ISSN 0020 1685, Inorganic Materials, 2012, Vol. 48, No. 5, pp. 451455. Pleiades Publishing, Ltd., 2012.

. Original Russian Text E.Yu. Vilkova, O.V. Timofeev, 2012, published in Neorganicheskie Materialy, 2012, Vol. 48, No. 5, pp. 530535.

Etching and Chemical Mechanical Polishing of ZnSe Using Inorganic Acids

E. Yu. Vilkovaa and O. V. Timofeeva,b
Institute of Chemistry of High Purity Substances, Russian Academy of Sciences, ul. Tropinina 49, Nizhni Novgorod, 603950 Russia bLobachevsky State University, pr. Gagarina 23, Nizhni Novgorod, 603600 Russia e mail: timofeev@ihps.nnov.ru
Received October 19, 2011
a

AbstractThe etching behavior of zinc selenide has been studied at temperatures from 20 to 90C in inor ganic acid solutions of different concentrations, with additions of H2O2 as an oxidant. The kinetic data obtained have been used to identify the mechanisms of the reactions involved and develop a chemical mechanical polishing procedure for polycrystalline zinc selenide. DOI: 10.1134/S002016851204019X

INTRODUCTION Optical components from zinc selenide are used primarily in laser optics and detectors of weak IR radi ation, including IR lasers, night vision systems, radi ometers, and IR pyrometers [1, 2]. The ability to prepare a defect free polished surface is of key importance in the fabrication of optical com ponents from zinc selenide. This can be achieved by combining abrasive and chemical polishing tech niques with chemical etching [3]. Most available data on the chemical and chemi calmechanical treatment of zinc selenide were obtained in the 1970s1980s. There is still consider able interest in zinc selenide: a number of reports have recently been concerned with chemical polishing of ZnSe [4] and polishing process automation. The pro cess, however, has not yet been studied in sufficient detail, nor have the mechanisms of the reactions of zinc selenide with the reactants involved been fully understood. Therefore, the study of the etching and chemical mechanical polishing of zinc selenide is of scientific and technological interest. The purpose of this work was to investigate the etching and chemical mechanical polishing (CMP) of zinc selenide with the use of inorganic acid solutions. EXPERIMENTAL AND CALCULATIONAL APPROACH The etching rate of polished zinc selenide surfaces in inorganic acid solutions was measured using a pro cedure described previously [5]. We etched high purity polycrystalline zinc selenide prepared by chem ical vapor deposition. In our experiments, we used zinc selenide disks 20 mm in diameter and 5 mm in

thickness. The disks were cut from the same plate and were pretreated in the same way. Etching was carried out in aqueous 1 M acid solu tions. The solutions were prepared using distilled water; concentrated sulfuric, hydrochloric, nitric, hydrobromic, and phosphoric acids; and hydrogen peroxide. Each experiment took 100 min. The tem perature was varied from 20 to 90C and was main tained with a stability of 0.1C. The experiments were run under static conditions. The etching results were used to evaluate the time dependent weight change of the zinc selenide samples and the etching rate. We used the formula [6, 7] w = g/(MSt), (1) where w is the etching rate [mol/(cm2 s)], g is the weight loss (g), M is the molecular weight, and S is the surface area of the sample (cm2). The activation energy of the process was evaluated using temperature dependent etching rate data in the form of an Arrhenius equation: (2) w = C ee E a (RT ). The surface density of particles passing into solu tion (ne) was determined as ne = Ce / (molecules/cm2), (3) where = 1013 Hz is the thermal vibration frequency of

solid particles (to within an order of magnitude) and Ce is the preexponential factor. From (3), we have

(4) log w = A + B, T where B = log Ce, A = tan, and Ea = 4.57A. From the logarithm of the etching rate as a func tion of inverse absolute temperature, we evaluated the

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Table 1. Temperature effect on the etching rate of zinc selenide in inorganic acid solutions Etching rate, mg/(h cm2) Solution H2SO4 + H2O2 H3PO4 + H2O2 HCl + H2O2 HBr + HNO3 HNO3 + H2O2 20C 0.32 0.02 0.21 0.01 0.049 0.002 0.041 0.001 0.33 0.07 30C 0.55 0.06 0.57 0.01 0.26 0.03 0.067 0.001 0.51 0.06 40C 0.64 0.02 0.86 0.06 0.41 0.06 0.59 0.01 0.9 0.2 50C 55C 60C 70C 90C

1.3 0.1 1.4 0.1 2.6 0.3 4.8 0.3 12.6 2.8 1.4 0.1 1.9 0.3 2.2 0.2 3.2 0.2 0.7 0.1 1.4 0.1 1.9 0.1 2.1 0.2 6.8 0.1 7.7 0.7

0.8 0.1 2.2 0.1 2.7 0.2 3.9 0.2 29.2 0.1 1.2 0.3 1.3 0.3 1.7 0.2 4.3 0.3 16.8 2.9

Table 2. Kinetic data for zinc selenide dissolution in inorganic acid solutions Solution 1 M H2SO4 + H2O2 HNO3 + H2O2 1 M H3PO4 + H2O2 1 M HCl + H2O2 1 M HBr + HNO3 Ea, kJ/mol 37.7 4.2 41.9 8.4 51.5 4.2 58.6 4.2 83.7 4.2 Ce, at/(cm2 s) 1.25 1021 1.37 1022 2.81 1023 2.68 1024 4.14 1028 ne, at/cm2 2.4 103 2.6 104 5.3 105 5.1 106 7.8 1010 ns, at/cm2 1.22 1015 1.22 1015 1.22 1015 1.22 1015 1.22 1015 ne/ns 1.96 1012 2.13 1011 4.34 1010 4.18 109 6.48 105

A and B coefficients: B was determined as the intercept on the vertical axis, and A as the slope of the plot. CMP experiments were carried out under identi cal, standard conditions: polishing temperature, 21 1C; spindle rocking rate, 54 rpm; polishing wheel rotation rate, 6 rpm. The pressure applied to the holder was 0.32 kgf/cm2. As an extender, we used distilled water. The reactive component (RC) was composed of solutions of inor ganic acids with additions of H2O2 as an oxidant. The RC was delivered to the polishing zone at intervals. RESULTS AND DISCUSSION Chemical etching. Table 1 illustrates the tempera ture effect on the etching rate of zinc selenide in acid solutions containing H2O2 as an oxidant. The etching rate of zinc selenide in each solution is seen to increase with temperature. These results were used to plot the logarithm of the etching rate of zinc selenide against 1/ (Fig. 1). From these data, we evaluated the activation energy, preex ponential factor, and fraction of dissolved particles. The results are presented in Table 2. It can be seen from Table 2 that the activation energy for the etching of polycrystalline zinc selenide in a H2SO4 + H2O2 solution is 37.7 kJ/mol. The amount of zinc selenide dissolved as a result of the reaction is 2.4 103 at/cm2. This value, derived from

experimental data, is much less than the surface den sity of atoms (ns). This suggests that not all of the poly crystalline zinc selenide surface is equally involved in the etching process. Consequently, the etching of zinc selenide is diffusion limited. Kinetic data for zinc selenide etching in solutions of nitric, phosphoric, and hydrochloric acids with H2O2 additions demonstrate that this process is under intermediate control, with activation energies of 41.9, 51.5, and 58.6 kJ/mol, respectively. When a mixture of nitric and hydrobromic acids of 1 M concentration was used, the amount of zinc selenide dissolved as a result of the reaction was 7.8 1010 at/cm2, and most of the polycrystal surface was involved in the reaction. The activation energy of this process, 83.7 kJ/mol, indicates that the rate limiting step is the chemical reaction. Thus, the present results provide some insight into the mechanisms of the reactions of zinc selenide with inorganic acid solutions. The most promise for CMP is offered by solutions of phosphoric, nitric, and hydrochloric acids with H2O2 additions, which react with zinc selenide under intermediate control. CMP. The CMP of zinc selenide using aqueous solutions of inorganic acids with H2O2 additions of dif ferent concentrations was characterized by the time dependent weight change of the zinc selenide samples. The plots in Figs. 2 and 3 are seen to be nonlinear, with a gradual decrease in material removal rate. From their
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ETCHING AND CHEMICAL MECHANICAL POLISHING OF ZnSe 12 11 10 pw 9 8 7 6 5 2.7 2.9 3.1 103/T, K1 (b) 12 11 10 pw 9 8 7 6 5 2.7 12 11 10 9 pw 0 8 7 6 5 2.7 2.9 3.1 103/T, K1 3.3 3.5 20 40 Time, min 60 2.9 3.1 3.3 103/T, K1 (c) 3.5 m 1.2 1.0 0.8 0.6 0.4 0.2 1 2 3 2 1 3.3 3.5 m 0.4 0.3 0.2 0.1 0 20 40 Time, min 60 () 2 1 0.8 0.7 0.6 0.5 1 2 3 4

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Fig. 2. Weight change as a function of CMP time for zinc selenide polished using ASM 2/1 diamond powder and (1) 1 M H3PO4 + 0.85 M H2O2, (2) 1 M HNO3 + 0.85 H2O2, (3) 1 M HCl + 0.85 M H2O2, and (4) 1 M HCl + 1 M HNO3 solutions.

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Fig. 3. Weight change as a function of CMP time for zinc selenide polished using ASM 2/1 diamond powder and (1) H3PO4 + 0.85 M H2O2, (2) H3PO4 + 1.7 H2O2, and (3) H3PO4 + 3.4 M H2O2 solutions.

Fig. 1. Arrhenius plot of the etching rate: (a) (1) H3PO4 + H2O2, (2) HBr + HNO3, (b) (1) H2SO4 + H2O2, (2) HCl + H2O2, (c) HNO3 + H2O2.

From our experimental data, we evaluated the material removal rate during CMP (Table 3). The low est material removal rate [14.75 mg/(h cm2)] was obtained with a 1 M HBr + HNO3 solution, and the highest material removal rate [35.29 mg/(h cm2)] was obtained with 1 M H3PO4 + 3.4 H2O2. It is worth pointing out that the mechanical polish ing rate of zinc selenide with the same materials and under the same polishing conditions was 7 mg/(h cm2). It follows from comparison of the CMP rate and the sum of the etching and mechanical polishing rates that the CMP rate in the case of 1 M HNO3 + 0.85 M H2O2, 1 M HCl + 0.85 H2O2, and 1 M H3PO4 + 1.7 M H2O2 solutions is three times the sum of the etching and

shape, we conclude that the polishing rate decreases throughout the experiment. This indicates that the effectiveness of mechanical processing (mechanical polishing rate) decreases because of the increase in the effective surface area of the parts being polished and a reduction in their roughness.
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()

20 m

(b)

20 m

Fig. 4. Photographs of zinc selenide surfaces after CMP with (a) 1 M HNO3 + H2O2 and (b) 1 M H3PO4 + 3.4 H2O2 solutions.

mechanical polishing rates and that the CMP rate in the case of 1 M H3PO4 + 3.4 M H2O2 is four times this sum. According to physicochemical mechanics con cepts [8], any solid can be mechanically activated, which increases its reactivity. It is, therefore, reason able to expect that, during CMP, chemical reaction and mechanical processing are accompanied by mechanical activation of the surface being polished. The material removal rate then increases by several times, as was observed in this study. To quantify the quality of polished surfaces, we used a computer vision technique [9]. Figure 4 shows photographs of zinc selenide surfaces after CMP with solutions of different compositions. Figure 5 shows the surface density and size of point defects. The number of dots was determined with an accuracy within 10%. According to visual examination results, the highest surface quality was offered by the zinc selenide samples after CMP with a 1 M HNO3 +

H2O2 solution. The lowest surface quality was observed after CMP with 1 M H3PO4 + 3.4 M H2O2. As seen in Fig. 5, the zinc selenide surface polished with a 1 M H3PO4 + 1.7 H2O2 solution as an RC has the largest number of dots, and the surface prepared using 1 M HCl + H2O2 has the smallest number of dots. The surface quality was shown to be influenced not only by the RC composition but also by the RC concentration. Comparison of the present experimental data on the material removal rate, surface quality, and surface geometry allowed us to identify several compositions suitable for the CMP of zinc selenide. Surface quality assessment showed that the surface quality achieved corresponded to the fourth surface finish class accord ing to the RF State Standard GOST 11141 84, with a deviation from planarity no greater than one interfer ence fringe.

Table 3. Material removal rate during the CMP of zinc selenide using RC solutions of different compositions Solution 1 M HBr + 1 M HNO3 1 M HNO3 + 0.85 M H2O2 1 M HCl + 0.85 M H2O2 1 M H3PO4 + 0.85 M H2O2 1 M H3PO4 + 1.7 M H2O2 1 M H3PO4 + 3.4 M H2O2 Material removal rate, mg/(h cm2) 14.75 0.06 21.42 0.02 23.89 0.03 25.15 0.03 29.41 0.03 35.29 0.04
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Etching rate (40C), mg/(h cm2) 0.59 0.01 0.9 0.2 0.41 0.06 0.86 0.06 1.1 0.2 1.3 0.3
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ETCHING AND CHEMICAL MECHANICAL POLISHING OF ZnSe 300 250 200 150 100 50 0 50 () Count 250 200 150 100 50 0 2 4 6 8 Diameter, m (d) Count 10 50 120 100 80 60 40 20 0 2 2 4 6 8 Diameter, m (e) (b) 200 180 160 140 120 100 80 60 40 20 0 10 20 Count 90 80 70 60 50 40 30 20 10 0 10 (c)

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4 6 Diameter, m (f)

10

180 160 140 120 100 80 60 40 20 0 2

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4 6 Diameter, m

10

4 6 8 Diameter, m

10

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4 6 8 Diameter, m

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Fig. 5. Dot size distributions on zinc selenide surfaces polished using (a) 1 M H3PO4 + 1.7 H2O2, (b) 1 M H3PO4 + 3.4 H2O2, (c) 1 M H3PO4 + 0.85 H2O2, (d) 1 M HNO3 + H2O2, (e) 1 M HBr + HNO3, and (f) 1 M HCl + H2O2 solutions.

CONCLUSIONS The etching behavior of zinc selenide has been studied in solutions of inorganic acids (sulfuric, hydrochloric, nitric, hydrobromic, and phosphoric) with additions of hydrogen peroxide as an oxidant. We obtained kinetic curves for zinc selenide etching at temperatures from 20 to 90 in inorganic acid solutions with additions of hydrogen peroxide as an oxidant. The present results demonstrate that, in HNO3 + H2O2, H3PO4 + H2O2, and HCl + H2O2 solutions, zinc selenide dissolution occurs under intermediate con trol, with a significant effect of diffusion processes in solution, which have activation energies of 41.9, 51.5, and 58.6 kJ/mol, respectively. In a HBr + HNO3 solu tion, the rate limiting step of zinc selenide etching is the chemical reaction, with an activation energy of 84 kJ/mol. That the CMP rate of zinc selenide is three to four times the sum of the etching and mechanical polishing rates points to mechanical activation of the surface being polished. The proposed RC compositions for CMP ensure good quality of optical surfaces and allow one to min imize surface roughness. REFERENCES
1. Spravochnik tekhnologa optika (Optical Technologists Handbook), Okatov, M.A. et al., Eds., St. Petersburg: Politekhnika, 2004.
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2. Gavrishchuk, E.M., Polycrystalline Zinc Selenide for IR Optical Applications, Inorg. Mater., 2003, vol. 39, no. 9, pp. 883898. 3. Borovskikh, U.P., Timofeev, O.V., Vilkova, E.Yu., and Popova, E.Yu., Chemomechanical Polishing of Zinc Selenide with Aqueous Solutions of Inorganic Acids and Bases, XIII Konferentsiya Vysokochistye veshchestva i materialy. Poluchenie, analiz, primenenie (XIII Conf. High Purity Substances and Materials: Preparation, Analysis, and Application, Nizhni Novgorod, 2007), Churbanov, M.F., Ed., Nizhni Novgorod: Yu.A. Niko laev, 2007, pp. 196197. 4. Tomashik, V.N. and Tomashik, Z.F., Chemical Polish ing of IIVI Semiconductors, Inorg. Mater., 1997, vol. 33, no. 12, pp. 12301233. 5. Timofeev, O.V. and Vilkova, E.Yu., Effect of Etching and Chemomechanical Polishing on the Surface Quality of Polycrystalline ZnSe, Inorg. Mater., 2010, vol. 46, no. 3, pp. 259263. 6. Orlova, G.M., Blinov, L.N., Belyakova, N.V., and Kozharina, T.P., Chemical Dissolution Kinetics of Lead Chalcogenides, Zh. Prikl. Khim. (Leningrad), 1975, no. 9, pp. 19451949. 7. Orlova, G.M. and Ermolaeva, T.P., Etching Behavior of IIVI Compounds, Zh. Prikl. Khim. (Leningrad), 1981, vol. 54, no. 9, pp. 19601963. 8. Rebinder, P.A., Fiziko khimicheskaya mekhanika (Physicochemical Mechanics), Moscow: Znanie, 1967. 9. Gavrishchuk, E.M., Vilkova, E.Yu., Kolesnikov, A.N., and Timofeev, O.V., Examination of Polished Surfaces of Zinc Chalcogenides Using Computer Recognition of Defects in Micrographs, Opt. Zh., 2010, vol. 77, no. 1, pp. 8794.