.16 on page 69), which leads to the conclusion that the nickel is heated at least to its melting point (1453C). Temperature calculations for the nodes at the interface, along the center-line of the laser path and at a path offset by 1mm from the center-line, have produced the data in Figure 5.5.
1500
Nickel m.p.
1400 1300
max
1200 1100 1000 900
offset=1mm offset=0
10
20
30
40
50
X (mm)
FIGURE 5.5: Calculated maximum temperatures at the Ni-invar interface. Values from points directly below the laser path and at 1mm offset.
It can be seen that the nodes directly under the laser path generally reach the melting temperature, with some exceptions near the material interfaces as those are reproduced by the model (Figure 5.1). Furthermore, the nodes that are slightly offset reach a maximum temperature below the melting point, especially when they are located directly over the copper layer. For nodes close to the layer interfaces the situation is even more acute. The most obvious explanation lies with the fact that some of these nodes lie at a larger depth from the surface than those, for example, in the central 20-30mm region. A concern for the actual embedding process is the maximum temperature that is reached by the stainless steel substrate during laser deposition. The reason for
112
CHAPTER 5: MODELING
this concern is dual. First, the thin-lm structure lies at the copper-steel interface and it should not be exposed at high temperatures so that thermal mismatch strains are minimized or steep temperature gradients so that thermal shock is avoided. Second, the stainless steel should not be treated for long times at elevated temperatures (>700C), so that precipitation of chromium at the grain boundaries, and the subsequent loss of corrosion resistance are avoided
900
offset=0
800
offset=2mm
Temperature (C)
700 600 500 400 300
1.5
2.5
3.5
4.5
Time (s)
FIGURE 5.6: Calculated temperature at the steel-copper interface. Values from a point which lies directly below the laser path.
The calculated data shown in Figure 5.6, imply that the heating rate reaches a maximum of 100Cs-1, and the 700C threshold is crossed for a very short time (in the order of ~0.5s) and for the region directly below the laser beam only. The experimental results have proven that the thin-lm structure and the enclosed sensor survive the heat exposure. If the results in Figure 5.4 can provide any condence to the validity of the simulation, then it can be inferred that the predicted temperatures and heating rates are indeed close to reality.
113
CHAPTER 5: MODELING
5.3 Summary
This chapter included the description and the results of a nite element analysis model which was used to calculate temperature proles at points of interest in the multilayer structure containing the thin-lm sensors. It was attempted to create a model that would represent the geometry of the actual substrate prior and during the embedding process and that would also simulate the moving heat source of the Nd:YAG laser used in the processing. The mesh density was adjusted so as to minimize non-physical temperature uctuations and allow the completion of one laser pass at a smaller-than-100h time-frame. Simplicity of calculations dictated the use of temperature-independent material properties, and the exclusion of convective and radiation cooling effects. The boundary conditions imposed were dened by the heat input of the laser on part of the surface, the contact with a heat sink at the bottom of the substrate, and the contact with a volume of powder (itself in contact with a heat sink) at the sides of the substrate. All other surfaces were considered insulated. The temperature prole of a point at the nickel-invar interface was calculated and the results were compared with experimental data. The qualitative agreement was satisfactory, and the discrepancies between calculation and experiment could be accounted for by the simplifying assumptions of the model. The calculations also predicted that there is remelting at the invar-nickel interface (as observed experimentally), and that the maximum temperature at the coppersteel interface does not exceed 700C for more than 0.5s. These results provide condence that the model can offer insight for the effect of the protective layers thickness on the maximum temperature at the copper-steel interface. Furthermore, a more rened model in terms of material properties and mesh density can be used to provide more accurate data. Use of this models results to perform a stress analysis on the structure based on thermal expansion coefcients
114
CHAPTER 5: MODELING
and elastic moduli is currently limited by the time and space necessary to complete the calculations.
115
Conclusions
The research described in the previous chapters focuses on the development of a technology that allows the inclusion of thermo-mechanical sensors in the body of metallic structures (tools, components, mechanisms). The inspiration for this work came from the need to monitor the temperature and deformation of structures in real time, in demanding environments (manufacturing, drilling, combustion, etc.) As a response to the push for automation in manufacturing, the main processes used were borrowed from elds with signicant progress towards this goal. In particular, the sensors and part of the necessary enclosure were deposited with thin-lm techniques, already widely used in the IC and coatings industries. The structures were built using Shape Deposition Manufacturing (SDM) in conjunction with Laser Deposition. SDM is a methodology that automates the design and manufacturing of geometrically complex objects using additive and subtractive techniques, whereas Laser Deposition is a process used to incrementally fabricate metal objects with a high quality of properties. Even though attempts to monitor temperature and strain with thin lm sensors were carried out in the past, mainly in turbomachinery facilities, certain things were achieved for the rst time, at the proof-of-concept level, during this research.
116
CHAPTER 6: CONCLUSIONS
Namely, it became possible to deposit pinhole-free dielectric layers on nonspecial commonly available substrates (e.g.: 304L stainless steel) with minimal preparation, relative to the prior practice, and, most importantly, outside a clean room environment. This accomplishment is generating hope that thin-lm deposition and shaping techniques could be integrated in a traditional manufacturing environment without the elevated costs of maintaining particlefree areas. The deposited strain sensors were tested in a four-point bend conguration and their response was perfectly linear in the elastic regime. The output of the experimental strain gage was also compared to that of a commercially available, calibrated sensor, which was loaded under the same conditions. The comparison provided a calibration for the deposited sensor and veried its linear response, and, most importantly, the absence of hysteresis a crucial feature for a strain sensor. In addition, the dielectric layers were grown directly on the substrates, without treating coatings that form thermally grown oxides, and with deposition rates signicantly higher (~10 times) than those achieved by more expensive techniques (i.e.: rf sputtering). In particular, all aluminum oxide lms were deposited using pulsed magnetron reactive sputtering, with maximum rates close to 0.8nms-1 at a power density of ~12Wcm-2. The lms were amorphous, since they were deposited on cool substrates (~100C), yet their dielectric strength was within the range of reported values for aluminum oxide. Most importantly, the sensors, after being enclosed in an insulating envelope, were embedded in a metallic structure using high-temperature techniques (i.e.: Laser Deposition). Since the particular technique creates a molten pool on a metal powder bed it was essential to protect the sensitive thin-lm structure during the process. This was achieved with a combination of protective layers which were
117
electroplated on the substrate and partially buried the sensor and its insulation. The protective layers were composed of copper and nickel. Finally, a nite element model was created in order to simulate the embedding process and thereby to provide insight and predictive capability with respect to the geometry of the protective layers (size and thickness) and the parameters of the laser (speed, pattern, power). The results of the model, which were compared with experimental temperature measurements and structure observations, proved encouraging for the applicability of the simulation not only for the embedding of sensors, but for the general additive process as well. At the current state there are a number of obstacles that still have to be overcome so that a fully functional tool or component can be manufactured and put in service. One of the most apparent is the shaping of the thin lms over curved surfaces, such as those produced by 5-axis machining. This feature will be vital in order to locate the contact pads for the sensors in a position far from the area that will engage in a harsh environment. Another very important issue is that of splicing and telemetry. For most cases it will be necessary to connect the sensor to an external signal processing device. This will have to happen at the contact pads, therefore the connections must be strong, reliable, and stable under high temperatures and probably embedded in a protective layer themselves. Advances in telemetry will allow the transfer of the signal to remote locations without the need for extensive wiring of some sort. In the extreme case where a rough signal processing circuit is fabricated and embedded inside the tooling, the results of such processing will still have to be communicated to remote systems. On another front, the act of embedding a structure inside another one exacerbates the issues already faced by many layered manufacturing techniques. Not only is there the problem of residual thermal stresses which affect the integrity of the structure, there is an extra discontinuity as well. This
118
discontinuity might act as a stress concentration, thus affecting the fatigue limit of the component or tool. Since inserted structure will generally be very thin, it will be a favorable site for crack initiation in an already non-continuous structure. Some of the problems outlined above can be remedied by using other type of sensors in order to measure thermo-mechanical response. Currently, at the Rapid Prototyping Laboratory there is active research in the area of embedding opticalber sensors in layered manufactured tools. Such sensors have the distinctive advantage of non-contact signal transfer as can be accessed by optical means. More importantly, they have no need for electrical insulation as their mode of operation is based on optical properties, and therefore they are more robust in terms of functionality. However, their placement cannot be easily automated or parallelized.
119
The thin-lm deposition system
Our thin lm deposition system consists of a stainless steel cylindrical chamber of 62 l capacity (diam:46cm, height:38cm), with two K.J. Lesker 1-KW magnetron guns. The chamber is evacuated with a Leybold TMP361 turbomolecular pump with a nominal maximum pumping speed of 400 l/s (for nitrogen) and capable of achieving an ultimate pressure of less than 1E-8 Pa. The turbomolecular pump is backed by an Alcatel Pascal 2021 mechanical pump with a pumping speed of 69 l/s and capable of achieving an ultimate pressure of less than 0.2 Pa. The mechanical pump is also used to pump the chamber down to a rough vacuum of 30 Pa before the gate valve to the turbomolecular pump is opened. It is suggested that the pressure at the foreline of the turbo pump remain in the 0.1-1 Pa range and never exceed 50 Pa. Moreover, it is strongly advised to avoid a very low pressure either at the foreline or the gate to the mechanical pump since this might lead to oil backstreaming from the mechanical pump. Oil backstreaming becomes a severe problem in the transition ow regime which is characterized by Knudsen numbers in the 0.01-1 range. The Knudsen number Kn=l/L, is the ratio of the mean free path l of a gas molecule to a characteristic distance L of the vacuum system. Therefore, for the foreline and roughing lines of our system, with a diameter of 3 cm, the mean free path should always be less than 0.03 cm to ensure that the lines are in the uid ow regime. The mean free path (in cm) for room temperatures is roughly inversely proportional to the gas
120
APPENDIX A
pressure (in Pa) [D. Smith], hence a pressure of at least 33 Pa is required at those lines before they are valved off. This is easy to achieve for the roughing line to the main chamber but difcult to maintain at the foreline during long pumpdown procedures. In such cases the injection (purge) of argon or nitrogen at the foreline is suggested so that the pressure stays within desired limits. We have not implemented such measures as of this writing. A recirculating water chiller is used to provide cool water (21 C) to the magnetron guns and the turbo pump. The guns should operate at a maximum temperature of 25 C and should be cooled with water owing at 1.9 l/min. The pump should operate in the 10-30 C range and the minimum suggested ow is 0.3 l/m. Our Tek-Temp TKD-100 chiller is capable of pumping 6.5 l/min at 550 KPa with a cooling capacity of 2 KW. Currently it operates at 300-350 KPa. The magnetron guns face upwards and accept disk-shaped targets which are 3 mm thick and 50 mm in diameter. The targets are clamped mechanically on the copper backing plate which is cooled by recirculating water and the plasma is conned on top of them with the aid of titanium ground shields. The guns are driven by an ENI RPG-50 5 KW power supply which can deliver a dc or pulsed dc signal at a preset level of power, voltage or current. The frequency of the pulsed dc signal can be varied between 50 and 250 KHz with a pulse width in the 400-3000 ns range, depending on the operating frequency. The principle of operation for the pulsed dc mode is outlined in a separate appendix [or chapter?]. The working gases are introduced into the chamber via a mass ow control system by MKS. The ow rate for argon and oxygen is adjusted by two mass ow controllers that have been calibrated for the particular gases. The pressure at the controller inlet is maintained at approximately 700 KPa with a gas regulator. The working pressure is measured with a MKS 127A Baratron capacitance manometer with a dynamic range of 1E5 and an accuracy of 1.33E-4 Pa. It is
121
APPENDIX A
suggested that the Baratron sensor is valved off during venting to avoid exposure to higher pressures and that its zero offset is corrected before every deposition. Before such a correction it is suggested that the Baratron remain at a pressure that is 2 orders of magnitude below its precision limit for 4-6 hours. The zero offset can be adjusted either mechanically with a set screw at the back of the sensor or digitally by the mass ow control system. The base pressure is measured by a Bayard-Alpert ionization gage (G100F by K.J. Lesker). This gage has an upper working pressure limit of 0.13 Pa and its emission current must always be switched off when pressure gets near this value. It is advisable that the gage is degassed for a few minutes before measuring the base pressure. The degassing procedure is most effective when it is performed during a bakeout and can only be initiated if the pressure is already below 1.3E-3 Pa. High pressures, mainly during venting and roughing procedures, are measured by a thermocouple pressure sensor. Such a sensor is also used to monitor the pressure at the foreline of the turbomolecular pump. Those sensors have a sensitivity low limit of 0.13 Pa. The chamber can be baked to accelerate the desorption of water molecules from the internal surfaces with the aid of 627 W heating tape that is wrapped around it. The chamber walls are also wrapped with aluminum foil to reduce the heat being lost by re-radiation to the environment. The heating tape is attached to a temperature control system but even when it is driven at full capacity, the internal surface temperature does not exceed 85 C. With a 10-hour bake-out followed by cooling for another 10-12 hours the turbomolecular pump can achieve pressures as low as 4E-5 Pa. This is quite good for a system that has 20 ports sealed with small O-rings and also a large O-ring that seals the top plate itself. Out of the 13 through-holes on the baseplate, 2 are used for the power feedthroughs to the magnetron guns, 1 for a type-K thermocouple feedthrough, 1 for a power feedthrough to the substrate holder, and 1 for a rotational feedthrough to the mechanical shutter. There is also one O-ringed seal for the push-pull transport feedthrough for the substrate holder.
122
APPENDIX A
The substrate holder is a construction of two parallel stainless steel plates which are connected with teon spacers and nylon screws to ensure electrical isolation. The bottom plate has a number of threaded holes so that substrates can be fastened to it. It is placed on an aluminum rack system, isolated from it by teon sliders, and can be translated from one gun to another with the aid of the aforementioned push-pull transport mechanism. The latter is attached to the top plate which serves also as a ground shield during sputter-etching of the substrates. The substrate holder is driven by the ENI power supply via a shielded copper wire during sputter-etching and is at a oating potential during deposition.
123
Positive masks of strain sensors
50 75 125 100
420 330
FIGURE B.1: The numbers denote the smallest linewidth in m.
124
Sample LabView le
The le below controls the laser and the robotic arm that carries it during the embedding process:
1 13 2 0 135 0.00 0.00 0.00 14 0.00 0.00 0.00 0.0 0.0 0.0 12 0 -35 0.0 0.0 20 11 10000 19 8 17 0 0 0 18 1 0 0 21 3 20 1 2 0 29 0.0 0.0 15 2 0 29 0.0 0.0 15 20 0 12 0 29 0.0 0.0 15 11 20000 17 0 0 0 12 17.9 35 0.0 0.0 15 11 3000 20 1 2 17.9 -36 0.0 0.0 15 2 17.9 -36 0.0 0.0 15 17 0 0 0 20 0 12 17.9 -36 0.0 0.0 15 11 20000 12 1.8 -24 0.0 0.0 15 11 1000 20 1 2 1.8 24 0.0 0.0 15 2 1.8 24 0.0 0.0 15 20 0
; ; ; ; ; ; ; ; ;
set's part center relative to pallet tool offset send and execute move wait on Labview side set laser power (10=full power) set current powder feeder rates (10=max.) turn on ALL powder feeders to be used wait on ADEPT side (during moves) open shutter
; PASS 1
; PASS 2
; PASS 3
125
APPENDIX C
12 1.8 24 0.0 0.0 15 11 20000 12 3.6 24 0.0 0.0 15 11 1000 20 1 2 3.6 -24 0.0 0.0 15 2 3.6 -24 0.0 0.0 15 20 0 12 3.6 -24 0.0 0.0 15 11 20000 12 5.4 -24 0.0 0.0 50 11 1000 20 1 2 5.4 24 0.0 0.0 15 2 5.4 24 0.0 0.0 15 20 0 12 5.4 24 0.0 0.0 15 11 20000 12 7.2 24 0.0 0.0 15 11 1000 20 1 2 7.2 -24 0.0 0.0 15 2 7.2 -24 0.0 0.0 15 20 0 12 7.2 -24 0.0 0.0 15 11 20000 12 9 -24 0.0 0.0 50 11 1000 20 1 2 9 24 0.0 0.0 15 2 9 24 0.0 0.0 15 20 0 12 9 24 0.0 0.0 15 11 20000 12 10.8 24 0.0 0.0 15 11 1000 20 1 2 10.8 -24 0.0 0.0 20 2 10.8 -24 0.0 0.0 20 20 0 12 10.8 -24 0.0 0.0 20 11 20000 12 12.6 -24 0.0 0.0 20 11 1000 20 1 2 12.6 24 0.0 0.0 20 2 12.6 24 0.0 0.0 20 20 0 12 12.6 24 0.0 0.0 20 11 20000 12 14.4 24 0.0 0.0 20 11 1000 20 1
; PASS 4
; PASS 5
; PASS 6
; PASS 7
; PASS 8
; PASS 9
126
APPENDIX C
2 14.4 -24 0.0 0.0 25 2 16.2 -24 0.0 0.0 25 2 16.2 24 0.0 0.0 25 2 16.2 24 0.0 0.0 25 19 0 20 0 12 16.2 25 0 0 25 11 2000 0
; PASS 10 ; PASS 11
127
ABAQUS heat transfer input le
This le is used to build the model described in Modeling on page 100 and simulate the embedding process.
*HEADING Heat transfer analysis for sample with 304L base (50x50x3) copper, nickel and invar layers TRANSIENT HEAT TRANSFER UNITS: SI (m,kg,s,K) ** ** ** APEX DEFINITION FOR SOLID MODEL (7 mm HIGH) ** *NODE 999,0,0,0 1043,.055,0,0 3499,0,.050,0 3543,.055,.050,0 42999,0,0,.007 43043,.055,0,.007 45499,0,.050,.007 45543,.055,.050,.007 ** ** ** ** NODE GENERATION FOR 304L + COPPER + NICKEL + INVAR ** ** 44 INTERVALS ALONG X ** ** X-EDGE AT 0,0-50,0 (Z=0) ** *NGEN, NSET=XEDGE1 999,1043,1 ** ** X-EDGE AT 0,50-50,50 (Z=0)
128
APPENDIX D
** *NGEN, NSET=XEDGE2 3499,3543,1 ** ** X-EDGE AT 0,0-50,0 (Z=7) ** *NGEN, NSET=XEDGE3 42999,43043,1 ** ** X-EDGE AT 0,50-50,50 (Z=7) ** *NGEN, NSET=XEDGE4 45499,45543,1 ** ** ** 50 INTERVALS ALONG Y ** ** BASE (Z=0) ** *NFILL, NSET=BASE XEDGE1,XEDGE2,50,50 ** ** TOP ** *NFILL, NSET=TOP (Z=7) XEDGE3,XEDGE4,50,50 ** ** ** BODY OF SUBSTRATE+LAYERS ** *NFILL, NSET=NALL BASE,TOP,14,3000 ** ** ** ** ** BOUNDARY DEFINITION *NSET,NSET=OUTBOUND,GENERATE 3999,6499,50 6999,9499,50 9999,12499,50 12999,15499,50 15999,18499,50 18999,21499,50 21999,24499,50 24999,27499,50 27999,30499,50 30999,33499,50 33999,36499,50 36999,39499,50 6499,6543 9499,9543 12499,12543
129
APPENDIX D
15499,15543 18499,18543 21499,21543 24499,24543 27499,27543 30499,30543 33499,33543 36499,36543 39499,39543 4043,6543,50 7043,9543,50 10043,12543,50 13043,15543,50 16043,18543,50 19043,21543,50 22043,24543,50 25043,27543,50 28043,30543,50 31043,33543,50 34043,36543,50 37043,39543,50 ** ** ** ** ** ELEMENT DEFINITION FOR 304L ** *ELEMENT, TYPE=DC3D8 1001,1001,1002,1052,1051,4001,4002,4052,4051 ** ** ELEMENT GENERATION FOR 304L (6 LAYERS, EACH 500 MICRONS THICK) ** *ELGEN, ELSET=ESTEEL 1001,40,1,1,50,50,50,6,3000,3000 ** ** ** ELEMENT DEFINTIION FOR 2ND LAYER ** *ELEMENT, TYPE=DC3D8 20001,20001,20002,20052,20051,23001,23002,23052,23051 ** ** ** ELEMENT GENERATION FOR 2nd LAYER ** *ELGEN 20001,40,1,1,30,50,50,2,3000,3000 ** ** ** ** ELEMENT SET GENERATION FOR COPPER IN 2ND LAYER ** *ELSET, ELSET=ECOPPER, GENERATE 20013,20028
130
APPENDIX D
20063,20078 20113,20128 20163,20178 20213,20228 20263,20278 20313,20328 20363,20378 20413,20428 20463,20478 20513,20528 20563,20578 20613,20628 20663,20678 20713,20728 20763,20778 20813,20828 20863,20878 20913,20928 20963,20978 23013,23028 23063,23078 23113,23128 23163,23178 23213,23228 23263,23278 23313,23328 23363,23378 23413,23428 23463,23478 23513,23528 23563,23578 23613,23628 23663,23678 23713,23728 23763,23778 23813,23828 23863,23878 23913,23928 23963,23978 ** ** ** ** ELEMENT SET GENERATION FOR NICKEL IN 2ND LAYER ** *ELSET, ELSET=ENICKEL2, GENERATE 20005,21455,50 20006,21456,50 20007,21457,50 20008,21458,50 20009,21459,50 20010,21460,50 20011,21461,50 20012,21462,50
131
APPENDIX D
20029,21479,50 20030,21480,50 20031,21481,50 20032,21482,50 20033,21483,50 20034,21484,50 20035,21485,50 20036,21486,50 21013,21028 21063,21078 21113,21128 21163,21178 21213,21228 21263,21278 21313,21328 21363,21378 21413,21428 21463,21478 23005,24455,50 23006,24456,50 23007,24457,50 23008,24458,50 23009,24459,50 23010,24460,50 23011,24461,50 23012,24462,50 23029,24479,50 23030,24480,50 23031,24481,50 23032,24482,50 23033,24483,50 23034,24484,50 23035,24485,50 23036,24486,50 24013,24028 24063,24078 24113,24128 24163,24178 24213,24228 24263,24278 24313,24328 24363,24378 24413,24428 24463,24478 ** ** ** ** ELEMENT SET GENERATION FOR INVAR IN 2ND LAYER ** *ELSET, ELSET=EINVAR2, GENERATE 20001,21451,50 20002,21452,50 20003,21453,50
132
APPENDIX D
20004,21454,50 20037,21487,50 20038,21488,50 20039,21489,50 20040,21490,50 23001,24451,50 23002,24452,50 23003,24453,50 23004,24454,50 23037,24487,50 23038,24488,50 23039,24489,50 23040,24490,50 ** ** ** ** ** ELEMENT DEFINITION FOR 3RD LAYER ** *ELEMENT, TYPE=DC3D8 26003,26003,26004,26054,26053,29003,29004,29054,29053 ** ** ** ELEMENT GENERATION FOR 3rd LAYER ** *ELGEN 26003,36,1,1,30,50,50,2,3000,3000 ** ** ** ** ** ELEMENT SET GENERATION FOR NICKEL IN 3RD LAYER ** *ELSET, ELSET=ENICKEL3, GENERATE 26011,26030 26061,26080 26111,26130 26161,26180 26211,26230 26261,26280 26311,26330 26361,26380 26411,26430 26461,26480 26511,26530 26561,26580 26611,26630 26661,26680 26711,26730 26761,26780 26811,26830 26861,26880 26911,26930
133
APPENDIX D
26961,26980 27011,27030 27061,27080 27111,27130 27161,27180 27211,27230 27261,27280 27311,27330 27361,27380 27411,27430 27461,27480 29011,29030 29061,29080 29111,29130 29161,29180 29211,29230 29261,29280 29311,29330 29361,29380 29411,29430 29461,29480 29511,29530 29561,29580 29611,29630 29661,29680 29711,29730 29761,29780 29811,29830 29861,29880 29911,29930 29961,29980 30011,30030 30061,30080 30111,30130 30161,30180 30211,30230 30261,30280 30311,30330 30361,30380 30411,30430 30461,30480 ** ** ** ** ELEMENT SET GENERATION FOR INVAR IN 3RD LAYER ** *ELSET,ELSET=EINVAR3, GENERATE 26003,27453,50 26004,27454,50 26005,27455,50 26006,27456,50 26007,27457,50 26008,27458,50
134
APPENDIX D
26009,27459,50 26010,27460,50 26031,27481,50 26032,27482,50 26033,27483,50 26034,27484,50 26035,27485,50 26036,27486,50 26037,27487,50 26038,27488,50 29003,30453,50 29004,30454,50 29005,30455,50 29006,30456,50 29007,30457,50 29008,30458,50 29009,30459,50 29010,30460,50 29031,30481,50 29032,30482,50 29033,30483,50 29034,30484,50 29035,30485,50 29036,30486,50 29037,30487,50 29038,30488,50 ** ** ** ** ELEMENT DEFINITION FOR 4TH LAYER (INVAR ONLY) ** *ELEMENT, TYPE=DC3D8 38009,32009,32010,32060,32059,35009,35010,35060,35059 ** ** ** ELEMENT GENERATION FOR INVAR IN 4TH LAYER (2 layers 500 microns each) ** *ELGEN, ELSET=EINVAR4 38009,24,1,1,30,50,50,2,3000,3000 ** ** ** ELEMENT DEFINITION FOR OUTER-LEFT LAYER (POWDER ONLY) ** *ELEMENT, TYPE=DC3D8 999,999,1000,1050,1049,3999,4000,4050,4049 ** ** ** ELEMENT GENERATION FOR POWDER IN 4TH LAYER (2 layers 500 microns each) ** *ELGEN, ELSET=OUT1 999,2,1,1,50,50,50,12,3000,3000 ** **
135
APPENDIX D
** ELEMENT DEFINITION FOR OUTER-RIGHT LAYER (POWDER ONLY) ** *ELEMENT, TYPE=DC3D8 1041,1041,1042,1092,1091,4041,4042,4092,4091 ** ** ** ELEMENT GENERATION FOR POWDER IN 4TH LAYER (2 layers 500 microns each) ** *ELGEN, ELSET=OUT2 1041,2,1,1,50,50,50,12,3000,3000 ** ** ** ** ELEMENT SET GENERATION FOR NICKEL AND POWDER ** *ELSET, ELSET=ENICKEL ENICKEL2,ENICKEL3 ** *ELSET, ELSET=EINVAR EINVAR2,EINVAR3,EINVAR4 ** ** *ELSET, ELSET=EPOWDER OUT1,OUT2 ** ** ** ** MATERIAL PROPERTIES ETC. ** ** ** *PHYSICAL CONSTANTS, ABSOLUTE ZERO=-273.15 ** ** *SOLID SECTION, MATERIAL=304L,ELSET=ESTEEL *MATERIAL, NAME=304L *CONDUCTIVITY 14.9 *DENSITY 7900 *SPECIFIC HEAT 477 ** ** *SOLID SECTION, MATERIAL=COPPER, ELSET=ECOPPER *MATERIAL, NAME=COPPER *CONDUCTIVITY 401 *DENSITY 8933 *SPECIFIC HEAT 385 **
136
APPENDIX D
** *SOLID SECTION, MATERIAL=NICKEL, ELSET=ENICKEL *MATERIAL, NAME=NICKEL *CONDUCTIVITY 90.7 *DENSITY 8900 *SPECIFIC HEAT 444 ** ** ** ** INVAR (SOLID) ** *SOLID SECTION, MATERIAL=INVARSOL, ELSET=EINVAR *MATERIAL, NAME=INVARSOL ** ** *CONDUCTIVITY 11 ** DENSITY DEFINED AS 100% OF THEORETICAL *DENSITY 8000 ** SPECIFIC HEAT FROM ** ASM METALS HANDBOOK, Low-Expansion alloys *SPECIFIC HEAT 515 ** LATENT HEAT IS THE ARITHMETIC MEAN FOR 64FE-36NI *LATENT HEAT 282290,1440,1450 ** ** ** ** INVAR (POWDER) ** *SOLID SECTION, MATERIAL=INVARPDR, ELSET=EPOWDER *MATERIAL, NAME=INVARPDR ** ** *CONDUCTIVITY 11 ** DENSITY DEFINED AS 50% OF THEORETICAL *DENSITY 4000 *SPECIFIC HEAT 515 ** ** ** ** INITIAL CONDITIONS *INITIAL CONDITION, TYPE=TEMPERATURE NALL,320 **
137
APPENDIX D
** ** AMPLITUDE DEFINITIONS ** ** LASER SPEED = 15 mm/sec ** *AMPLITUDE, NAME=E1, TIME=STEP TIME 0,0,0.167,1,0.333,0 *AMPLITUDE, NAME=E2, TIME=STEP TIME 0.167,0,0.333,1,0.5,0 *AMPLITUDE, NAME=E3, TIME=STEP TIME 0.333,0,0.5,1,0.667,0 *AMPLITUDE, NAME=E4, TIME=STEP TIME 0.5,0,0.667,1,0.834,0 *AMPLITUDE, NAME=E5, TIME=STEP TIME 0.667,0,0.834,1,1.,0 *AMPLITUDE, NAME=E6, TIME=STEP TIME 0.834,0,1.,1,1.167,0 *AMPLITUDE, NAME=E7, TIME=STEP TIME 1.,0,1.167,1,1.333,0 *AMPLITUDE, NAME=E8, TIME=STEP TIME 1.167,0,1.333,1,1.5,0 *AMPLITUDE, NAME=E9, TIME=STEP TIME 1.333,0,1.5,1,1.667,0 *AMPLITUDE, NAME=E10, TIME=STEP TIME 1.5,0,1.667,1,1.834,0 *AMPLITUDE, NAME=E11, TIME=STEP TIME 1.667,0,1.834,1,2.,0 *AMPLITUDE, NAME=E12, TIME=STEP TIME 1.834,0,2.,1,2.167,0 *AMPLITUDE, NAME=E13, TIME=STEP TIME 2.,0,2.167,1,2.333,0 *AMPLITUDE, NAME=E14, TIME=STEP TIME 2.167,0,2.333,1,2.5,0 *AMPLITUDE, NAME=E15, TIME=STEP TIME 2.333,0,2.5,1,2.667,0 *AMPLITUDE, NAME=E16, TIME=STEP TIME 2.5,0,2.667,1,2.834,0 *AMPLITUDE, NAME=E17, TIME=STEP TIME 2.667,0,2.834,1,3.,0 *AMPLITUDE, NAME=E18, TIME=STEP TIME 2.834,0,3.,1,3.167,0 *AMPLITUDE, NAME=E19, TIME=STEP TIME 3.,0,3.167,1,3.333,0 *AMPLITUDE, NAME=E20, TIME=STEP TIME 3.167,0,3.333,1,3.5,0 ** ** ** ** DEFINITION OF ELEMENT SETS ** FOUR ELEMENTS MAKE UP AN ELEMENT SET WITH SIZE 2X2.5 mm ** ** *ELSET,ELSET=S101421
138
APPENDIX D
23451,23452 23401,23402 *ELSET,ELSET=S101422 29453,29454 29403,29404 *ELSET,ELSET=S101423 29455,29456 29405,29406 *ELSET,ELSET=S101424 29457,29458 29407,29408 *ELSET,ELSET=S101425 41459,41460 41409,41410 *ELSET,ELSET=S101426 41461,41462 41411,41412 *ELSET,ELSET=S101427 41463,41464 41413,41414 *ELSET,ELSET=S101428 41465,41466 41415,41416 *ELSET,ELSET=S101429 41467,41468 41417,41418 *ELSET,ELSET=S101430 41469,41470 41419,41420 *ELSET,ELSET=S101431 41471,41472 41421,41422 *ELSET,ELSET=S101432 41473,41474 41423,41424 *ELSET,ELSET=S101433 41475,41476 41425,41426 *ELSET,ELSET=S101434 41477,41478 41427,41428 *ELSET,ELSET=S101435 41479,41480 41429,41430 *ELSET,ELSET=S101436 41481,41482 41431,41432 *ELSET,ELSET=S101437 29483,29484 29433,29434 *ELSET,ELSET=S101438 29485,29486 29435,29436
139
APPENDIX D
*ELSET,ELSET=S101439 29487,29488 29437,29438 *ELSET,ELSET=S101440 23489,23490 23439,23440 ** ** ** ** ** OUTPUT DEFINITIONS ** *PREPRINT, MODEL=NO,HISTORY=NO *RESTART,WRITE,OVERLAY ** ** ** ** STEP DEFINITIONS ** ** ** STEP 2 ** *STEP, INC=2000 *HEAT TRANSFER,END=PERIOD,DELTMX=1500 .002,20,.00001 ** ** ** BOUNDARY CONDITION FOR BASE (T=350 CELSIUS) ** BOUNDARY CONDITION FOR OUTER INVAR POWDER (T=320 CELSIUS) ** *BOUNDARY BASE,11,,350 OUTBOUND,11,,320 ** ** ** ** *DFLUX,AMPLITUDE=E1 S101440,S2,3.3E8 *DFLUX,AMPLITUDE=E2 S101439,S2,3.3E8 *DFLUX,AMPLITUDE=E3 S101438,S2,3.3E8 *DFLUX,AMPLITUDE=E4 S101437,S2,3.3E8 *DFLUX,AMPLITUDE=E5 S101436,S2,3.3E8 *DFLUX,AMPLITUDE=E6 S101435,S2,3.3E8 *DFLUX,AMPLITUDE=E7 S101434,S2,3.3E8 *DFLUX,AMPLITUDE=E8 S101433,S2,3.3E8
140
APPENDIX D
*DFLUX,AMPLITUDE=E9 S101432,S2,3.3E8 *DFLUX,AMPLITUDE=E10 S101431,S2,3.3E8 *DFLUX,AMPLITUDE=E11 S101430,S2,3.3E8 *DFLUX,AMPLITUDE=E12 S101429,S2,3.3E8 *DFLUX,AMPLITUDE=E13 S101428,S2,3.3E8 *DFLUX,AMPLITUDE=E14 S101427,S2,3.3E8 *DFLUX,AMPLITUDE=E15 S101426,S2,3.3E8 *DFLUX,AMPLITUDE=E16 S101425,S2,3.3E8 *DFLUX,AMPLITUDE=E17 S101424,S2,3.3E8 *DFLUX,AMPLITUDE=E18 S101423,S2,3.3E8 *DFLUX,AMPLITUDE=E19 S101422,S2,3.3E8 *DFLUX,AMPLITUDE=E20 S101421,S2,3.3E8 ** ** ** *NODE FILE NT *END STEP
141
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THIN-FILM THERMO-MECHANICAL SENSORS EMBEDDED IN METALLIC STRUCTURES

Anastasios Golnas December 1999

Copyright by Anastasios Golnas 2000 All Rights Reserved

Friedrich B. Prinz (Principal Adviser)

1.2 Thin-lm Sensors

1.2.2 Manufacturing Issues

1.3 Basics of Sensor Physics

1.3.2 Thermocouple Sensors

2 kBT -------- -------------------------S = 6 e(E0 EF )

1.4 Deposition Processes

FIGURE 1.1: Generic hysteresis curve in a reactive sputtering system.

P(Q)=Pn(Q)-P(Q), for Q>QT, will be constant. This pressure difference

+100V time -300V

FIGURE 1.2: Asymmetric bipolar dc voltage as applied to a magnetron target.

1.4.3 Laser Assisted Deposition

1.5 Dissertation Outline

2.1 Cleanliness and Surface Quality

CHAPTER 2: PROPOSED SOLUTION

CHAPTER 2: PROPOSED SOLUTION

2.4 Thermal Protection

3.1 Substrate preparation

3.1.2 Grinding and polishing

TABLE 3.2: Sputter-etching process parameters.

<10-4 Pa 1503sccm 6.00.2Pa 100 W 201kHz/1056 ns 325-330V 600s

3.1.5 Discussion of cleaning processes

Substrate CLD CLS CLN

Carbon (at%) 23.4 21.0 28.7

Oxygen (at%) 57.3 60.5 53.0

Iron (at%) 8.1 9.5 8.2

Chromium (at%) 8.5 6.3 8.2

Etching time (s) 90 300 90 300 90 300

Oxygen (at%) 13.5 9.9 14.8 11.3 10.1 8.4

Iron (at%) 51.7 56.1 59.2 59.5 60.7 64.2

Chromium (at%) 13.8 14.3 10.1 10.2 11.2 16.1

3.2 Bottom insulation layer

Dielectric strength (kV/mm) 9.9-15.8 15-25 >200c 15.8-19.8

Thermal expansion coefcientb ( K-1) 8.0 0.3-0.4

Cost of metallic target (US $cm-3) ~12 ~20 ~40

Al2O3 SiO2 Ta2O5 Si3N4

3.2.1 Determination of transition oxygen ow

980425: fresh target

990416: old target

Voltage (increasing flow) Voltage (decreasing flow)

P = m1 + m2 * Qox m1 m2 R 0.7830 0.0137 0.9921

P = m1 + m2 * Qox m1 m2 R 0.7778 0.0137 0.9995

Oxygen Flow (sccm)

Oxygen flow (sccm)

Oxygen flow (sccm)

Target 980425 990416 N/A

Offset (Pa) 0.77780.0022 0.78300.0037 0.78560.0038

Slope (Pa/sccm) 0.01370.0002 0.01370.0005 0.01380.0004

Voltage (V) 194 164 0

TABLE 3.7: Characteristics of the voltage-ow hysteresis curves in Figure 3.1.

Vmax-Vmin (Volts) 100 77

Vinita (Volts) 286 240

Qc (sccm) 9.4 4.8

QTd (sccm) 6.6, 5.8 4.6, 3.4

Oxygen flow (sccm)

(b) 240 220 6.0 200 6.5

Transition O2 flow (sccm)

7.0 6.5 6.0 5.5 5.0 4.5

180 160 140

Error 0.5210 0.0027 NA NA

-2.2602 0.0383 0.13146 0.98545