The InN epitaxy via controlling In bilayer
© Zhou et al.; licensee Springer. 2014
Received: 3 November 2013
Accepted: 18 December 2013
Published: 6 January 2014
The method of In bilayer pre-deposition and penetrated nitridation had been proposed, which had been proven to have many advantages theoretically. To study the growth behavior of this method experimentally, various pulse times of trimethylindium supply were used to get the optimal indium bilayer controlling by metalorganic vapour phase epitaxy. The results revealed that the InN film quality became better as the thickness of the top indium atomic layers was close to bilayer. A following tuning of nitridation process enhanced the quality of InN film further, which means that a moderate, stable, and slow nitridation process by NH3 flow also plays the key role in growing better-quality InN film. Meanwhile, the biaxial strain of InN film was gradually relaxing when the flatness was increasingly improved.
KeywordsInN epitaxy MOVPE Bilayer control Penetrated nitridation
The unique properties of InN are currently attracting much interest in the research community [1, 2]. Because of its lowest effective mass and the highest electron drift velocity among all III-nitride semiconductors , InN is promising for high-speed and high-frequency electronic devices. And recently, the band gap of InN, which is considered as 1.9 eV, is renewed to approximately 0.7 eV [4–6], covering a broad range of wavelength from near infrared at approximately 1.5 μm to ultraviolet at approximately 200 nm based on its direct band gap alloying with GaN and AlN [7–9]. However, the achievement of high crystalline quality InN film is still a great challenge, which attributed to the lack of lattice-matched substrate, the low dissociation temperature (approximately 600°C), the low pyrolysis efficiency of NH3 at 500 to 600°C, the pre-reaction of the precursors before arriving at the substrate surface, and also the InN clustering effect [10–14].
In order to achieve high-quality InN film, effort has been made by researchers with different methods such as optimizing growth temperature, controlling V/III ratio, introducing buffer layer, or employing pulsed atomic layer epitaxy technique [15, 16]. However, the crystalline quality of InN film is still far below a satisfactory level due to the existence of huge quantity of defects . To elucidate the original difficulty in In film deposition, the formation kinetics of InN with N and In atoms on the In polar GaN surface has been systematically studied by first-principles calculations , it was found that the pre-deposition of In bilayer on the surface could improve the In migration on the surface and the smoothness of In film.
In this work, the epitaxy method of In bilayer controlling and penetrated nitridation was employed for the InN film growth on GaN template. In order to determine critical trimethylindium (TMI) flow required for forming In bilayer, the pulse time of TMI supply was optimized. The results revealed that the film quality became better as the thickness of the top indium atomic layers was close to bilayer. Based on the In bilayer deposition, a moderate, stable, and slow nitridation process by NH3 flow also played the key role in growing better-quality InN film. X-ray diffraction (XRD) measurements confirmed the gradual relaxation of biaxial strain in InN epilayers during increment of the smoothness.
Growth of samples
The thickness of film was measured by in situ growth monitoring curves (Panalytical X'pert PRO X, Panalytical, Almelo, The Netherlands). The surface morphology and smoothness of the as-grown samples were characterized by atomic force microscopy (AFM, PicoSPM and PSI XE-100, Molecular Imaging, Ann Arbor, MI, USA) and scanning electron microscopy (SEM, LEO 1530, LEO Elektronenmikroskopie GmbH, Oberkochen, Germany) equipped with an energy-dispersive X-ray spectrometer (EDX). The structural quality and the In composition of InN films were evaluated by X-ray diffraction (XRD) in a X’ Pert PRO system.
Results and discussion
Figure 3 shows the SEM images of surface morphology and cross sections of samples A to D. From the top view of sample A (A1), one can see some obvious dark holes on the surface, indicating the formation of vacancies due to In accumulation in droplets. The formation of holes and droplets easily leads to a pretty rough surface (rms = 33, from AFM scanning result), as shown in Figure 3A2. As we know, the melting temperature of metal In is only about 157°C. Thus, under the growth temperature of InN (550°C), the pulsed deposition of In for a long duration time may form a thick liquid In layer on the surface. By the effect of surface tension, In droplets in large size would come into being quickly. This is the main reason governing the surface roughness. In order to reduce the roughness, the pulse time of TMI is reduced to 8 s for sample B. The obtained InN film shows better flatness (rms = 20) and dark holes have been well removed (Figure 3B2). According to the theoretical simulation of the kinetics of InN formation , if the thickness of indium film is larger than two atomic layers, the nitridation of this In film could not well form a InN epilayers in correct stoichiometric ratio (1:1) and the excessive In will lead to roughness. Thus, the TMI pulse time was further decreased down to 4 s. As shown in Figure 3C1, the islands of sample C begin to show regular shape relatively and the surface becomes more flat (rms = 14). Meanwhile, it can be observed that there are some islands in larger size, as indicated by arrow. The number of these types of large islands further increases in sample D (Figure 3D1), in which the TMI pulse time was set to 3 s. This trend of quality deterioration implies that the indium film deposited during the TMI period turns to be less than one atomic layer and fail to construct indium bilayer. This insufficient coverage of indium layer could not provide the advantage of nitridation of indium bi-layer structure. On the contrary, over-nitridation under N-rich condition leads to the deterioration of the InN film quality of sample D. Therefore, it could be determined that 4-s pulsed supply of TMI in sample C is the optimal setting.
XRD peak position of (002) diffraction and main lattice constants of InN films for our samples
Through using various pulse times of TMI supply, we achieved optimal indium bilayer control by metalorganic vapour phase epitaxy. When the top indium multilayer was getting close to bilayer, InN film quality had been gradually improved due to high surface migration and good structure consistency of indium bilayer forming. The absorption spectra also confirmed that the InN film which was grown via optimal indium pre-deposited controlling had the fewest defects and impurities. Furthermore, an optimization of ammonia flow during the nitridation stage made an extraordinary improvement of the InN film's flatness; it means that based on the In bilayer controlling deposition, a moderate, stable, and slow nitridation process also plays the key role in growing better-quality InN film. Meanwhile, the biaxial strain of InN film was gradually relaxing when the parameters of growth was optimizing, implying that the mismatch stress of InN heteroepitaxy can be well relaxed via this growth method.
This work was partly supported by ‘973’ programs (2012CB619301 and 2011CB925600) and the NNSF (61227009, 11204254, and 91321102).
- Mohammad SN, Morkoc H: Progress and prospects of group-III nitrids semiconductors. Prog Quantum Electron 1996, 20: 361–525. 10.1016/S0079-6727(96)00002-XView ArticleGoogle Scholar
- Gan CK, Srolovitz DJ: First-principles study of wurtzite InN (0001) and (0001̅) surfaces. Phys Rev B 2006, 74: 115319.View ArticleGoogle Scholar
- Chin VWL, Tansley TL, Osotchan T: Electron mobilities in gallium, indium, and aluminum nitrides. J Appl Phys 1994, 75: 7365. 10.1063/1.356650View ArticleGoogle Scholar
- Wu J, Walukiewicz W, Yu KM, Ager JW III, Haller EE, Lu H, Schaff WJ, Saito Y, Nanishi Y: Unusual properties of the fundamental band gap of InN. Appl Phys Lett 2002, 80: 3967. 10.1063/1.1482786View ArticleGoogle Scholar
- Inushima T, Mamutin VV, Vekshinb VA, Ivanov SV, Sakon T, Motokawa M, Ohoya S: Physical properties of InN with the band gap energy of 1.1 eV. J Crystal Growth 2001, 227–228: 481–485.View ArticleGoogle Scholar
- Yu Davydov V, Klochikhin AA, Seisyan RP, Emtsev VV, Ivanov SV, Bechstedt F, Furthmuller J, Harima H, Mudryi AV, Aderhold J, Semchinova O, Graul J: Absorption and emission of hexagonal InN. evidence of narrow fundamental band. Gap Phys Status Solidi (b) 2002, 229: R1. 10.1002/1521-3951(200202)229:3<R1::AID-PSSB99991>3.0.CO;2-OView ArticleGoogle Scholar
- Akasaki I, Amano H, Koide N, Kotaki M, Manabe K: Conductivity control of GaN and fabrication of UV/blue GaN light emitting devices. Physica B 1993, 185: 428. 10.1016/0921-4526(93)90274-AView ArticleGoogle Scholar
- Nakamura S, Senoh M, Mukai T: P-GaN/N-InGaN/N-GaNDouble- heterostructure blue-light-emitting diodes. Jpn J Appl Phys 1993, 32: L8. 10.1143/JJAP.32.L8View ArticleGoogle Scholar
- Nakamura S, Senoh M, Nagahama S, Iwasa N, Yamada T, Matsushita T, Kiyoku H, Sugimoto Y: InGaN-based multi-quantum-well-structure laser diodes. Jpn J Appl Phys 1996, 35: L74. 10.1143/JJAP.35.L74View ArticleGoogle Scholar
- MacChesney JB, Bridenbaugh PM, O’Connor PB: Thermal stability of indium nitride at elevated temperatures and nitrogen pressures. Mater Res Bull 1970, 5: 783. 10.1016/0025-5408(70)90028-0View ArticleGoogle Scholar
- Ambacher O, Brandt MS, Dimitrov R, Metzger T, Stutzmann M, Fischer RA, Miehr A, Bergmaier A, Dollinger G: Thermal stability and desorption of Group III nitrides prepared by metal organic chemical vapor deposition. J Vac Sci Technol B 1996, 14: 3532. 10.1116/1.588793View ArticleGoogle Scholar
- Ganand CK, Srolovitz DJ: First-principles study of wurtzite InN (0001) and (000–1) surfaces. Phys Rev B 2006, 74: 115319.View ArticleGoogle Scholar
- Johnson MC, Konsek SL, Zettl A, Bourret-Courchesne ED: Nucleation and growth of InN thin films using conventional and pulsed MOVPE. J Cryst Growth 2004, 272: 400. 10.1016/j.jcrysgro.2004.08.057View ArticleGoogle Scholar
- Kandalam AK, Blanco MA, Pandey R: Theoretical Study of AlnNn, GanNn, and InnNn (n = 4, 5, 6) Clusters. J Phys Chem B 2002, 106: 1945. 10.1021/jp0140062View ArticleGoogle Scholar
- Wang H, Jinag DS, Zhu JJ, Zhao DG, Liu ZS, Wang YT, Zhang SM, Yang H: The influence of growth temperature and input V/III ratio on the initial nucleation and material properties of InN on GaN by MOCVD. Semicond Sci Technol 2009, 24: 055001. 10.1088/0268-1242/24/5/055001View ArticleGoogle Scholar
- Laskar MR, Ganguli T, Kadir A, Hatui N, Rahman AA, Shah AP, Gokhale MR, Bhattacharya A: Influence of buffer layers on the microstructure of MOVPE grown a-plane InN. J Cryst Growth 2011, 315: 233. 10.1016/j.jcrysgro.2010.08.019View ArticleGoogle Scholar
- Huang Q, Li S, Cai D, Kang J: Kinetic behavior of nitrogen penetration into indium double layer improving the smoothness of InN film. J Appl Phys 2012, 111: 113528. 10.1063/1.4728993View ArticleGoogle Scholar
- Wang X, Chen S, Lin W, Li S, Chen H, Liu D, Kang J: Structural properties of InN films grown in different conditions by metalorganic vapor phase epitaxy. J Mater Res 2011, 26: 775. 10.1557/jmr.2010.87View ArticleGoogle Scholar
- Jones RE, Yu KM, Li SX: [J]: Evidence for p-type doping of InN. Phys Rev Lett 2006, 96: 125505.View ArticleGoogle Scholar
- Denny Kamaruddin H, Koros WJ: Some observations about the application of Fick's first law for membrane separation of multicomponent mixtures. J Membr Sci 1997, 135: 147–159. 10.1016/S0376-7388(97)00142-7View ArticleGoogle Scholar
- Strite S, Morkoc H: GaN, AIN, and InN: a review. J Vac Sci Technol B 1992, 10: 4.Google Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.