Thin Solid Films 315 1998.

214221

Measurement of fracture toughness of ultra-thin amorphous carbon films

Xiaodong Li, Bharat Bhushan
) Computer Microtribology and Contamination Laboratory, Department of Mechanical Engineering, The Ohio State Uniersity, Columbus, OH 43210-1107, USA Received 8 May 1997; accepted 16 September 1997

Abstract The nanoindentation fracture of ultra thin amorphous carbon films on silicon by a conical indenter was studied, and compared with the nanoindentation fracture of the same films on silicon by a cube corner indenter. It is found that the conical indenter gives an indentation fracture similar to that by the cube corner indenter. The cube corner indenter results in a larger stress concentration leading to fracture of films at lower loads. Based on the analysis of the energy release in cracking, the fracture toughness of the films was calculated. The results show that the conical indenter gives the same fracture toughness values as the cube corner indenter and these calculated values are in good agreement with those measured by conventional methods. q 1998 Elsevier Science S.A.
Keywords: Fracture toughness; Nanoindentation; Energy release; Amorphous carbon films

1. Introduction The successful performance and reliability of thin films is often limited by their mechanical properties. Among the mechanical properties of interest, hardness, elastic modulus and fracture toughness are measured using indentation methods w14x. Although nanoindentation methods are used routinely in characterization of the elastic modulus and hardness of thin films, the development of measuring fracture toughness of thin films lags far behind. Conventional fracture toughness measurement is based on the radial cracking which occurs when brittle materials are indented by a sharp indenter. The length of radial cracks is known to correlate with the fracture toughness and is used to calculate fracture toughness w2,3x. However, a problem is encountered in extending the method into the nanoindentation regime in that there are well defined loads, called cracking thresholds, below which indentation cracking does not occur in most brittle materials. For a Vickers indenter which is widely used in microindentation experiments, cracking thresholds in most ceramics are about 0.25 N or more, i.e., loads well above those which would normally be used in nanoindentation. The thresholds for a Berkovich indenter routinely used in nanoindentation experiments for measuring hardness and elastic modulus. were gener)

Corresponding author.

ally found to be slightly higher. Although cracking thresholds can be reduced down to 5 mN w5x by using a cube corner indenter, the corresponding indentation depth about 250 nm for most brittle materials. exceeds 10% thickness of ultra-thin films on the order of 10 nm thickness. and the elastic-plastic zone may expand to the substrate. For these cases, conventional fracture toughness measurement based on the radial cracking cannot be used. Furthermore, at shallow indentation depths, it is difficult to measure radial crack length under scanning electron microscope SEM.. Therefore, it is necessary to find other methods to measure fracture toughness of ultra-thin films. Load-displacement studies in nanoscale indentation of films have been conducted by various researchers e.g., w4,68x.. The indentation fracture mechanics of brittle materials by Vickers and Berkovich indenters have been widely studied for many years. In an earlier study, a technique to measure fracture toughness of thin films using a cube corner indenter has been developed w9x. In the present paper, a conical indenter was used. On the basis of understanding of the nanoindentation fracture of silicon, fracture mechanisms of amorphous carbon films on silicon in nanoindentation were studied. The fracture toughness of these films was calculated using the methodology established by the cube corner indenter and compared with the fracture toughness obtained by the nanoindentation using the conical indenter.

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2. Experimental Amorphous carbon films of 400 nm thickness were deposited on polished 100. single-crystal silicon substrate rms surface roughness 23 nm. by cathodic arc and ion beam deposition techniques w8x. The kinetic energies for cathodic arc deposition and ion beam deposition are 100 2500 and 50500 eV, respectively. Nanoindentations as a function of load were made using a commercially available instrument. This instrument monitors and records the dynamic load and displacement of the indenter during indentation with a force resolution of about 75 nN and displacement resolution of about 0.1 nm w4x. A conical indenter with an included angle of 908 and a tip radius of 0.1 m m were used. In order to compare with the nanoindentation fracture of the same films on silicon by the cube corner indenter, the same indentation experiment as used in our

previous work w9x was used: approached the surface; loaded to peak load over 10 s; held the indenter at peak load for 10 s; and unloaded completely. Indentations and associated crack patterns were observed using SEM.

3. Results 3.1. Silicon The load-displacement curves of indentations made at 10, 30 and 100 mN peak indentation loads using the conical indenter and corresponding SEM micrographs of indentations on silicon are shown in Fig. 1. The load-displacement curves of indentation made at 10 and 30 mN are smooth. SEM micrographs show that at 10 mN peak indentation load no cracks are observed except the residual

Fig. 1. Load-displacement curves of indentations made at 10, 30 and 100 mN peak indentation loads using the conical indenter a. and the SEM micrographs of indentations b. on silicon. Arrow indicates discontinuity during unloading portion of the curve.

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Fig. 2. Load-displacement curves of indentations made at 20 and 30 mN peak indentation loads using conical indenter a. and the SEM micrographs of indentations b. on the ion beam carbon film on silicon. Arrow indicates a step during loading portion of the load-displacement curve.

Fig. 3. Load-displacement curves of indentations made at 20 and 22.5 mN peak indentation loads using the cube corner indenter a. and the SEM micrographs of indentations b. on the ion beam carbon film on silicon. Arrow indicate a step during loading portion of the load-displacement curve w9x.

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indent mark. At 30 mN peak indentation load, four radial cracks were generated, emanating along preferred directions. Armstrong et al. w10x observed the same phenomenon and suggested that the preferred directions are the 112: directions in silicon. The load-displacement curve of indentation made at 100 mN peak indentation load, exhibits several short displacement discontinuities during the loading step and a discontinuity in the unloading curve. In addition to the four radial cracks having propagated, the tearing of material outside the indent region and significant delamination are observed in the 100 mN SEM micrograph. This indicates that lateral cracking occurred during unloading, which is believed to be associated with the discontinuity in displacement during unloading w11x. Compared with the nanoindentations made on silicon using a cube corner indenter w9x, it is noted that at the same peak indentation load, the cube corner indenter gives higher indentation depth and exhibits much lower radial and lateral cracking threshold loads than the conical indenter. This indicates that the cube corner indenter penetrates into the material easier than the conical indenter at a given load. This suggests that cube corner indenter results in a larger stress concentration leading to the radial and lateral cracking than the conical indenter. For both indenters, however, the indentation depths at the radial cracking threshold loads exceed the 10% thickness of ultra-thin films on the order 10 nm in thickness.

3.2. Amorphous carbon films on silicon substrate The load-displacement curves of indentations made at 20 and 30 mN peak indentation loads using the conical indenter together with the SEM micrographs of indentations on the ion beam carbon film on silicon are shown in Fig. 2. The load-displacement curve of indentation made at 20 mN peak indentation load is smooth whereas that made at 30 mN peak indentation load exhibits a step in the loading curve. The 20 mN SEM micrograph shows that in addition to several radial cracks, ring-like through-thickness cracking is observed with the film around the indenter overhanging the edge of the indentation. Also we note that the film around the indenter has bulged upwards, indicating delamination and buckling. Since no steps are observed in the loading curve of indentation made at 20 mN peak indentation load, it is believed that the film under the indenter was not separated instantaneously from the bulk film via the ring-like through-thickness cracking but occurred over a period of time w9x. At 30 mN peak indentation load, partial ring-like spalling is observed around the indenter and the other parts of the film have bulged upwards as shown in Fig. 2b. This partial ring-like spalling is believed to result in the step in the loading curve. Comparison of the data obtained using the cube corner indenter shown in Fig. 3 w9x, shows a good correspondence between the step in the loading curve and morphology of ring-like through-thickness cracking and spalling.

Fig. 4. Load-displacement curves of indentations made at 30 and 350 mN peak indentation loads using conical indenter a. and the SEM micrographs of indentations b. on the cathodic arc carbon film on silicon. Arrow indicates a step during loading portion of the load-displacement curve.

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The load-displacement curves of indentations made at 30 and 350 mN indentation loads using the conical indenter together with the SEM micrographs of indentations on the cathodic arc carbon film on silicon are shown in Fig. 4. At 30 mN peak indentation load, a step is present at about 20 mN in the loading curve and correspondingly a ring-like through-thickness cracking is observed. No interface cracks are found on the indentation surface. The film around the indenter has not bulged upwards. This observation suggests that no delamination and buckling occurred. Therefore, it is believed that this step results from the ring-like through-thickness cracking and not from interfacial cracking. We note that the radius of the ring-like crack is equal to the contact radius between the indenter and the film at the indentation depth at which the step started to occur in

the loading curve. This indicates that the ring-like through-thickness cracking occurred at the contact edges. At the peak indentation loads up to 350 mN limit load of the nanoindenter., radial cracking, delamination and buckling are observed without spalling. No steps are observed in the corresponding loading curves. The four radial cracks which occurred along the preferred directions are believed to result from the silicon substrate and not from the film. The lateral cracks which formed in the silicon substrate are clearly observed, which is believed to be associated with the discontinuity in displacement in the unloading curve w11x. For the data obtained using the cube corner indenter w9x, steps are found in the loading curves of indentations made at 30, 100 and 200 mN peak indentation loads as shown by arrows in Fig. 5a. The 30 mN SEM micrograph

Fig. 5. Load-displacement curves of indentations made at 30, 100 and 200 mN peak indentation loads using the cube corner indenter a. and the SEM micrographs of indentations b. on the cathodic arc carbon film on silicon. Arrows indicate steps during loading portion of the load-displacement curve w9x.

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shows ring-like through-thickness cracking with small lips of material overhanging the edge of the indentation. The steps at about 23 mN in the loading curves of indentations made at 30 and 100 mN peak indentation loads are believed to result from this ring-like through-thickness cracking. The step at 175 mN in the loading curve of indentation made at 200 mN peak indentation load is caused by spalling, which cannot be found at the peak indentation loads up to 350 mN using the conical indenter. Comparison of Figs. 25 shows that the cube corner and conical indenters give similar nanoindentation fracture for the films used in this study. The cube corner indenter has lower critical loads for ring-like through-thickness cracking and spalling than the conical indenter. This suggests that the cube corner indenter results in a larger stress concentration leading to fracture of films at lower loads. In addition to the difference between the stress distributions caused by the cube corner and conical indenters, the edges of the cube corner indenter cut through the films during indentation, making the fracture of the films much easier than the conical indenter.
Fig. 6. Schematic of various stages in nanoindentation fracture for the filmrsubstrate system.

4. Analysis and discussion It is found from Fig. 1a that for the silicon substrate, there are not any long steps in the loading curves except several short discontinuities. The same result was obtained in the case of using the cube corner indenter w9x. This suggests that the steps in the loading curves of indentations made on the films in Figs. 25, result from the film and not from the substrate. The cube corner and conical indenter give similar indentation fracture of the films. As we established in our previous work w9x, fracture process progresses in three stages: 1. first ring-like through-thickness cracks form around the indenter by high stresses in the contact area, 2. delamination and buckling occur around contact area at the filmrsubstrate interface by high lateral pressure, 3. second ring-like through-thickness cracks and spalling are generated by high bending stresses at the edges of the buckled film, see Fig. 6. In the first stage, if the film under the indenter is separated from the bulk film via the first ring-like through-thickness cracking, a corresponding step will be present in the loading curve. If discontinuous cracks form and the film under the indenter is not separated from the remaining film, no step appears in the loading curve because the film still supports the indenter and the indenter cannot suddenly advance into the material. In the second stage, for the films used in the present study, the advances of the indenter during the radial cracking, delamination and buckling are not big enough to form steps in the loading curve because the film around the indenter still supports the indenter, but generate discontinuities which change the slope of the loading curve with increasing indentation loads. In the third stage, the

stress concentration at the end of the interfacial crack cannot be relaxed by the propagation of the interfacial crack. With an increase in indentation depth, the height of the bulged film increases. When the height reaches a critical value, the bending stresses caused by the bulged film around the indenter will result in the second ring-like through-thickness crack formation and spalling at the edge of the buckled film as shown in Fig. 6, which leads to a step in the loading curve. This is a single event and results in the separation of the part of the film around the indenter from the bulk film via cracking through films. The step in the loading curve is totally from the film cracking and not from the interfacial cracking or the substrate cracking. It is well known that the area under the load-displacement curve is the work performed by the indenter during elastic-plastic deformation of the filmrsubstrate system. The strain energy release in the firstrsecond ring-like cracking and spalling can be calculated from the corresponding steps in the loading curve. Fig. 7 shows a modeled load-displacement curve. OACD is the loading curve. DE is the unloading curve. Since the first ring-like through-thickness cracking does not always lead to a step in the loading curve in some films like the ion beam carbon film used in this study Fig. 2a and Fig. 3a., the second ring-like through-thickness crack should be considered. It should be emphasized that the edge of the buckled film is far from the indenter, therefore, it does not matter if the indentation depth exceeds the film thickness or if deformation of the substrate occurs around the indenter when we measure fracture toughness of the film from the

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Fig. 7. Schematic of a load-displacement curve, showing a step during the loading cycle and associated energy release.

released energy during the second ring-like through-thickness cracking spalling.. Suppose that the second ring-like through-thickness cracking occurs at AC. Now, let us consider the loading curve OAC. If the second ring-like through-thickness crack does not occur, it can be understood that OA will be extended to OB to reach the same displacement as OC. This means that the crack formation changes the loading curve OAB into OAC. For point B, the elastic-plastic energy stored in the filmrsubstrate system should be OBF. For point C,the elastic-plastic energy stored in the filmrsubstrate system should be OACF. Therefore, the energy difference before and after the crack generation is the area of ABC, i.e., this energy stored in ABC will be released as strain energy to create the ring-like through-thickness crack. According to the theoretical analysis in our previous work w9x, the fracture toughness of thin films can be written as K IC s

1 y n 2 . 2p C R

/ /
t

1r2

1.

where E is the elastic modulus, n is the Poissons ratio, 2p C R is the crack length in the film plane, U the strain energy difference before and after cracking, and t is the film thickness. Based on Eq. 1., the fracture toughness of both films has been calculated. U is assessed from the steps in Fig. 2a, Fig. 3a and Fig. 5a at the peak indentation loads of 30, 22.5 and 200 mN, respectively. The loading curve is

extrapolated along the tangential direction of the loading curve from the starting point of the step up to reach the same displacement as the step. The area between the extrapolated line and the step is the estimated strain energy difference before and after cracking. C R is measured from SEM micrographs in Fig. 2b, Fig. 3b and Fig. 5b. Second ring-like crack is where the spalling occurs. The calculated fracture toughness values are shown in Table 1. For the data obtained using the conical indenter, the calculated fracture toughness value for the ion beam carbon film on silicon is 5.4 MPa6m. In the case of using the cube corner indenter, the calculated fracture toughness values are 4.9 MPa6m for the ion beam carbon film on silicon and 10.9 MPa6m for the cathodic arc carbon film on silicon. The conical and cube corner indenters give very close fracture toughness values. These calculated fracture toughness values for both amorphous carbon films in this study are comparable with the fracture toughness of diamond 311 MPa6m. or diamond films 56 MPa6m. w12x and other ceramic coatings w13x measured by a well known radial crack technique. A higher deposition kinetic energy will result in a larger fraction of sp 3-bonded carbon in amorphous network w8x. The sp 3-bonded carbon exhibits the outstanding properties of diamond w8x. Thus, the higher kinetic energy for the cathodic arc deposition could be one of the possible reasons why the cathodic arc carbon film exhibits a higher fracture toughness value than the ion beam carbon film. Next, we discuss the effect of residual stresses on the fracture toughness measurement. We assume that the residual stresses are distributed uniformly in the film and the film has a homogeneous structure. In the second stage of the fracture process, the compressive stresses on the film surface and the tensile stresses on the bottom of the film produced by indentation are basically equal. Therefore, before the third stage, the elastic strain energy stored in the film produced by indentation process should not be affected by the residual stresses in the film. Since the energy release in cracking comes from the stored elastic strain energy, the fracture toughness value measured by this methodology should not be affected by the residual stresses in the films. However, the residual stresses will affect the fracture toughness of the film having a heterogeneous structure andror non-uniformly distributed residual stresses. For this kind of film, the effect of residual stresses on fracture toughness is more complex and needs further study.

Table 1 Mechanical properties of cathodic arc and ion beam carbon films Film Ion beam Ion beam Cathodic arc Indenter conical cube corner cube corner t m m. 0.4 0.4 0.4 Peak indentation load mN. 30 22.5 200 E GPa. 150 150 300

n
0.25 0.25 0.25

U nNm. 2.4 1.6 7.1

C R m m. 4.6 4.0 7.0

K IC MPa6m. 5.4 4.9 10.9

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5. Conclusions The nanoindentation fracture of amorphous carbon films by the conical indenter was studied. Good correspondence between a step in the loading curve and morphology of ring-like cracking and spalling was found. Comparison of the nanoindentation fracture of the films by the conical and cube corner indenters shows that the conical and cube corner indenters give similar fracture process. The fracture toughness of the films were calculated from the steps in the loading curves in terms of the energy release in cracking. The results show that the cathodic arc carbon film has a higher fracture toughness than the ion bean carbon film. Compared with the conical indenter, the cube corner indenter is recommended to be used for measurement of fracture toughness of hard thin films because of lower contact area, it results in lower critical load for ring-like through-thickness cracking and spalling.

References
w1x B.R. Lawn, T.R. Wilshaw, J. Mater. Sci. 10 1975. 10491081. w2x B.R. Lawn, A.G. Evans, D.B. Marshall, Elasticrplastic indentation damage in ceramics: the medianrradial crack system, J. Am. Ceram. Soc. 63 1980. 574581. w3x B.R. Lawn, Fracture of Brittle Solids, 2nd edn., Cambridge Univ. Press, Cambridge, UK, 1993. w4x B. Bhushan, Nanomechanical properties of solid surface and thin films, in: B. Bhushan Ed.., Handbook of MicrorNanotribology, CRC Press, Boca Raton, FL, 1995. w5x G.M. Pharr, D.S. Harding, W.C. Oliver, Measurement of fracture toughness in thin films and small volumes using nanoindentation methods, Mechanical Properties and Deformation Behavior of Materials having Ultra-fine Microstructures, in: M. Nastasi, D.M. Parkin, H. Gleiter Eds.., NATO ASI Series E: Applied Sciences, Vol. 233, Kluwer Academic Publishers, Dordrecht, The Netherlands, 1993, pp. 449461. w6x A.J. Whitehead, T.F. Page, Thin Solid Films 220 1992. 277283. w7x N.G. Chechenin, J. Bottiger, J.P. Krog, Thin Solid Films 261 1995. 228235. w8x B.K. Gupta, B. Bhushan, Thin Solid Films 270 1995. 391398. w9x X. Li, D. Diao, B. Bhushan, Fracture mechanisms of thin amorphous carbon films in nanoindentation, Acta Mater. 45 1997. 44534461. w10x R.W. Armstrong, A.W. Ruff, H. Shin, Mater. Sci. Eng. A 209 1996. 9196. w11x G.M. Pharr, The anomalous behavior of silicon during nanoindentation, in: W.D. Nix, J.C. Bravman, E. Arzt, L.B. Freund Eds.., Thin Films: Stresses and Mechanical Properties III, Materials Research Society Symposium Proceedings, Vol. 239, Materials Research Society, Pittsburgh, PA, 1992, pp. 301312. w12x J.E. Field, C.S.J. Pickles, Diamond Related Mater. 5 1996. 625634. w13x D.F. Diao, K. Kato, K. Hokkirigawa, Fracture mechanisms of ceramic coatings in indentation, ASME J. Tribol. 116 1994. 860 869.

Acknowledgements The authors would like to thank John C. Mitchell for assistance with SEM. The research was supported by the Office of Naval Research, Department of Navy Contract No. N00014-96-1-10292.. The content of the information does not necessarily reflect the position or policy of the Government, and no official endorsement should be inferred.