WO2013192001A1 - Plasma-assisted atomic layer epitaxy of cubic and hexagonal inn films and its alloys with ain at low temperatures - Google Patents

Plasma-assisted atomic layer epitaxy of cubic and hexagonal inn films and its alloys with ain at low temperatures Download PDF

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WO2013192001A1
WO2013192001A1 PCT/US2013/045569 US2013045569W WO2013192001A1 WO 2013192001 A1 WO2013192001 A1 WO 2013192001A1 US 2013045569 W US2013045569 W US 2013045569W WO 2013192001 A1 WO2013192001 A1 WO 2013192001A1
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inn
cubic
hexagonal
nitrogen
plasma
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Neeraj Nepal
Charles R. EDDY
Nadeemmullah A. MAHADIK
Syed B. Qadri
Michael J. MEHL
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US Department of Navy
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Priority to CN201380032385.3A priority patent/CN104471676B/en
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides

Definitions

  • indium nitride has the smallest direct band gap, largest electron saturation velocity and mobility, and smallest electron effective mass. It has long been an attractive semiconductor material for application in optical, electrical, and optoelectronic device technologies such as solar-cells and high electron mobility and high frequency devices.
  • the most thermodynamically stable phase of the InN is a wurtzite structure (a hexagonal phase), however, the growth of zincblende (a cubic phase) InN on InAs/GaAs has been
  • Cubic InN has a smaller band gap and superior electronic properties as its lattice is isotropic and possesses lower phonon scattering.
  • a method for growing indium nitride (InN) materials comprises growing hexagonal and/or cubic InN using a pulsed growth method at a temperature lower than 300 °C
  • FIG. 1 shows variation of growth rate (GR) and In/N ratio with a
  • TMI trimethylindium
  • FIG. 3 shows a schematic of the possible structure of a face centered cubic (fee) InN phase and how it would align to an a-plane sapphire unit cell.
  • FIG. 4 depicts the variation of Al content in Al x In 1-x N with the AIN/InN cycles ratios in the whole range of x as determined by x-ray photoelectron spectroscopy.
  • A1N and InN layers were grown as claimed in claims 1-5. First the InN was grown on GaN and then the A1N. Number of layers of InN and A1N were varied to get required concentration of Al content;
  • low temperature means temperatures lower than 300 °C, and if otherwise specified can refer to yet lower temperatures such as lower than 280 °C, lower than 260 °C, lower than 240 °C, lower than 220 °C, lower than 200 °C, lower than 180 °C, and so on.
  • Indium precursors include trimethylindium (TMI) and others known in the art.
  • Aluminum precursor includes trimethylaluminum (TMA) and others known in the art.
  • the term “and/or” includes any and all combinations of one or more of the associated listed items.
  • the term “about” when used in conjunction with a stated numerical value or range denotes somewhat more or somewhat less than the stated value or range, to within a range of +10% of that stated.
  • Fiji 200 atomic layer deposition/epitaxy (ALE) system on a-plane sapphire, semi-insulating Si(l l l), and GaN/sapphire templates. Sapphire substrates were used to ensure unambiguous
  • FIG. 1 shows variation of growth rate (GR) and In/N ratio with a
  • TMI trimethylindium
  • the GR was decreased from 0.83 to 0.73 A with increasing temperature from 160 to 183 °C. It remains constant for a small temperature window and decreases again to 0.51 A at 220 °C.
  • T g between 220-260 °C
  • the GR remains constant.
  • the temperature range between 220-260 °C is the second atomic layer epitaxy (ALE) window.
  • ALE atomic layer epitaxy
  • InN growth is N-rich (In/N ⁇ 1) and it is In-rich ( In/N > 1) for the high temperature ALE window.
  • An In/N ratio of 2.8+0.7 has been measured on MBE grown InN (see Piper et al., J. Vac. Sci. Technol.
  • T g 183°C
  • T g 240°C
  • 183°C bottom
  • the third order peak was examined, which was not measurable since it occurs at much higher angles and the sample is only 60 nm thick. Also, the d-spacings of the first two peaks do not match to any InN phases in the ICDD database. The results suggest that the InN on a sapphire at 183 °C has a highly oriented epitaxial structure. Further analysis of the data reveals that the d spacings (6.68 A) of the first peak do not match to any of the known InN phases in the reported international center for diffraction data (ICDD) database and instead corresponds to a face centered cubic (FCC) structure which has not been reported before. The XRD data was corroborated by electron microscopy as described in Cryst. Growth Des. 2013, 13, 1485-1490, incorporated herein by reference.
  • FIG. 3 shows a schematic of the alignment of a face centered cubic (fee) InN phase unit cell with an a-plane sapphire substrate unit cell. From the measured lattice parameter of the InN film assuming the FCC structure, we see that it has only a 2.8% mismatch with the in-plane c-direction and a 18.9% mismatch with the in-plane m-direction of sapphire. This is further indication that this is the most likely phase of the grown InN film on a-plane sapphire.
  • Table 1 summarizes different parameters and their values to synthesize various materials.
  • Each ALE cycle consisted of first a 60 ms trimethylindium (TMI) pulse (which was empirically found as self-limited ALE growth mode, with longer pulses not providing significantly greater growth), which were added to a constant 30 and 100 seem flow of UHP argon carrier gas. After each TMI pulse, the main pumping valve was closed for 5 sec so that the surface would saturate with In atoms. A 20 second long 300 watt N 2 plasma exposure was used to provide nitrogen precursor to the indium saturated surface. To remove unreacted precursors, the deposition chamber was purged with UHP argon for 10 s after each pulse. The reactor chuck was heated resistively, and the temperature was calibrated using thermocouple and by pyrometer by CNT. The values of parameters given are examples. Other values are possible.
  • AlInN ternary alloys are realized over the entire desired stoichiometry range - this is believed to be the first time this was accomplished.
  • the values of parameters given are examples. Other values are possible.
  • Table 1 growth parameters for ALE of InN

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

Described herein is a method for growing indium nitride (InN) materials by growing hexagonal and/or cubic InN using a pulsed growth method at a temperature lower than 300 °C. Also described is a material comprising InN in a face-centered cubic lattice crystalline structure having an NaCl type phase.

Description

TITLE
Plasma-Assisted Atomic Layer Epitaxy of Cubic and Hexagonal InN and its alloys with A1N at Low Temperatures
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This Application claims the benefit of U.S. Provisional Application 61/661,016 filed on June 18, 2012.
BACKGROUND
[0002] Among Ill-nitride semiconductors, indium nitride (InN) has the smallest direct band gap, largest electron saturation velocity and mobility, and smallest electron effective mass. It has long been an attractive semiconductor material for application in optical, electrical, and optoelectronic device technologies such as solar-cells and high electron mobility and high frequency devices. The most thermodynamically stable phase of the InN is a wurtzite structure (a hexagonal phase), however, the growth of zincblende (a cubic phase) InN on InAs/GaAs has been
demonstrated at 450 °C by plasma assisted molecular beam epitaxy (MBE) . Cubic InN has a smaller band gap and superior electronic properties as its lattice is isotropic and possesses lower phonon scattering.
BRIEF SUMMARY
[0003] In one embodiment, a method for growing indium nitride (InN) materials, comprises growing hexagonal and/or cubic InN using a pulsed growth method at a temperature lower than 300 °C
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] FIG. 1 shows variation of growth rate (GR) and In/N ratio with a
trimethylindium (TMI) pulse of 0.06 seconds.
[0005] FIG. 2 depicts the x-ray diffraction (XRD) peaks from three of the samples - namely InN (60nm) on GaN/Al203 template with Tg=183°C (top) and on a-plane A1203 with Tg= 240°C (middle) and 183°C (bottom)). [0006] FIG. 3 shows a schematic of the possible structure of a face centered cubic (fee) InN phase and how it would align to an a-plane sapphire unit cell.
[0007] FIG. 4 depicts the variation of Al content in AlxIn1-xN with the AIN/InN cycles ratios in the whole range of x as determined by x-ray photoelectron spectroscopy. A1N and InN layers were grown as claimed in claims 1-5. First the InN was grown on GaN and then the A1N. Number of layers of InN and A1N were varied to get required concentration of Al content;
DETAILED DESCRIPTION
Definitions
[0008] Before describing the present invention in detail, it is to be understood that the terminology used in the specification is for the purpose of describing particular embodiments, and is not necessarily intended to be limiting. Although many methods, structures and materials similar, modified, or equivalent to those described herein can be used in the practice of the present invention without undue experimentation, the preferred methods, structures and materials are described herein. In describing and claiming the present invention, the following terminology will be used in accordance with the definitions set out below.
[0009] As used herein, "low temperature" means temperatures lower than 300 °C, and if otherwise specified can refer to yet lower temperatures such as lower than 280 °C, lower than 260 °C, lower than 240 °C, lower than 220 °C, lower than 200 °C, lower than 180 °C, and so on.
[0010] Indium precursors include trimethylindium (TMI) and others known in the art. [0011] Aluminum precursor includes trimethylaluminum (TMA) and others known in the art.
[0012] As used in this specification and the appended claims, the singular forms "a", "an," and "the" do not preclude plural referents, unless the content clearly dictates otherwise.
[0013] As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. [0014] As used herein, the term "about" when used in conjunction with a stated numerical value or range denotes somewhat more or somewhat less than the stated value or range, to within a range of +10% of that stated.
Description [0015] InN layers were simultaneously grown using a Cambridge Nano Tech (CNT)
Fiji 200 atomic layer deposition/epitaxy (ALE) system on a-plane sapphire, semi-insulating Si(l l l), and GaN/sapphire templates. Sapphire substrates were used to ensure unambiguous
characterization of the electrical transport properties of the ALE InN layers on an insulator. Wafers were solvent cleaned and rinsed with deionized (DI) water before any further surface pretreatments. Si(l 11), GaN/sapphire, and sapphire surfaces were pretreated with HF, HF and 15% HC1, and solvents, respectively. The growth was carried out in an ultrahigh purity (UHP) argon (Ar) ambient. After ex situ surface pretreatment, substrates were treated with the 50 seem N2 plasma at 300 watts before InN growth. About 150 to 1100 cycles of ALE deposition (see below) were used to synthesize InN films on different substrates simultaneously. The values of parameters given in this paragraph are examples, with other values possible.
[0016] FIG. 1 shows variation of growth rate (GR) and In/N ratio with a
trimethylindium (TMI) pulse of 0.06 seconds. The GR was decreased from 0.83 to 0.73 A with increasing temperature from 160 to 183 °C. It remains constant for a small temperature window and decreases again to 0.51 A at 220 °C. For Tg between 220-260 °C, the GR remains constant. The temperature range between 220-260 °C is the second atomic layer epitaxy (ALE) window. In the first low temperature ALE window the InN growth is N-rich (In/N <1) and it is In-rich ( In/N > 1) for the high temperature ALE window. An In/N ratio of 2.8+0.7 has been measured on MBE grown InN (see Piper et al., J. Vac. Sci. Technol. A 23, 617 (2005)). Thus, the ALE InN has better stoichiometry. [0017] FIG. 2 depicts the XRD peaks from three of the samples - namely InN (60nm) on GaN/Al203 template with Tg=183°C (top) and on a-plane A1203 with Tg= 240°C (middle) and 183°C (bottom)). In the bottom plot, there are a set of peaks that could be indexed to either a face centered cubic (FCC) structure with the (200) and (400) indices, or a CsCl structure with (110) and (220) indices. Also measured were the 24 hr long Laue diffraction (LD) patterns on this sample in transmission as well as grazing incidence reflection mode. In both modes Laue spots were observed, indicating that this sample has an epitaxial nature and not a powder/polycrystalline nature. This is also confirmed with the second order peak in the bottom plot which has resolved in the KcCi and K<¾ components (inset). This peak is obtained via a 15 summation scan to enhance the signal. The FWHM values are 494 and 371 arc-sees for the first and second order peaks, respectively. The first order peak is a convolution of the two Kcc components. In order to confirm the structure, the third order peak was examined, which was not measurable since it occurs at much higher angles and the sample is only 60 nm thick. Also, the d-spacings of the first two peaks do not match to any InN phases in the ICDD database. The results suggest that the InN on a sapphire at 183 °C has a highly oriented epitaxial structure. Further analysis of the data reveals that the d spacings (6.68 A) of the first peak do not match to any of the known InN phases in the reported international center for diffraction data (ICDD) database and instead corresponds to a face centered cubic (FCC) structure which has not been reported before. The XRD data was corroborated by electron microscopy as described in Cryst. Growth Des. 2013, 13, 1485-1490, incorporated herein by reference.
[0018] FIG. 3 shows a schematic of the alignment of a face centered cubic (fee) InN phase unit cell with an a-plane sapphire substrate unit cell. From the measured lattice parameter of the InN film assuming the FCC structure, we see that it has only a 2.8% mismatch with the in-plane c-direction and a 18.9% mismatch with the in-plane m-direction of sapphire. This is further indication that this is the most likely phase of the grown InN film on a-plane sapphire.
[0019] There has been a previous report {see ref. 21) of cubic InN growth at 450 °C by plasma-assisted molecular beam epitaxy (MBE) on InAs/GaAs, but the InN is demonstrated to have a ZnS (zincblende) phase rather than a NaCl-type phase as obtained herein.
[0020] Table 1 summarizes different parameters and their values to synthesize various materials. Each ALE cycle consisted of first a 60 ms trimethylindium (TMI) pulse (which was empirically found as self-limited ALE growth mode, with longer pulses not providing significantly greater growth), which were added to a constant 30 and 100 seem flow of UHP argon carrier gas. After each TMI pulse, the main pumping valve was closed for 5 sec so that the surface would saturate with In atoms. A 20 second long 300 watt N2 plasma exposure was used to provide nitrogen precursor to the indium saturated surface. To remove unreacted precursors, the deposition chamber was purged with UHP argon for 10 s after each pulse. The reactor chuck was heated resistively, and the temperature was calibrated using thermocouple and by pyrometer by CNT. The values of parameters given are examples. Other values are possible.
[0021] For the ALE growth of AlInN, In and A1N layers were grown layer by layer in the fashion of a digital alloy. To grow Alo.90Ino.ioN, A1N and InN were grown alternatively. For an A1N for every two cycles of InN results Alo.79Ino.21N. For an A1N for every three cycles of InN results Alo.68lno.32N. Thus by changing the combination of number layers of InN and A1N, AlxIni_ XN films can be obtained in for a wide range of x via atomic layer epitaxy. In this manner, AlInN ternary alloys are realized over the entire desired stoichiometry range - this is believed to be the first time this was accomplished. The values of parameters given are examples. Other values are possible.
Table 1 : growth parameters for ALE of InN
Figure imgf000007_0001
Table II: growth parameters for ALE of A1N
Figure imgf000007_0002
[0022] The techniques described herein are expected to provide a crystalline material having low oxygen impurity by ex situ and in situ surface treatment. Moreover, in situ surface treatment with the atomic hydrogen, nitrogen, mixture of hydrogen and nitrogen, and/or ammonia plasma is possible. It is possible to vary purge time with the pumping speed in order to control carbon impurities.
Concluding Remarks [0023] All documents mentioned herein are hereby incorporated by reference for the purpose of disclosing and describing the particular materials and methodologies for which the document was cited.
[0024] Although the present invention has been described in connection with preferred embodiments thereof, it will be appreciated by those skilled in the art that additions, deletions, modifications, and substitutions not specifically described may be made without departing from the spirit and scope of the invention. Terminology used herein should not be construed as being "means-plus-function" language unless the term "means" is expressly used in association therewith.
References
Each of the following is incorporated herein by reference, particularly for the teaching for which it was cited.
1. Y. Nanishi, Y. Saito, and T. Yamaguchi, Jpn. J. Appl. Phys. 42, 2549 (2003) and the
references therein.
2. A. G. Bhuiyan, A. Hashimoto, and A. Yamamoto, J. Appl. Phys. 94, 2779 (2003).
3. N. Dietz, M. Alevli, V. Woods, M. Strassburg, H. Kang, and I. T. Ferguson, Phys. Status Solidi B 242, 2985 (2005).
4. R. P. Bhatta, B. D. Thorns, A. Weerasekera, A. G. U. Perera, M. Alevli, and N. Dietz, J.
Vac. Sci. Technol. 25, 967 (2007).
5. Shou-Yi Kuo, Fang-I Lai, Wei-Chun Chen, Woei-Tyng Lin, Chien-Nan Hsiao, Hsin-I Lin, and Han-Chang Pan, Diamond & Related Materials 20, 1188 (2011).
6. M. A. Hafez and H. E. Elsayed-Ali, J. Vac. Sci. Technol. A 27, 696 (2009).
7. K. S. Boutros, F. G. Mcintosh, J. C. Roberts, S. M. Bedair, E. L. Piner, and N. A. El- Masry. Appl. Phys. Lett. 67, 1856 (1995). C. Ozgit, I. Donmez, M. Alevli, and N. Biyikli, J. Vac. Sci. Technol. A 30, 01A124 (2012).
N. H. Karam, T. Parodos, P. Colter, D. McNulty, W. Rowland, J. Schetzina, N. El-Masry, and S. M. Bedair, Appl. Phys. Lett. 67, 94 (1995).
K. Kim, N. Kwak, and S. Lee, Electron. Mater. Lett. 5, 83 (2009).
M. Alevli, C. Ozgit, I. Donmez, and N. Biyikli, Phys. Status Solidi A 209, 266 (2012). O. Ambacher, M. S. Brandt, R. Dimitrov, T. Metzger, M. Stutzmann, R. A. Fischer, A. Miehr, A. Bergmaier, and G. Dollinger, J. Vac. Sci. Technol. B 14, 3532 (1996). InN dissociation temp 630
M. Y. Duan, L He, M. Xu, M. Y. Xu, Shuyan Xu, and K. Ostrikov, Phys. Rev. B 81, 033102 (2010).
A. Yamamoto, T. Shin-ya, T. Sugiura, A. Hashimoto, J. Cryst. Growth, 189/190, 461 (1998).
J. G. Lozano, F. M. Morales, R. Garcia, D. Gonzalez, V. Lebedev, Ch. Y. Wang, V. Cimalla, and O Ambacher, Appl. Phys. Lett. 90, 091901 (2007).
A. Janotti and C, G. Van de Walle, Appl. Phys. Lett. 92, 032104 (2008).
L. F. J. Piper, T. D. Veal, M. Walker, I. Mahboob, C. F. McConville, H. Lu, and W. J. Schaff, J. Vac. Sci. Technol. A 23, 617 (2005)
C. G. Van de Walle, J. L. Lyons, and A. Janotti, Solidi A 207, 1024 (2010).
T. Matsuoka, H. Okamoto, M. Nakao, H. Harima, and E. Kurimoto, Appl. Phys. Lett. 81, 1246 (2002).
M. C. Lee, H. C. Lin, Y. C. Pan, C. K. Shu, J. Ou, W. H. Chen, and W. K. Chen, Appl. Phys. Lett. 73, 2606 (1998).
A.P. Lima, A. Tabata, J.R. Leite, S. Kaiser, D. Schikora, B. Schottker, T. Frey, D.J. As, and K. Lischka, J. Cryst. Growth, 201/202, 396 (1999).

Claims

CLAIMS What is claimed is:
1. A method for growing indium nitride (InN) materials, comprising growing hexagonal and/or cubic InN using a pulsed growth method at a temperature lower than 300 °C.
2. The method of Claim 1, using N2 plasma as a nitrogen precursor.
3. The method of Claim 1, using trimethylindium as an indium precursor.
4. The method of Claim 1, wherein said hexagonal and/or cubic InN consists of a homogenous phase of either hexagonal or cubic InN.
5. The method of Claim 1, wherein said temperature is intentionally varied during said growing in order to control conductivity of said hexagonal and/or cubic InN.
6. The method of Claim 1, further comprising in situ surface treatment with atomic hydrogen, nitrogen, a mixture of hydrogen and nitrogen, and/or ammonia plasma.
7. The method of Claim 1, further comprising variation of purge time with the pumping speed, thereby controlling formation of carbon impurities.
8. The method of Claim 1, wherein said temperature is lower than 200 °C.
9. The method of Claim 8, using N2 plasma as a nitrogen precursor.
10. The method of Claim 8, wherein said hexagonal and/or cubic InN consists of a homogenous phase of either hexagonal or cubic InN.
11. The method of Claim 8, wherein said temperature is intentionally varied during said growing in order to control conductivity of said hexagonal and/or cubic InN.
12. The method of Claim 8, further comprising in situ surface treatment with atomic hydrogen, nitrogen, a mixture of hydrogen and nitrogen, and/or ammonia plasma.
13. The method of Claim 8, further comprising variation of purge time with the pumping speed, thereby controlling formation of carbon impurities.
14. The method of Claim 1, wherein said pulsed growth method comprises pulsed growth of an film at a temperature lower than 300 °C by via alternate pulses of indium precursor and nitrogen precursor.
15. The method of Claim 14, using N2 plasma as said nitrogen precursor.
16. The method of Claim 14, wherein said film has a homogenous phase.
17. The method of Claim 14, further comprising in situ surface treatment with atomic hydrogen, nitrogen, a mixture of hydrogen and nitrogen, and/or ammonia plasma.
18. The method of Claim 14, further comprising variation of purge time with the pumping
speed, thereby controlling formation of carbon impurities.
19. A material comprising InN in a face-centered cubic lattice crystalline structure having an NaCl type phase.
PCT/US2013/045569 2012-06-18 2013-06-13 Plasma-assisted atomic layer epitaxy of cubic and hexagonal inn films and its alloys with ain at low temperatures Ceased WO2013192001A1 (en)

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JP2015517411A JP2015525484A (en) 2012-06-18 2013-06-13 Plasma-assisted atomic layer epitaxy of cubic and hexagonal InN and its alloys with AlN at low temperatures
SG11201408484TA SG11201408484TA (en) 2012-06-18 2013-06-13 Plasma-assisted atomic layer epitaxy of cubic and hexagonal inn films and its alloys with ain at low temperatures
EP13806353.2A EP2862199A4 (en) 2012-06-18 2013-06-13 PLASMA-ASSISTED ATOMIC LAYER EPITAXY OF CUBIC AND HEXAGONIC INN FILMS AND ITS ALLOYS WITH LOW-TEMPERATURE ALN
CN201380032385.3A CN104471676B (en) 2012-06-18 2013-06-13 Plasma-assisted atomic layer epitaxy of cubic and hexagonal InN and its alloys with AlN at low temperature

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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10347722B2 (en) * 2015-03-04 2019-07-09 Lehigh University Artificially engineered III-nitride digital alloy
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CN113897677B (en) * 2021-09-30 2023-04-28 中国科学院苏州纳米技术与纳米仿生研究所 Indium nitride crystal and method for growing same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007254175A (en) * 2006-03-20 2007-10-04 Univ Of Tokushima Group III nitride semiconductor thin film and group III nitride semiconductor light emitting device
US20070257264A1 (en) * 2005-11-10 2007-11-08 Hersee Stephen D CATALYST-FREE GROWTH OF GaN NANOSCALE NEEDLES AND APPLICATION IN InGaN/GaN VISIBLE LEDS
US7521274B2 (en) * 2006-03-10 2009-04-21 Stc.Unm Pulsed growth of catalyst-free growth of GaN nanowires and application in group III nitride semiconductor bulk material
KR20090107403A (en) * 2007-02-09 2009-10-13 나노간 리미티드 Semiconductor device and manufacturing method thereof
US20110147791A1 (en) * 2009-12-21 2011-06-23 Alliance For Sustainable Energy, Llc Growth of coincident site lattice matched semiconductor layers and devices on crystalline substrates

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61260622A (en) * 1985-05-15 1986-11-18 Res Dev Corp Of Japan Growth for gaas single crystal thin film
JP3752810B2 (en) * 1997-11-26 2006-03-08 昭和電工株式会社 Epitaxial wafer, manufacturing method thereof, and semiconductor device
JP4214585B2 (en) * 1998-04-24 2009-01-28 富士ゼロックス株式会社 Semiconductor device, semiconductor device manufacturing method and manufacturing apparatus
JP3898575B2 (en) * 2002-06-12 2007-03-28 ソニー株式会社 Method for forming GaInN layer
CN101443887B (en) * 2006-03-10 2011-04-20 Stc.Unm公司 Pulsed growth of GAN nanowires and applications in group III nitride semiconductor substrate materials and devices
JPWO2007119433A1 (en) * 2006-03-20 2009-08-27 財団法人神奈川科学技術アカデミー III-V nitride layer and method for producing the same
JP2007284305A (en) * 2006-04-18 2007-11-01 Osaka Univ Magnetic alkaline earth metal nitride and method for producing the same
JP2008177525A (en) * 2006-12-20 2008-07-31 Showa Denko Kk Group III nitride semiconductor light emitting device manufacturing method, group III nitride semiconductor light emitting device, and lamp
JP2008177523A (en) * 2006-12-20 2008-07-31 Showa Denko Kk Method for producing group III nitride compound semiconductor light emitting device, group III nitride compound semiconductor light emitting device, and lamp
CN101445956A (en) * 2007-11-28 2009-06-03 中国科学院半导体研究所 Method for epitaxial growth of nitride films
US20100038656A1 (en) * 2008-08-04 2010-02-18 Goldeneye Nitride LEDs based on thick templates
US8541817B2 (en) * 2009-11-06 2013-09-24 Nitek, Inc. Multilayer barrier III-nitride transistor for high voltage electronics
JP2011198885A (en) * 2010-03-18 2011-10-06 Mitsui Eng & Shipbuild Co Ltd Atomic layer deposition method and method therefor
US8945305B2 (en) * 2010-08-31 2015-02-03 Micron Technology, Inc. Methods of selectively forming a material using parylene coating
KR101883840B1 (en) * 2011-08-31 2018-08-01 엘지이노텍 주식회사 Light emitting diode

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070257264A1 (en) * 2005-11-10 2007-11-08 Hersee Stephen D CATALYST-FREE GROWTH OF GaN NANOSCALE NEEDLES AND APPLICATION IN InGaN/GaN VISIBLE LEDS
US7521274B2 (en) * 2006-03-10 2009-04-21 Stc.Unm Pulsed growth of catalyst-free growth of GaN nanowires and application in group III nitride semiconductor bulk material
JP2007254175A (en) * 2006-03-20 2007-10-04 Univ Of Tokushima Group III nitride semiconductor thin film and group III nitride semiconductor light emitting device
KR20090107403A (en) * 2007-02-09 2009-10-13 나노간 리미티드 Semiconductor device and manufacturing method thereof
US20110147791A1 (en) * 2009-12-21 2011-06-23 Alliance For Sustainable Energy, Llc Growth of coincident site lattice matched semiconductor layers and devices on crystalline substrates

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
BHUIYAN ASHRAFUL GHANI ET AL., JOURNAL OF APPLIED PHYSICS, vol. 94, no. 5, September 2003 (2003-09-01), pages 2779 - 2808
C. PINQUIER ET AL., PHYSICAL REVIEW. B, CONDENSED MATTER AND MATERIALS PHYSICS, vol. 73, no. 11, March 2006 (2006-03-01)
K. MITAMURA, PHYSICA STATUS SOLIDI. RAPID RESEARCH LETTERS, vol. 1, no. 5, October 2007 (2007-10-01), pages 211 - 213
KELLER S. ET AL., PROCEEDINGS OF INTERNATIONAL WORKSHOP ON NITRIDE SEMICONDUCTORS, 24 September 2000 (2000-09-24), pages 233 - 236
See also references of EP2862199A4
STEFANO ORLANDO ET AL., PHYSICA STATUS SOLIDI. C, vol. 9, no. 3-4, 13 March 2012 (2012-03-13), pages 993 - 996
ZHANG ET AL., APPLIED PHYSICS LETTERS, vol. 79, no. 7, 13 August 2001 (2001-08-13), pages 915 - 917

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