Semiconductor device manufacturing: process – Formation of semiconductive active region on any substrate
Reexamination Certificate
2000-02-03
2003-03-04
Mulpuri, Savitri (Department: 2812)
Semiconductor device manufacturing: process
Formation of semiconductive active region on any substrate
C438S479000, C438S483000
Reexamination Certificate
active
06528394
ABSTRACT:
This application claims priority under 35 U.S.C. §§119 and/or 365 to 99-3957 filed in Korea on Feb. 5, 1999; the entire content of which is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method of growing a high quality gallium nitride (GaN) film at a high growth rate, which is useful in applications such as homoepitaxy blue laser diodes or electronic devices.
2. Description of the Related Art
Growth methods used to deposit GaN films on a sapphire substrate can be classified into metal organic vapor phase epitaxy (MOVPE), molecular beam epitaxy (MBE) and hydride vapor phase epitaxy (HVPE). (references: [1] H. P. Maruska and J. J. Tietjin, Appl. Phys. Lett. 15 (1969), pp. 327; [2] H. M. Manasevit, F. M. Erdmann and W. I. Simpson, J. Electrochem. Soc. 118 (1971), pp. 1864; [3] S. Yoshida, S. Misawa and S. Gonda, Appl. Phys. Lett. 42 (1983), pp. 427). Among these three techniques, HVPE has an advantage of a high growth rate, which is several tens of times higher than that of the other two techniques, so that it is suitable for growing a thick film or bulk monocrystalline. However, HVPE cannot provide high quality GaN films with a mirror surface at the high growth rate.
High quality GaN films having a mirror surface have been obtained by MOVPE and by incorporating a buffer layer into the structure. However, MOPVE is not appropriate for growing a thick GaN film due to its low growth rate in the order of 1 &mgr;m/hour. Due to this reason, HVPE has been adapted in GaN film growth on a sapphire substrate in spite of the resulting GaN film having a rough surface and poor crystalline characteristics. Also, to avoid this problem, aluminum nitride (AlN), zinc oxide (ZnO) or low-temperature GaN films have been used as an interface buffer layer, without a distinct quality improvement in the resulting GaN films. (references: [4] H. Amano, N. Sawaki, and Y. Toyada, Appl. Phys. Lett. 48 (1986), pp. 353; [5] S. Nakamura, Jpn. J. Appl. Phys. 30 (1991), pp. 1705; and [6] T. Detchprohm, H. Amano, K. Hiramatsu and I. Akasaki, J. Cryst. Growth 128 (1993), pp. 384).
Conventional procedures for growing GaN films by HVPE are illustrated in FIG.
1
. Referring to
FIG. 1
, first a sapphire substrate is loaded into a reactor for HVPE (S
1
). Then ammonia (NH
3
) reaction gas is supplied onto the substrate for nitridating the surface of the sapphire substrate (S
2
) and then growing a GaN film on the substrate (S
3
). In either case, in the step S
1
, prior to the introduction of the sapphire substrate into the reactor, a buffer layer is grown with AlN or ZnO to a thickness of several hundreds of angstroms by sputtering or chemical vapor deposition (CVD). Then, the steps S
2
and S
3
are carried out. However, the growth of the GaN layer by the HVPE illustrated in
FIG. 1
is not enough, resulting in rough surface characteristics as can be seen in FIG.
2
A. Furthermore, an X-ray rocking curve shown in
FIG. 2B
exhibits poor crystalline characteristics at a full width of half maximum (FWHM) value of 1000 arcsec or more (the GaN film 2 &mgr;m thick) The term “nitridation” refers to the unintentional formation of thin film, for example, an AlN film, on a sapphire substrate by flow of NH
3
reaction gas onto the substrate, but not to intentional formation of a buffer layer of AlN.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method of growing a high quality gallium nitride (GaN) film at a high growth rate, which is able to provide a mirror-like surface by using a modified hydride vapor phase epitaxy (HVPE) technique on the resulting GaN film, wherein good crystalline characteristics can be obtained even at a high growth rate.
In one embodiment, the present invention provides a method of growing a GaN film on a sapphire substrate by HVPE, the method including: loading the sapphire substrate into a reactor; nitridating the resulting sapphire substrate; treating the sapphire substrate by flowing a gas mixture of ammonia (NH
3
) and hydrochloric acid (HCl) onto the sapphire substrate; nitridating the sapphire substrate treated with the gas mixture; and growing the GaN film on the sapphire substrate.
Preferably, a silicon (SiC) carbide substrate, an oxide substrate or a carbide substrate is used in place of the sapphire substrate.
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Maruska, H.P. et al., “The Preparation and Properties of Vapor-Deposited Single-Crystal-Line GaN.” Applied Physics Letters, vol. 15, No. 10, Nov. 15, 1969.
Yoshida, S., et al., “Improvements on the electrical and luminescent properties of reactive molecular beam epitaxially grown GaN films by using AIN-coated sapphire substrates.” Applied Physics Letters, vol. 42, No. 5, Mar. 1, 1983, pp. 427-429.
Amano, H., et al., “Metalorganic vapor phase epitaxial growth of a high quality GaN film using an AIN buffer layer.” Applied Physics Letters, vol. 48, No. 5, Feb. 3, 1986, pp. 353-355.
Nakamura, Shuji, “GaN Growth Using GaN Buffer Layer.” Japanese Journal of Applied Physics, vol. 30, No. 10A, Oct. 1991, pp. L1705--L1707.
Detchprohm, T., et al., “The growth of thick GaN film on sapphire substrate by using ZnO buffer layer.” Journal of Crystal Growth 128 (1993), pp. 384-390.
Manasevit, H.M., et al., “The Use of Metalorganics in the Preparation of Semiconductor Materials.” Metalorganics and Semiconductor Materials, vol. 118, No. 11, Nov. 1971, pp. 1864-1868.
Burns Doane Swecker & Mathis
Mulpuri Savitri
Samsung Electronics Co,. Ltd.
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