BASIC LAB REPORT

M104 ETCHING OF SEMICONDUCTOR

GROUP 104 Hafid Suharyadi hasu@tf.uni-kiel.de

Torben Waldmann tow@tf.uni-kiel.de

7 December 2012

FACULTY OF ENGINEERING KIEL UNIVERSITY

Table of Contents
1. 2. 3. Introduction ....................................................................................................................................1 Theory..............................................................................................................................................1 Experiment .....................................................................................................................................1 3.1 3.2 4. 5. 6. 7. Equipment and Materials....................................................................................................1 Procedure .................................................................................................................................2

Results .............................................................................................................................................3 Discussion ................................................................................................................................... 10 Summary ...................................................................................................................................... 11 References ................................................................................................................................... 11

1. Introduction Recent update aim 2. Theory Polar-nonpolar relation of H2O and Copper Contact angle based on hidrophobil, hydrophobic Microscope work based on reflectivity

3. Experiment 3.1 Equipment and Materials For every procedure, deionized water and air jet, were used to clean the sample. The optical microscope was used to analyze the sample surface.

a) Polishing i. Solution consists of 60 ml HF (48% aq. solution), 100 ml HNO3 (65% aq. solution), 60 ml CH3COOH (96% aq. solution). ii. A thermometer. iii. 4 pieces of unpolished silicon wafer, 2.5x2.5 cm2.

b) Defect Etching i. SECCO solution consists of K2Cr2O7 (1.452 g), H2O (33 ml), and HF (67 ml). ii. A piece of polished silicon.

c) Structuring i. ii. iii. iv. 70 g KOH pellets. 40 ml Isopropanol. Two thermometers. Two pieces of polished silicon.
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3.2

Procedure a) General After submerging the samples in the etchant solutions, those were rinsed in deionized water and dried with air jet. The pictures of silicon surface were photographed by the optical microscope in various magnifications.

b) Polishing Four pieces of unpolished wafer silicon, without overlap, were polished by immersing those in an etchant, which was thermally isolated and consisted of HNO3 and HF with CH3COOH as a solvent. Two main steps are oxidative reaction with HNO3 (equation 1-4) and dissolution reaction of SiO2 with HF (equation 4-5). This procedure aimed to remove the layer of samples close to the surface, and to produce a shiny and flat surface of silicon. This was maintained for 8 min 30 s. A thermometer was used to monitor temperature of solution.

c) Defect Etching The areas near defects of polished surface were investigated. One of polished silicon pieces was used and put into the SECCO solution for 5 min. The sample was cleaned with DI water and dried with an air jet.

d) Pyramid Etching In this experiment, two of remaining samples were used, in which one sample was put in KOH solution by treated in room temperature (20C) and and another was in 80C. KOH solution with two thermometers were used and two magnetic stirrers were used to stir the solution. Finally samples are washed in DI water and dried by the air jet again.

4. Results a) Unpolished Sample. The smoothness or roughness of the silicon surface is determined qualitatively by the optical microscope image [1]. Before polishing, the pictures of samples show some roughness surfaces. The layer of silicon may contain contaminants that will be removed by etching process. At the figure 1 and 2, one can see that very grainy and coarse structure is observed.

Figure 1. The optical microscope image of unpolished sample, grainy structure, 50x.

Figure 1. The optical microscope image of unpolished sample, grainy structure, not all planes in-focus, 1000x.

b) Polished-etched Sample The quality surface of samples after polishing determined from microscope images is pointed to the influence of etching solutions on their surfaces. As explained by reactions on equations 1-5, the etching mechanism is performed by chemical reaction that occurs to form the volatile compounds and atoms, which are desorbed from the sample surface. At this experiment, one can see the flat surface and mirrored face from these four samples. It is expected that the silicon in native or SiO2 amorphous has been consumed partially during SiO2 growth. Based on figure 3, a roughness on atomic scale is reduced. On the figure 4, with using higher magnification, one can see that no roughness is visible. Some dark areas appeared are created by microscope lens which is not clean.

Since the temperature was increasing for 15.2C (17.3C - 32.5C), one could expect that the state of the products was exothermic, relating to

oxidation process. At the last of this step, gas brown that relates to the formation of NO2 (equation 1) was observed.

Figure 3. The optical microscope image of polished sample, still micro-rough surface, 50x.

Figure 4. The optical microscope image of polished sample, the best achievable focal contrast at 1000x.

c) Defect-etched Sample If the silicon defects are found, one should carefully identify them. In general, the crystalline defects delineated by SECCO give elliptical etch pits [2,3]. This method is applied in failure analysis of wafer fabrication.

The main advantages in using SECCO is a rapid chemical etching method to delineate crystalline defects on silicon wafer, in welldefined etching pits with elliptical shape, and fast and simple in preparing the solution [2,3].

At this part of experiment, it is not easy to identify the defects. One factor is that etching process possibly does not remove the substrate layer completely, or not well polished. From figure 5, three black dots are appeared on the silicon surface. The red circle (close view at figure 6) indicates the area near defects on the surface.

r Figure 5. The optical microscope image of defect etched sample with 1000x.

Figure 6. Close-up view of defect area three black dots.

d) Pyramid-etched Sample The pyramidal structures in term of geometric allow light to be more easily coupled into the silicon and absorbed into the solar cells. The structuring step was done by removing the damage on the surface and producing straight-up pyramid on a surface. This method is using alkaline solutions with considering its higher etching rates. However, due to the anisotropy of single crystalline silicon, etching rates in alkaline solution varies with the different crystal orientation. Etching rate ratio of crystalline planes in [110]:[100]:[111] is approximately 160:100:1 at room temperature[4].

Atom arrangement at the silicon crystal [111] plane is the tightest one. There is only one free covalent bond per atom at the interface and other three bonds in inter-layer integrity. In contrast to this plane, the difference is less tight arrangement of silicon atoms on the [110] crystal plane with two free covalent bonds at the interface, thus those are preferentially dissolved. Macroscopically, the silicon surface is attacked at the random places in an inverse-pyramidal manner, as the etching occurs only at the tip of this inverse-pyramid, the structure is maintained but grows in size.

As the temperature increases, the etching rate and will increase and the pyramids formed will increase as well. The phenomena can be explained by the chemical kinetics and the Arrhenius Law.
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( ) where v is the rate for the chemical reaction, Ea is the energy activation, R is the Boltzmann constant, k is the reaction rate constant, k0 is the constant, T is the etching temperature, and C and D are the reaction orders in respect to OH- and H2O respectively [5]. The diffusion rate (the transportation rate of reactants to the surface or products from the surface) can be enhanced by stirring to remove the silicate solute from the silicon interface. Therefore, by applying sufficient stirring, the spontaneously formed oxide film can be removed [4,5].

The figure 7 shows the surface of sample that is etched in KOH solution at 20C. The surface of this sample is slight rough and no pyramids are found in this sample.

Figure 7. The optical microscope image of etched sample in KOH solution, time 30 min, temperature 20C, 200x.

In contrast to the sample of figure 7, the pyramid structures appear on the surface that is etched at the 80C, as showed in figure 8. One

can see that the morphology of silicon surface change visibly. The pyramid structure with various sizes of square base forms randomly on the surface. This result agrees with the report [5] in which a tendency for forming pyramids on silicon wafer surface is indicated at 50C rather than at 25C. Figure 9 shows the close view of pyramid structure on silicon surface.

Figure 8. The optical microscope image of etched sample in KOH solution, time 30 min, temperature 80C, 200x.

Figure 9. The optical microscope image of etched sample in KOH solution, time 30 min, temperature 80C, 1000x.

5. Discussion The roughness of the silicon surface is determined qualitatively by the optical microscope image. In the unpolished sample (fig. 1 & 2), a very grainy and coarse surface is observed. The effects of several solutions as etchant and temperature to the morphology of silicon surface in this experiment are described below.

After polishing, the surface of sample is changed. With low magnification, the roughness on atomic scale (fig. 3) is reduced visibly. It is expected that the substrate containing SiO2 amorphous has been consumed partially during SiO2 growth. Otherwise the flat surface (fig. 4) is appeared by higher magnification due to a good reflectivity and low micro-roughness of the sample. The reaction state is described as an exothermic leading to the increase of temperature.

At the defect etching, an area expected as a defect area is presented by figure 5. The three black dots on the silicon surface (in red circle of the fig. 6) may be interpreted as a kind of defects that are appeared after removing very thin layer of substrate.

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The different etching temperatures lead to the different morphology of silicon surface. At the higher temperature, the forming of pyramid on the silicon surface is appeared visibly. The size distribution is more than inhomogeneous; as there were no etch seeds, in order to preferenciate certain spots. In contrast to the sample treated at room temperature, the surface is slight rough and no pyramids are found. This difference can be explained by considering the rate of chemical reactions as a function of the temperature.

6. Summary The wet etching accompanied by the morphology change of silicon surface has been studied. A morphology change after polishing has been observed for removing a substrate from the silicon surface. For the defect etching part, the area with three black dots may be expected as the preferentially etched areas near defects. A further work is important to observe this defect area precisely. At structuring, the pyramids with inhomogeneous size have been observed visibly on the silicon surface treated at the higher temperature, in contrast to the sample treated at room temperature. 7. References [1] Lab instruction M104, TF CAU Kiel. [2] R.B. Heimann, M.B. Ives and P. Zaya. Influence of surface films on the development of pits during etching silicon. Journal of Crystal growth 57 (1982) 48-56. [3] http://silicon.tf.unikiel.de/matwis/amat/def_en/kap_6/backbone/r6_1_1.html#_4 [4] Seidel, L. Csepregi, A. Heuberger. Baumgrtel, Anisotropic etching of crystalline silicon in alkaline solutions. J. Electrochem. Soc. 137 (1990) 36123626. [5] Yuan Fulong, Guo Yongfeng, Liang Yingchun, Yan Yongda, Fu Honggang, Cheng Kai, Luo Xichun. Micro-fabrication of crystalline silicon by controlled alkali etching. Journal of Materials Processing Technology 149 (2004) 567572.

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