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Journal of Crystal Growth 257 (2003) 110115

Growth and characterizations of bulk ZnSe single crystal by chemical vapor transport
Huanyong Li, Wanqi Jie*
" State Key Laboratory of Solidication Processing, Northwest Polytechnic University, Xian 710072, Peoples Republic of China Received 11 December 2002; accepted 24 January 2003 Communicated by T. Hibiya

Abstract The bulk ZnSe single crystal was grown from the vapor by Zn(NH4)3Cl5 transport from ZnSe polycrystals source, which was synthesized from commercial grade high-purity elements, selenium and zinc. The growth temperature between the source and the growing ZnSe single crystal was 898915 C and the temperature difference of the growth tube was 1418 C. The orange ZnSe single crystal of F9 25 mm was obtained. The studies on the features and habit of the growth surface show that the growth surface of as-grown ZnSe crystal was composed of {1 1 1}and {1 0 0} faces. The crystal quality of ZnSe crystal was investigated by RO-XRD. The FWHM value of RO-XRD patterns of ZnSe (1 1 1) face is 24 s. The photoluminescence spectrum is dominated by two broad peaks located at 439 and 418 nm, respectively. The etch pit density is about (57) 104 cm2. The absorption edge is very sharp and is located at about 465 nm. All of the above results indicate that a ZnSe single crystal with high crystalline quality and high purity can be grown from the vapor by Zn(NH4)3Cl5 transport. r 2003 Elsevier B.V. All rights reserved.
PACS: 81.05.Dz; 81.10.Bk Keywords: A1. Transport agent; A2. Chemical vapor transport; B1. Zn(NH4)3Cl5; B1. ZnSe

1. Introduction ZnSe, as a wide-band-gap semiconductor (Eg 2:67 eV at room temperature), has been identied as an important contender for the fabrication of blue light-diodes and nonlinear opto-electronic components [13]. In the process of opto-electronic devices, GaAs was usually
*Corresponding author. Tel.: +86-029-8495414; fax: +86029-8495414. E-mail address: jwq@nwpu.edu.cn (W. Jie).

employed as the substrate, but it is preferable to use bulk ZnSe single crystal as the substrate because homoepitaxial-type components with a simple structure and high performance light emitting can be achieved. For this purpose, great efforts have been devoted to grow ZnSe single crystals with high purity and low defect density. The chemical vapor transport (CVT) is known to be superior to others for the preparation of bulk ZnSe single crystals with low twin and dislocation densities. The chemical transport agent plays a key role during the growth of the ZnSe single crystal.

0022-0248/$ - see front matter r 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0022-0248(03)01431-3

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The transport agents react with ZnSe source materials and transport them along the temperature gradient to a cooler zone of the furnace where the ZnSe single crystal is grown. Different traditional chemical transport agents such as I2, H2 and H2O [46] bring about various mechanisms corresponding to various CVT techniques, making them essentially different methods. However, when the traditional transport agents are used, the experimental procedure would be complicated and a reservoir to isolate the transport agent would be necessary [7,8] due to their volatility or relatively high vapor pressure at room temperature. In the present research, some results of bulk ZnSe single crystal with high purity and high quality grown from the vapor by Zn(NH4)3Cl5 transport will be reported.

Fig. 1. Temperature prole of the CVT furnace.

2. Experiment 2.1. Preparation of the source materials The transport agent Zn(NH4)3Cl5 was synthesized and puried according to the procedure described in the literature [9]. ZnSe polycrystals were synthesized by the chemical vapor reacting with high purity elements (Zn(6N),Se(5N), EMEI Semiconductor Materials Ltd.) in a quartz ampoule. Special care was taken for washing the ampoule to avoid contamination of the sample by the ampoule. After being loaded with Zn and Se and evacuated to the vapor pressure lower than 1 104 Pa, the ampoule was sealed. It was heated using H2O2 ame with moderate intensity until a few yellow ZnSe polycrystals formed in the ampoule. Then the ampoule was held at reaction temperature 1010 1025 C in a vertical furnace. Synthesized ZnSe was in the form of yellow-orange particles. Then the ZnSe particles were ground to a powder of less than several mm in size and reserved. 2.2. Growth of single crystal The CVT method was employed to grow a ZnSe single crystal. The ampoule was washed with

aquaregia and rinsed with distilled water and acetone. It was then heated up to 1050 C and kept at this temperature for 24 h to evaporate impurities. After cooling down, it was charged with ZnSe powder and Zn(NH4)3Cl5 transport agent and sealed off under high vacuum (1 104 Pa). Then the ampoule with a length of about 1112 cm was placed into a double-zone furnace controlled by Eurotherm controllers with the accuracy of 70.5 and adjusted in a reversed temperature zone for 12 h in order to clean microcrystals near the tip. Then the ampoule was positioned in the furnace with the temperature difference DT 12218 C between the two ends of the ampoule. The temperature gradient in the growth zone was less than 1.5 C cm1. The growth temperature was between 898 C and 915 C. The temperature prole of the furnace is shown in Fig. 1. In order to avoid any inuence of mechanical vibration to crystal quality, the ampoule was kept motionless during the growth process. After about 21 days, the ampoule was slowly cooled at a rate of 60 C/h to room temperature. The grown crystal with F9 25mm size was obtained in the top of the ampoule, as shown in Fig. 2. 2.3. Measure conditions and apparatus ZnSe samples cleaved along the (1 1 1) cleavage plane were supplied for characterization. The crystallographic properties were estimated by

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be written as ZnNH4 3 Cl5 -ZnCl2 g 3HCl g 3NH3 g; 1

ZnSe s 2HCl g"ZnCl2 g H2 Se g: 2 At the growth temperature of 898915 C, the following reactions will also exist in the closed tube [11]: 2HCl g"Cl2 g H2 g; H2 Se g"H2 g 0:5Se2 g:
Fig. 2. As-grown bulk ZnSe single crystal.

3 4

Neglecting dissociation of ZnSe via Eq. (5) and neglecting dissociation of ZnCl2 via Eq. (6) [12]: ZnSe s"Zn g 0:5Se2 g; 5 6

RO-XRD patterns obtained by the modied Rigacu D/max-3C X-ray diffractometer. The photoluminescence spectra were measured at room temperature. The excition source was an HeCd laser (l 325 nm) with the intensity of about 30 W. The absorption measure was carried out on a UV-1100 type UVVIS Photometer. The etch pit distribution density was observed by LEICA QUAMTIMT 500 type optic microscopes.

ZnCl2 g"Zn g Cl2 g:

3. Results and discussions 3.1. Analysis on the characterizations of Zn(NH4)3Cl5 Zn(NH4)3Cl5, as a double salt, has a wide application in battery, electroplating and welding elds [9]. However, it has not been reported in the literatures that the compound was used as a chemical transport agent in CVT system or in the chemically activated sublimation system. The advantages of the novel transport agent are as follows: (1) It is easy to handle due to its higher thermostability and relatively lower vapor pressure than traditional transport agents [46,9]. The studies on the thermal behavior of Zn(NH4)3Cl5 indicates that its thermal decomposition process takes place at about 210340 C [10]. (2) In the case of ZnSe polycrystals with Zn(NH4)3Cl5, Zn(NH4)3Cl5 dissociates and acts as HCl, ZnCl2 and NH3. The main reactions of the transport can

In the process of crystal growth, there are high concentrations of ZnCl2, HCl and NH3 in the gas components because one molecular Zn(NH4)3Cl5 can produce three molecular HCl, three molecular NH3 and one molecular ZnCl2. Under the conditions of high concentration in HCl gas, the gas partial pressure of H2 will be very high [11] so that the dissociation of H2Se will be prevented according to Eq. (4) to a great degree and the partial pressure of H2Se will be large enough. Accordingly, the dominant gas species are ZnCl2, HCl, NH3 and H2Se, and Eqs. (1) and (2) are the main reactions relevant to the ZnSe transport. This has been demonstrated early by the experiment in Ref. [13]. (3) Unlike iodine, the decomposition products of Zn(NH4)3Cl5 will cause very little Cl contamination, even at high Zn(NH4)3Cl5 concentration [11,14]. Nevertheless, ZnCl2 can offer a route to obtain ZnSe crystal with plentiful zinc, which is similar to adding excess Zn into the starting materials in melt [15] and adding a Zn reservoir in physical vapor transport system [16,17]. This will be proved in our experiments and discussed in the following text. The NH3 gas in the closed system, analogous to the inert gas, possesses the advantages of adjusting the growth rate of ZnSe and to obtain the high-quality single crystal. (4) The production of volatile species at growth temperature from the decomposition of ZnSe polycrystals is that of H2Se gas, not selenium

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Fig. 3. Dependence of log K on temperature T:

Fig. 4. (a) The morphology of ZnSe surface, (b) Schematic illustration of the surface.

gas. This avoids the difculties of the experimental handle and theoretical analysis on the transport of ZnSe due to the non-emerging of Sen(n 228) in selenium vapor [18]. The temperature dependence of the equilibrium constant K of Eq. (2) was calculated using thermodynamic data [18,19,20], resulting in Eq. (7) and Fig. 3. log K 3315:96 0:14 ln T T 2167:43 3:13 106 T 1:35: T2

According to Eq. (7) and the curve in Fig. 3, the equilibrium constant K increases with increasing temperature in the ZnSeHClZnCl2 system. Thus, the ZnSe crystal is deposited at the growth zone because the source zone is kept hotter than the growth zone. The above analysis show that Zn(NH4)3Cl5 is a multi-function transport agent. 3.2. Characterizations of ZnSe single crystal Fig. 2 shows the photograph of a typical asgrowth ZnSe crystal inside the conically shaped self-seeded growth ampoule. The crystal is transparent orange. XRD analysis shows that the as# grown ZnSe crystal is composed of (1 1 1), 1 1 1 and two narrow (1 0 0), (0 0 1) faces. The photograph of a typical ZnSe crystal with cubic habit is shown in Fig. 4(a), and the indices are schematically represented in Fig. 4(b). This result coincides

with the ZnSe crystal grown by I2 transport [7]. The composition of the as-grown crystal was determined by EDAX. The crystal has a stoichiometry ratio of Zn:Se=1.01:1, which proves that the crystal contains excess zinc. This is attributed to zinc from the transport agent Zn(NH4)3Cl5. The RO-XRD was used to investigate the structure and crystalline characterizations of an as-grown ZnSe crystal. RO-XRD is a simple, quick and precise method for valuating crystals quality and determining crystals orientation [21]. The RO-XRD pattern is obtained by rotating the crystal along its surface normal axle during the y scanning at the xing 2y0 of the studied crystal face. The RO-XRD pattern of the dominant (1 1 1) clearage face is used to valuate the crystalline quality of as-grown ZnSe. Fig. 5(a) shows the ROXRD pattern of ZnSe(1 1 1)face, which was measured during y scanning at xing 2y0 27:22 . This RO-XRD pattern is a symmetrical one, consisting of two branches with an FWHM value of 24 s and intensity of 58300 cps. The F value, which is the angle between the surface normal axle and the (1 1 1) face normal axle, is calculated to be 3.1 . According to Fig. 5(a), there are some step lines between two dominant peaks, meaning that the ZnSe specimen contains some polycrystallinity at its edge. This can be attributed to the crystalline disorder caused by the ampoule wall when the crystal touches the wall during growth. When y scanning is carried out at xing 2y0 of 31.53 , 45.23 and 53.64 , respectively, the corresponding RO-XRD

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Fig. 5. (a) RO-XRD pattern of as-grown ZnSe (1 1 1) face. Test condition: CuK1, 35 kV, 10 mA, xing 2y0 27:22 ; Result: y1 12:06 y2 15:16 , f y2 y1 3:1 , FWHM=24 s, intensity=58,300 cps. (b) RO-XRD patterns of the same ZnSe specimen when xing 2y0 were 31.53 , 45.23 and 53.64 for (2 0 0), (2 2 0) and (3 1 1) micro-face, respectively. Test condition: CuK1, 35 kV, 10 mA.

Fig. 6. PL spectrum of ZnSe single crystal at room temperature (Inserter: PL spectrum of synthesized ZnSe polycrystals).

patterns of the same specimen do not have any dominated peak (Fig. 5(b)). Considering that the RO-XRD method can reveal the detailed crystalline information and FWHM value of RO-XRD is usually in good agreement with that of the double crystal rocking curve [22], the high crystalline quality of as-grown ZnSe crystal can be obtained by the above results. Photoluminescence measurement is a powerful and sensitive tool for studying the effects of purication and contamination during the crystal growth process. The HeCd laser was used as the excitation source. The photoluminescence spectrum of an as-grown ZnSe single crystal at room temperature is shown in Fig. 6. The PL peak located at 439 nm (2.8 eV) can be associated with the excitonic emission line [23], which is analogous to the excited state of FX (n 2) [24,25]. It is the ngerprint of a high-quality ZnSe sample. The

Fig. 7. Absolute spectrum of ZnSe of on the ZnSe (1 1 1) face (1 mm thick).

emission line at low intensity could be due to the noise of the PL system or the instabilities of the exciting laser. The broad emission at 418 nm (3.0 eV) is not known to date. This emission band is analogous to the broad line (3.1 eV) described in the literature [26], but it was regarded as the noise of the measurement system by Fang et al. The study about this emission is being carried out. No self-activated luminescence band was detected in the low-energy side of the PL spectrum. This means that the ZnSe crystal does not contain impurities and zinc vacancy [26,27]. Compared with the PL spectrum with only SA luminescence of synthesized ZnSe polycrystals (Fig. 6 inserter), we can conclude that an as-grown ZnSe single crystal with high purity can be grown by Zn(NH4)3Cl5 transport in our system.

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Acknowledgements The authors are grateful for the nancial support of the project by Prominent Young Scientist Foundation of China (59825109). References
[1] H. Luo, J.K. Furdyna, Semicond. Sci. Technol. 10 (1995) 1041. [2] A. Ishibashi, I. Crystal Growth 159 (1996) 555. [3] B.S. Wherrett, J. Crystal Growth 159 (1996) 766. [4] S. Fujiwara, Y. Namikawa, M. Irikura, K. Matsumoto, T. Kotani, J. Crystal Growth 219 (2000) 353. [5] T. Muranoi, T. Shiohara, J. Crystal Growth 146 (1995) 49. [6] J. Mimila, R. Triboalet, Mater. Lett. 24 (1995) 221. [7] T. Koyama, T. Yodo, H. Oka, K. Yamashita, T. Yamasaki, J. Crystal Growth 91 (1988) 639. [8] S. Fujiwara, H. Morishita, T. Kotani, K. Matsumoto, T. Shirakawa, J. Crystal Growth 186 (1998) 60. [9] S.C. Ma, The Handbook of Inorganic Compound, ShaanXi Sci. & Tech. Press, Xi" n, 1988, p. 278. a [10] H. Li, R. Hu, W. Jie, Chinese J. Appl. Chem. 20 (4) (2003) 312. [11] M. Nishio, H. Ogawa, J. Crystal Growth 78 (1986) 218. [12] O. Senthil Kumar, S. Soundeswaran, R. Dhanasekaran, Crystal Growth Design 2 (6) (2002) 585. [13] H.J. Hovel, A.G. Milnes, J. Electrochem. Soc.: Solid State Sci. 116 (6) (1969) 843. [14] R. Triboukt, F. Rabago, R. Legros, J. Crystal Growth 59 (1982) 172. [15] J.F. Wang, A. Mino, M. Ishiki, J. Crystal Growth 229 (2001) 69. [16] H. Hartmann, D. Siche, J. Crystal Growth 138 (1994) 260. [17] K. Mochizuki, K. Matsumoto, T. Yasuda, Y. Segawa, K. Kimoto, J. Crystal Growth 135 (1994) 318. [18] G. Perrier, Mater. Sci. Eng. B(14) (1992) 369. [19] R.F. Brebrick, L. Haochieh, J. Phase Equilibria 17 (6) (1996) 495. [20] K. Matsumoto, G. Shimaoka, J. Crystal Growth 79 (1986) 723. [21] Z.Q. Guo, T. Fu, N. Wang, H.Z. Fu, Mater. Charact. 44 (2000) 431. [22] H. Li, W. Jie, Function Materials, 14 (5) (2003) 376. (in Chinese). [23] N. Sankar, K. Ramachandran, J. Crystal Growth 247 (2003) 157. [24] E. Tournie, C. Morhain, G. Neu, J.P. Faurie, R. Triboulet, J.O. Ndap, Appl. Phys. Lett. 68 (10) (1996) 1356. [25] R. Triboulet, J.O. Ndap, A. Mromson-Carli, P. Lemasson, C. Morhain, G. Neu, J. Crystal Growth 159 (1996) 156. [26] C.S. Fang, Q.T. Gu, J.Q. Wei, Q.W. Pan, W. Shi, J.Y. Wang, J. Crystal Growth 209 (2000) 542. [27] C. Su, S. Feth, L.J. Wang, S.L. Lehoczky, J. Crystal Growth 224 (2001) 32. [28] F. Allegretti, A. Carrara, S. Pizzini, J. Crystal Growth 128 (1993) 646.

Fig. 8. Photograph of etch pits (magnication 50 ).

In order to characterize the optical quality of the ZnSe crystal, the absorption measurement was carried out at room temperature in the optical edge region. The absorption edge is very sharp and is located at about 465 nm (Fig. 7), corresponding to that reported in the literature [28]. This is in good agreement with the energy band gap of 2.67 eV. An as-grown ZnSe crystal was also etched in boiling NaOH 30% for 20 min to check the etch pit distribution density. The average etch pit density was about (47) 104/cm2, as shown in Fig. 8. The low-angle grain boundaries and twins were not detected.

4. Conclusions The compound, Zn(NH4)3Cl5, was employed as the transport agent for the growth of a bulk ZnSe single crystal. The ZnSe crystal with F9 25 mm was grown by CVT in a closed system. The characterizations of a ZnSe single crystal were studied by RO-XRD, PL measurement, absorption and etched pit density. The results demonstrated that a ZnSe single crystal with high crystalline quality and high purity can be grown from the vapor by Zn(NH4)3Cl5 transport.