Journal of the Korean Physical Society, Vol. 42, February 2003, pp.

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Growth and Impurity Study of GaN Single Crystal Grown by Na Flux

Sang Eon Park
COMTECS Ltd, Advanced Materials Research Laboratory, Daegu 704-702

Chae-Ryong Cho
Korea Basic Science Institute, Busan Branch, Busan 609-735

Sung Kyu Kim and Se-Young Jeong

Department of Physics, Pusan National University, Busan 609-735 We have employed a Na ux method to grow GaN single crystal. Two kinds of crucibles were used to grow GaN crystal. GaN single crystals inside the crucibles exhibit plate-like morphologies. The depth prole of elements of GaN crystal was measured by using secondary ion mass spectroscopy. The nature of blue luminescence(BL) and donor-acceptor emissions of GaN single crystal were investigated at low temperature. The BL was eliminated by using InconelTM instead of SUSTM as a crucible. The purity of GaN crystal was strongly dependent on the ingredients of the crucible used and we notably reduced the quantity of unintentionally doped impurities.
PACS numbers: 81.05.Ea, 81.10.-h, 78.30.Fs. 78.55.Cr Keywords: Crystal growth, Na, PL, GaN

I. INTRODUCTION GaN-based nitride thin lms have been developed for blue and ultra-violet laser diodes and detectors by many research groups [1, 2]. These GaN-based optoeletronic and microwave devices are manufactured on sapphire substrates. Dislocation density and many defects in the device are due to the lattice mismatch and thermal expansion coecients between substrates and GaN lm [3, 4]. Bulk GaN single crystals must be a suitable substrate for the fabrication of high quality nitridebased light-emitting diodes(LEDs). GaN lm possesses a high density of grain boundaries, dislocation densities (1010 1011 /cm3 ) and various point defects. Understanding the nature of these defects and their potential inuence on device properties is of increasing importance for optimization of device performance [5]. The defects in the band gap of GaN are usually characterized by luminescence. The yellow luminescence is a broad Gaussian-shaped emission centered at 2.2 2.3 eV and appears to be a universal feature in GaN grown by metalorganic vapor-phase epitaxy and molecular beam epitaxy [610]. The origin of the yellow luminescence emission is still being debated. At room temperature, the donoracceptor(DA) emission superimposes on the near band edge emission. It was reported that DA emission originates from shallow acceptor and shallow donor recombination and their phonon replicas [7,11,12]. In particular,
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the basic material properties of GaN epitaxial layers concern PL bands peaked in the red(1.8 eV, Si and Mg codoped), the yellow(2.2 eV, Si-doped or undoped), and the blue (2.8 eV, Mg-doped) spectra. The yellow and blue luminescence are often found in undoped material [7,12]. In this paper, we have investigated the characteristics of PL in GaN single crystal grown using SUS and Inconel growth cells.

II. EXPERIMENTAL The crystal growth proceeded by rst adjusting the temperature and pressure of the reactor cells to the desired level using the SUS and Inconel growth cells [13, 14]. SUS and Inconel were made of 18 %Cr - 8 %Ni and 72 %Ni - 15 %Cr - 8 %Fe, respectively. We will represent here SUSTM and InconelTM as trademarks. Both SUSTM and InconelTM cells contained NaN3 powder, which acted as a source of nitrogen upon heating, and pure(4N) Ga metal as reactants. The InconelTM cell( Fe + Cr 30 % ) has less Fe and Cr impurities than the SUSTM cell(Fe + Cr 70 %). After processing, the reactor cell was extracted from the reactor. Most of the grown crystal was in the Na melts. We could not conrm whether the crystal nucleated on the growth cell or in the melt near the melt surface. The structure of the grown GaN crystals has been studied by X-ray diraction [13]. Secondary ion mass spectroscopy (SIMS) analysis was performed with a magnetic-sector-based instrument (Cameca IMS-

syjeong@pusan.ac.kr

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Journal of the Korean Physical Society, Vol. 42, February 2003

Fig. 1. Optical microscope images of GaN crystal grown by (a) SUS cell and (b) Inconel cell.

4f). O2 + -ion beams were used as the primary ion sources to detect positive secondary ions. The primary beam was accelerated through 8.0 keV and its intensity was approximately 100 nA. The dependence of PL on the temperature was measured from 5 K to 300 K for the purpose of examining the optical qualities of the prepared crystal using a closed cycle helium cryostat. A He-Cd laser, with 325 nm (55 mW) emission wavelength, was used as the excitation source.

III. RESULTS AND DISCUSSION GaN bulk crystal grown inside SUSTM and InconelTM cells exhibits plate-like morphologies 4 5 mm in size, as shown in Fig. 1. All crystals showed strong and well dened single crystalline XRD patterns. The XRD pattern conrmed the oriented growth with the (0001) of GaN. The structural symmetries of GaN grown by the SUSTM and InconelTM cell were determined using the -scan of (10 11) peak with a -rotation axis parallel to the c-axis of the GaN crystals. The six diraction peaks were observed at regular 60o increments. Although SIMS analysis of an ionimplanted standard sample is necessary to obtain a quantitative content of impurity, the relative contents can be explained by the incorporation of impurities due to the dierent growth cell. The Ga, N, Fe and Cr elements are evaluated by using an O2 + primary beam. Fig. 2(a) and 2(b) shows the SIMS depth proles for GaN single crystals grown by SUSTM and InconelTM cell, respectively. A depth prole analysis was performed for Ga, N and the other impurities, Fe and Cr. The yield of the ion of Ga and N was constant throughout the depth of GaN single crystal. Anomalous behavior of the Fe and Cr elements yielded from GaN crystal grown using the SUSTM cell was stronger than for that grown using the InconelTM cell, especially in the surface region. It was veried that the impurity incorporation depends on the elements of the growth cell. The nature of blue-band luminescence (BL) and DA emission of undoped GaN grown using the various crucibles and a ux method was investigated using a low-temperature PL system. We compared the photoluminescence spectra of GaN single crystal grown by using the SUSTM cell with that by the InconelTM cell. In the case of the SUSTM cell, as shown in Fig. 3, there

are three PL bands usually observed in the range of 2.5 3.5 eV; i) Normally the near-band-edge transition at 3.4 eV is observed. ii) Under low temperature from 5 K to 175 K, an ultraviolet(UV) band is observed at about 3.27 eV that involves donor-acceptor pair (DAP) luminescence due to optical transitions from a shallow donor to a shallow acceptor. Shallow DAP emission was followed by several phonon replicas. iii) Broad blue luminescence centered near 2.9 eV is obtained. The intensity of the BL emission was even higher than that of the near band edge emission. The 2.9 eV PL emission band has revealed a fatigue eect that could be explained by the metastable nature of the related defect [8]. Various proposals have been made as to the nature of defect responsible for the 2.9 eV band in undoped GaN [7, 12, 15]. Two principal mechanisms have been proposed. One of them comprises a transition from the conduction band or shallow donor to a deep acceptor, which was assumed to be an isolated VGa (Ga vacancy) or hydrogenated VGa [8]. In an alternative model, the 2.9 eV band was attributed to transition from the deep donor VN Mg ( substitution Mg for N vacancy ) to the shallow acceptor [7, 12, 16]. The width of the emission band related to the deep point defect can be explained by the strength of the electron-phonon coupling and energy of the zero vibrational state of the defect. The full width at half-maximum (FWHM) for the blue emission bands

Fig. 2. Typical SIMS depth proles of Ga, N, Fe and Cr for GaN crystal grown by (a) SUS cell (b) Inconel cell.

Growth and Impurity Study of GaN Single Crystal Grown by Na Flux Sang Eon Park et al.

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Fig. 3. PL spectra of the GaN crystal grown by a ux method inside SUS cell.

is described by a conguration coordinate model [12,17], as follows ; W(T) = W(0) coth( o e ) 2kT (1)

where o e is the energy of the excited phonon. The FWHM of the BL emission was tted by the above equation with the results of experiments, as shown in Fig. 4. The Gaussian t yielded each maximum for all the measured samples. The value of W(0) and o e is 515 meV and 48.7 meV, respectively. The BL peak may arise from complexes of extended defects and native-point defects or impurities. The transition between impurities related to deep level shows generally a broad peak and quenching of the PL intensity. Thermal quenching of this band begins at T > 200K. The impurities related to elements of the SUSTM cell may explain all the defect-related sub-bandgap PL bands showing strong electron-lattice coupling. The tem-

perature dependence of the BL band energy is also not consistent with Varshnis equation including the relaxation of lattice and participation of phonons [18]. In the case of the InconelTM cell, as shown in Fig. 5, there are two PL peaks, the near band to band transition at 3.4 eV and DAP luminescence with phonon replica at low temperature. The intensity of the band-edge emission at 5 K shows several tens times higher than that at room temperature in the case of the GaN grown in the the InconelTM cell, as compared to SUSTM cell. An analysis of the spectra from the SUSTM cell and InconelTM cell has shown that the ne structure is formed by series of sharp peaks, associated with local and lattice phonons, at low temperature. The deep centers involved in DA recombination are suggested to arise from self-compensation and to be vacancy-dopant associates [7]. The blue bands in nominally undoped GaN may arise from distant DA pairs involving residual impurities, as well as the vacancy associates. The phonon replica in the SUSTM cell may be repeated at the energies related to the vibrational state of a point defect. Observation of ne structure enables us to determine the vibrational characteristics of the defect in the ground state [12]. In the case of GaN crystal grown by InconelTM cell, the energy band gap with temperature, E(T), may be tted to the expression of Varshnis equation [18,19] E(T) = E(0)g T2 T + (2)

The parameters and are tting parameters. E(0)g is the energy of the band gap at 0 K. From the tting of Varshnis equation, the dependence of the temperature of the near band edge emission is well dened due to the relaxation of lattice constant, as shown in the inset of Fig. 5. The tting values of and are 4.0 104 eV/K and -810 K, respectively. In the case of GaN crystal grown by SUSTM cell, the temperature dependence of the energy

Fig. 4. Temperature dependence of FWHM of the 2.9 eV band for GaN crystal grown by SUS cell. The blank cycle is a t using a conguration coordinate (CC) model. The inset shows that the Gaussian t yielded each maximum for the sample measured at room temperature.

Fig. 5. PL spectra of the GaN crystal obtained inside the Inconel cell are presented from 5 K to 300 K. The inset shows the t of Varshnis equation according to the near band edge emission.

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Journal of the Korean Physical Society, Vol. 42, February 2003 [3] S. D. Lester, F. A. Ponce, M. G. Craford and D. A. Steigerwald, Appl. Phys. Lett. 66, 1249 (1995). [4] M. Koike, S. Yamasaki, S. Nagai, N. Koide, S. Asami, H. Amamo and I. Akassaki, Appl. Phys. Lett. 68, 1403 (1996). [5] I. Grzegory, Mat. Sci. Eng. B 82, 30 (2001). [6] S. J. Chung, O. H. Cha, C-H. Hong, E-K. Suh, H. J. Lee, Y. S. Kim and B. H. Kim, J. Korean Phys. Soc. 37, 1003 (2000). [7] U. Kaufmann, M. Kunzer, H. Obloh, M. Majer, Ch. Manz, A. Ramakrishman and B. Santic, Phys. Rev. B 59, 5561 (1999). [8] S. J. Xu, G. Li, S. j. Chua, X. C. Wang and W. Wang, Appl. Phys. Lett. 72, 2451 (1998). [9] E. F. Schubert, I. D. Goepfert and J. M. Redwing, Appl. Phys. Lett. 71, 3224 (1997). [10] S. K. Noh, C. R. Lee, S. E. Park, I. H. Lee, I. H. Choi, S. J. Son, K. Y. Lim and H. J. Lee, J. Korean Phys. Soc. 32, 851 (1998). [11] G. Popovici, G. Y. Xu, A. Botchkarev, W. Kim, H. Tang, A. Salvador, H. Morkoc, R. Strange and J. O. White, J. Appl. Phys. 82, 4020 (1997). [12] M. A. Reshchikov, F. Shahedipour, R. Y. Korotkov, B. W. Wessels and M. P. Ulmer, J. Appl. Phys. 87, 3351 (2000). [13] C. -R. Cho, S. E. Park, Y. C. Cho and S. -Y. Jeong, Mater. Res. Soc. Symp. Proc. 680E, 9.10 (2001). [14] H. Yamane, M. Shimada, T. Sekiguchi and F. J. DiSalvo, J. Crystal Growth 186, 8 (1998). [15] I. K. Shmagin, J. F. Muth, J. H. Lee, R. M. Kolbas, C. M. Balkas, Z. Sitar and R. F. Davis, Appl. Phys. Lett. 71, 455 (1997). [16] M. A. Reshchikov, G. C. Yi and B. W. Wessels, Phys. Rev. B 59, 13176 (1999). [17] C. C. Klick and J. H. Schulman, Luminescence in Solids in Solid Sate Physics (Academic Press, New York, 1957), Vol. 5. [18] Y. P. Varshni, Physica, 34, 149 (1967). [19] B. Monemar, Phys. Rev. B 10, 676 (1974).

band gap is also consistent with Varshnis equation. The tting values of and are 2.0 103 eV/K and -3500 K, respectively. Since comes out negative, no physical meaning can be ascribed to this relation for GaN [19].

IV. SUMMARY The BL emissions were almost eliminated by simply exchanging the growth cell for an Inconel cell as the result of reduced quantities of Fe, Cr. From the correlation between PL and the impurities of GaN for two kinds of growth cell conditions, it has been veried that the impurity incorporation should depend on the elements of cell material. Impurities related to ingredients of the growth cell are readily incorporated into GaN single crystal grown by Na ux. It is necessary to carry out a further study on whether the DAP emission originates from recombination between shallow donors and shallow acceptors, such as Fe, Cr, and vacancy-dopant associates.

ACKNOWLEDGMENTS This work was supported by grant No. R14-2002-02901000-0 from the ABRL Program of the Korea Science & Engineering Foundation and in part by Korea Research Foundation Grant(KRF-2000-DP0105).

REFERENCES
[1] S. Nakamura and G. Fasol, The blue laser diodes GaN Based Light Emitters and Lasers (Springer-Verlag, Berlin, 1997). [2] I. Ferguson, M. Schurman and I. Eliashevich, J. Korean Phys. Soc. 39, S433 (2001).