Citation:

# Metalorganic chemical vapor deposition of InN quantum dots and nanostructures

• Light: Science & Applications  10, Article number: 5 (2021)
• Corresponding author:
Caroline E. Reilly (cereilly@ucsb.edu)
Revised: 21 June 2021
Accepted: 06 July 2021
Published online: 20 July 2021
• Using one material system from the near infrared into the ultraviolet is an attractive goal, and may be achieved with (In, Al, Ga)N. This Ⅲ-N material system, famous for enabling blue and white solid-state lighting, has been pushing towards longer wavelengths in more recent years. With a bandgap of about 0.7 eV, InN can emit light in the near infrared, potentially overlapping with the part of the electromagnetic spectrum currently dominated by Ⅲ-As and Ⅲ-P technology. As has been the case in these other Ⅲ–Ⅴ material systems, nanostructures such as quantum dots and quantum dashes provide additional benefits towards optoelectronic devices. In the case of InN, these nanostructures have been in the development stage for some time, with more recent developments allowing for InN quantum dots and dashes to be incorporated into larger device structures. This review will detail the current state of metalorganic chemical vapor deposition of InN nanostructures, focusing on how precursor choices, crystallographic orientation, and other growth parameters affect the deposition. The optical properties of InN nanostructures will also be assessed, with an eye towards the fabrication of optoelectronic devices such as light-emitting diodes, laser diodes, and photodetectors.
•  [1] Heinrichsdorff, F. et al. Room-temperature continuous-wave lasing from stacked InAs/GaAs quantum dots grown by metalorganic chemical vapor deposition. Appl. Phys. Lett. 71, 22–24 (1997). doi: 10.1063/1.120556 [2] Duan, J. et al. Semiconductor quantum dot lasers epitaxially grown on silicon with low linewidth enhancement factor. Appl. Phys. Lett. 112, 251111 (2018). [3] Kaiander, I. N. et al. 1.24 μm InGaAs/GaAs quantum dot laser grown by metalorganic chemical vapor deposition using tertiarybutylarsine. Appl. Phys. Lett. 84, 2992–2994 (2004). [4] Alkhazraji, E. et al. Effect of temperature and ridge-width on the lasing characteristics of InAs/InP quantum-dash lasers: a thermal analysis view. Opt. Laser Technol. 98, 67–74 (2018). [5] Pierścińska, D. et al. Above room temperature operation of InGaAs/AlGaAs/GaAs quantum cascade lasers. Semicond. Sci. Technol. 33, 035006 (2018). [6] Nelson, J. et al. Steady-state carrier escape from single quantum wells. IEEE J. Quantum Electron. 29, 1460–1468 (1993). doi: 10.1109/3.234396 [7] Herrmann, K. H., Tomm, J. W. & Al-Otaibi, H. Temperature dependent carrier escape from quantum well states in GaAs/GaAlAs graded index laser structures. Semicond. Sci. Technol. 14, 293–297 (1999). [8] Kapteyn, C. M. A. et al. Electron escape from InAs quantum dots. Phys. Rev. B 60, 14265–14268 (1999). [9] Davydov, V. Y. et al. Band gap of InN and in-rich InxGa1-xN alloys (0.36 < x < 1). Phys. Status Solidi (B) 230, R4–R6 (2002). [10] Van De Walle, C. G. & Neugebauer, J. Universal alignment of hydrogen levels in semiconductors, insulators and solutions. Nature 423, 626–628 (2003). [11] Wu, J. Q. When group-Ⅲ nitrides go infrared: new properties and perspectives. J. Appl. Phys. 106, 011101 (2009). [12] Nötzel, R. InN/InGaN quantum dot electrochemical devices: new solutions for energy and health. Natl Sci. Rev. 4, 184–195 (2017). [13] Mi, Z. T. & Zhao, S. R. Extending group-Ⅲ nitrides to the infrared: recent advances in InN. Phys. Phys. Status Solidi (B) 252, 1050–1062 (2015). [14] Mi, Z. T. et al. High-performance quantum dot lasers and integrated optoelectronics on Si. Proc. IEEE 97, 1239–1249 (2009). [15] Chen, S. M. et al. Electrically pumped continuous-wave Ⅲ–Ⅴ quantum dot lasers on silicon. Nat. Photonics 10, 307–311 (2016). [16] Arakawa, Y. & Sakaki, H. Multidimensional quantum well laser and temperature dependence of its threshold current. Appl. Phys. Lett. 40, 939–941 (1982). doi: 10.1063/1.92959 [17] Asada, M., Miyamoto, Y. & Suematsu, Y. Gain and the threshold of three-dimensional quantum-box lasers. IEEE J. Quantum Electron. 22, 1915–1921 (1986). [18] Suski, T. et al. The discrepancies between theory and experiment in the optical emission of monolayer In(Ga)N quantum wells revisited by transmission electron microscopy. Appl. Phys. Lett. 104, 182103 (2014). [19] Chèze, C. et al. In/GaN(0001)-$(\sqrt 3 \times \sqrt 3 {\mathrm{R}}30^\circ)$ adsorbate structure as a template for embedded (In, Ga)N/GaN monolayers and short-period superlattices. Appl. Phys. Lett. 110, 072104 (2017). [20] Yoshikawa, A. et al. Proposal and achievement of novel structure InN/GaN multiple quantum wells consisting of 1 ML and fractional monolayer InN wells inserted in GaN matrix. Appl. Phys. Lett. 90, 073101 (2007). [21] Yoshikawa, A. et al. Fabrication and characterization of novel monolayer InN quantum wells in a GaN matrix. J. Vac. Sci. Technol. B: Microelectron. Nanometer Struct. Process., Meas., Phenom. 26, 1551–1559 (2008). [22] Gorczyca, I. et al. Theoretical study of nitride short period superlattices. J. Phys.: Condens. Matter 30, 063001 (2018). http://smartsearch.nstl.gov.cn/paper_detail.html?id=4dfd35b0355806d585cf5b5022b3448b [23] Wu, R. Y. et al. Electronic and optical properties of InGaN quantum dot based light emitters for solid state lighting. J. Appl. Phys. 105, 013117 (2009). [24] Ruffenach, S. et al. Recent advances in the MOVPE growth of indium nitride. Phys. Status Solidi (A) 207, 9–18 (2010). [25] Bhuiyan, A. G., Hashimoto, A. & Yamamoto, A. Indium nitride (InN): a review on growth, characterization, and properties. J. Appl. Phys. 94, 2779–2808 (2003). [26] Meissner, C. et al. Volmer-weber growth mode of InN quantum dots on GaN by MOVPE. Phys. Status Solidi C. 6, S545–S548 (2009). [27] Bonef, B. et al. Quantitative investigation of indium distribution in InN wetting layers and dots grown by metalorganic chemical vapor deposition. Appl. Phys. Express 13, 065005 (2020). [28] Rodriguez, P. E. D. S. et al. Near-infrared InN quantum dots on high-In composition InGaN. Appl. Phys. Lett. 102, 131909 (2013). [29] Nörenberg, C. et al. Stranski-Krastanov growth of InN nanostructures on GaN studied by RHEED, STM and AFM. Phys. Status Solidi (A) 194, 536–540 (2002). [30] Chen, H. J. Y. et al. Effects of substrate pre-nitridation and post-nitridation processes on InN quantum dots with crystallinity by droplet epitaxy. Surf. Coat. Technol. 324, 491–497 (2017). [31] Stanchu, H. V. et al. Kinetically controlled transition from 2D nanostructured films to 3D multifaceted InN nanocrystals on GaN(0001). CrystEngComm 20, 1499–1508 (2018). [32] Yoshikawa, A. et al. Growth of InN quantum dots on N-polarity GaN by molecular-beam epitaxy. Appl. Phys. Lett. 86, 153115 (2005). [33] Norman, D. P. et al. Effect of temperature and Ⅴ/Ⅲ ratio on the initial growth of indium nitride using plasma-assisted metal-organic chemical vapor deposition. J. Appl. Phys. 109, 063517 (2011). [34] Yun, S. H. et al. Synthesis of InN nanowires grown on droplets formed with Au and self-catalyst on Si(111) by using metalorganic chemical vapor deposition. J. Mater. Res. 25, 1778–1783 (2010). [35] Kim, E. et al. Length-controlled and selective growth of individual indium nitride nanowires by localized laser heating. Appl. Phys. Express 12, 056501 (2019). [36] Uner, N. B., Niedzwiedzki, D. M. & Thimsen, E. Nonequilibrium plasma aerotaxy of InN nanocrystals and their photonic properties. J. Phys. Chem. C. 123, 30613–30622 (2019). [37] Dhar Dwivedi, S. M. M. et al. Oblique angle deposited InN quantum dots array for infrared detection. J. Alloy. Compd. 766, 297–304 (2018). [38] Chao, C. K. et al. Catalyst-free growth of indium nitride nanorods by chemical-beam epitaxy. Appl. Phys. Lett. 88, 233111 (2006). [39] Song, W. Q. et al. Synthesis and morphology evolution of indium nitride (InN) nanotubes and nanobelts by chemical vapor deposition. CrystEngComm 21, 5356–5362 (2019). [40] Lan, Z. H. et al. Growth mechanism, structure and IR photoluminescence studies of indium nitride nanorods. J. Cryst. Growth 269, 87–94 (2004). [41] Liu, H. Q. et al. Ultrastrong terahertz emission from inn nanopyramids on single crystal ZnO substrates. Adv. Opt. Mater. 5, 1700178 (2017). [42] Madapu, K. K., Polaki, S. R. & Dhara, S. Excitation dependent Raman studies of self-seeded grown InN nanoparticles with different carrier concentration. Phys. Chem. Chem. Phys. 18, 18584–18589 (2016). [43] Liu, H. Q. et al. Controllable synthesis of [11−2−2] faceted InN nanopyramids on ZnO for photoelectrochemical water splitting. Small 14, 1703623 (2018). [44] Briot, O., Maleyre, B. & Ruffenach, S. Indium nitride quantum dots grown by metalorganic vapor phase epitaxy. Appl. Phys. Lett. 83, 2919–2921 (2003). [45] Parish, G. et al. SIMS investigations into the effect of growth conditions on residual impurity and silicon incorporation in GaN and AlxGa1-xN. J. Electron. Mater. 29, 15–20 (2000). [46] Ruffenach, S. et al. Alternative precursors for MOVPE growth of InN and GaN at low temperature. J. Cryst. Growth 311, 2791–2794 (2009). [47] Stringfellow, G. B. Organometallic Vapor-Phase Epitaxy: Theory and Practice 2nd edn. (Academic Press, 1999). [48] Lund, C. et al. Metal-organic chemical vapor deposition of N-polar InN quantum dots and thin films on vicinal GaN. J. Appl. Phys. 123, 055702 (2018). [49] Ivaldi, F. et al. Influence of a GaN cap layer on the morphology and the physical properties of embedded self-organized InN quantum dots on GaN(0001) grown by metal-organic vapour phase epitaxy. Jpn. J. Appl. Phys. 50, 031004 (2011). [50] Ku, C. S., Chou, W. C. & Lee, M. C. Optical investigations of InN nanodots capped by GaN at different temperatures. Appl. Phys. Lett. 90, 132116 (2007). [51] Meissner, C. et al. Indium nitride quantum dot growth modes in metalorganic vapour phase epitaxy. J. Cryst. Growth 310, 4959–4962 (2008). [52] Ruffenach, S. et al. Growth of InN quantum dots by MOVPE. Phys. Status Solidi (C. ) 2, 826–832 (2005). [53] Bi, Z. X. et al. Self-assembled InN quantum dots on side facets of GaN nanowires. J. Appl. Phys. 123, 164302 (2018). [54] Reilly, C. E. et al. MOCVD growth and characterization of InN quantum dots. Phys. Status Solidi (B) 257, 1900508 (2020). [55] Porowski, S. & Grzegory, I. Thermodynamical properties of Ⅲ–Ⅴ nitrides and crystal growth of GaN at high N2 pressure. J. Cryst. Growth 178, 174–188 (1997). [56] Gautier, S. et al. GaN materials growth by MOVPE in a new-design reactor using DMHy and NH3. J. Cryst. Growth 298, 428–432 (2007). [57] Hsu, Y. J., Hong, L. S. & Tsay, J. E. Metalorganic vapor-phase epitaxy of GaN from trimethylgallium and tertiarybutylhydrazine. J. Cryst. Growth 252, 144–151 (2003). [58] Lee, R. T. & Stringfellow, G. B. Pyrolysis of 1, 1 dimethylhydrazine for OMVPE growth. J. Electron. Mater. 28, 963–969 (1999). [59] Sartel, C. et al. Low temperature homoepitaxy of GaN by LP-MOVPE using Dimethylhydrazine and nitrogen. Superlattices Microstruct. 40, 476–482 (2006). [60] Suntola, T. Atomic layer epitaxy. Thin Solid Films 216, 84–89 (1992). [61] Kobayashi, N., Makimoto, T. & Horikoshi, Y. Flow-rate modulation epitaxy of GaAs. Jpn. J. Appl. Phys. 24, L962–L964 (1985). [62] Horikoshi, Y. Advanced epitaxial growth techniques: atomic layer epitaxy and migration-enhanced epitaxy. J. Cryst. Growth 201-202, 150–158 (1999). [63] Karam, N. H. et al. Growth of device quality GaN at 550 ℃ by atomic layer epitaxy. Appl. Phys. Lett. 67, 94–96 (1995). doi: 10.1063/1.115519 [64] Ke, W. C. et al. Impacts of ammonia background flows on structural and photoluminescence properties of InN dots grown on GaN by flow-rate modulation epitaxy. Appl. Phys. Lett. 89, 263117 (2006). [65] Reilly, C. E. et al. Flow modulation metalorganic vapor phase epitaxy of GaN at temperatures below 600 ℃. Semicond. Sci. Technol. 35, 095014 (2020). [66] Bernardini, F., Fiorentini, V. & Vanderbilt, D. Spontaneous polarization and piezoelectric constants of Ⅲ–Ⅴ nitrides. Phys. Rev. B 56, R10024–R10027 (1997). [67] Schulz, S. & O'Reilly, E. P. Theory of reduced built-in polarization field in nitride-based quantum dots. Phys. Rev. B 82, 033411 (2010). [68] Keller, S. et al. Recent progress in metal-organic chemical vapor deposition of (000$\bar 1$) N-polar group-Ⅲ nitrides. Semicond. Sci. Technol. 29, 113001 (2014). [69] Keller, S. et al. Properties of N-polar AlGaN/GaN heterostructures and field effect transistors grown by metalorganic chemical vapor deposition. J. Appl. Phys. 103, 033708 (2008). [70] Wong, M. H. et al. N-polar GaN epitaxy and high electron mobility transistors. Semicond. Sci. Technol. 28, 074009 (2013). [71] Li, H. R. et al. Enhanced mobility in vertically scaled N-polar high-electron-mobility transistors using GaN/InGaN composite channels. Appl. Phys. Lett. 112, 073501 (2018). [72] Rajan, S. et al. N-polar GaN/AlGaN/GaN high electron mobility transistors. J. Appl. Phys. 102, 044501 (2007). [73] Masui, H. et al. Luminescence characteristics of N-polar GaN and InGaN films grown by metal organic chemical vapor deposition. Jpn. J. Appl. Phys. 48, 071003 (2009). [74] Lund, C. et al. Properties of N-polar InGaN/GaN quantum wells grown with triethyl gallium and triethyl indium as precursors. Semicond. Sci. Technol. 34, 075017 (2019). [75] Segev, D. & Van De Walle, C. G. Origins of fermi-level pinning on GaN and InN polar and nonpolar surfaces. EPL (Europhys. Lett. ) 76, 305–311 (2006). [76] Mahboob, I. et al. Origin of electron accumulation at wurtzite InN surfaces. Phys. Rev. B 69, 201307 (2004). [77] Mahboob, I. et al. Intrinsic electron accumulation at clean InN surfaces. Phys. Rev. Lett. 92, 036804 (2004). [78] Reilly, C. E. et al. Infrared luminescence from N-polar InN quantum dots and thin films grown by metal organic chemical vapor deposition. Appl. Phys. Lett. 114, 241103 (2019). [79] Park, S. H. & Chuang, S. L. Crystal-orientation effects on the piezoelectric field and electronic properties of strained wurtzite semiconductors. Phys. Rev. 59, 4725–4737 (1999). [80] Buzynin, Y. N. et al. InN layers grown by MOCVD on a-plane Al2O3. Phys. Status Solidi (A) 215, 1700919 (2018). [81] Moret, M. et al. MOVPE growth and characterization of indium nitride on C-, A-, M-, and R-plane sapphire. Phys. Status Solidi (A) 207, 24–28 (2010). [82] Hsu, L. H. et al. Enhanced photocurrent of a nitride–based photodetector with InN dot-like structures. Optical Mater. Express 4, 2565–2573 (2014). [83] Chan, P. et al. Growth by MOCVD and photoluminescence of semipolar $(20\overline{21})$ InN quantum dashes. J. Cryst. Growth 563, 126093 (2021). [84] Burstein, E. Anomalous optical absorption limit in InSb. Phys. Rev. 93, 632–633 (1954). [85] Khan, N. et al. High mobility InN epilayers grown on AlN epilayer templates. Appl. Phys. Lett. 92, 172101 (2008). [86] Lozano, J. G. et al. Nucleation of InN quantum dots on GaN by metalorganic vapor phase epitaxy. Appl. Phys. Lett. 87, 263104 (2005). [87] Dwivedi, S. et al. InN nanowires based near-infrared broadband optical detector. IEEE Photonics Technol. Lett. 31, 1526–1529 (2019). [88] Krishna, S. et al. Ultrafast photoresponse and enhanced photoresponsivity of indium nitride based broad band photodetector. Sol. Energy Mater. Sol. Cells 172, 376–383 (2017). [89] Winden, A. et al. Spectral sensitivity tuning of vertical InN nanopyramid-based photodetectors. Jpn. J. Appl. Phys. 52, 08JF05 (2013). [90] Tekcan, B. et al. A near-infrared range photodetector based on indium nitride nanocrystals obtained through laser ablation. IEEE Electron Device Lett. 35, 936–938 (2014). [91] Lai, W. J. et al. Near infrared photodetector based on polymer and indium nitride nanorod organic/inorganic hybrids. Scr. Materialia 63, 653–656 (2010).
###### 通讯作者: 陈斌, bchen63@163.com
• 1.

沈阳化工大学材料科学与工程学院 沈阳 110142

Figures(9)

## Article Metrics

Article views(72) PDF downloads(3) Citation(0) Citation counts are provided from Web of Science. The counts may vary by service, and are reliant on the availability of their data.

## Metalorganic chemical vapor deposition of InN quantum dots and nanostructures

• 1. Materials, University of California, Santa Barbara, CA 93106, USA
• 2. Electrical and Computer Engineering, University of California, Santa Barbara, CA 93106, USA
• ###### Corresponding author: Caroline E. Reilly, cereilly@ucsb.edu;

Abstract: Using one material system from the near infrared into the ultraviolet is an attractive goal, and may be achieved with (In, Al, Ga)N. This Ⅲ-N material system, famous for enabling blue and white solid-state lighting, has been pushing towards longer wavelengths in more recent years. With a bandgap of about 0.7 eV, InN can emit light in the near infrared, potentially overlapping with the part of the electromagnetic spectrum currently dominated by Ⅲ-As and Ⅲ-P technology. As has been the case in these other Ⅲ–Ⅴ material systems, nanostructures such as quantum dots and quantum dashes provide additional benefits towards optoelectronic devices. In the case of InN, these nanostructures have been in the development stage for some time, with more recent developments allowing for InN quantum dots and dashes to be incorporated into larger device structures. This review will detail the current state of metalorganic chemical vapor deposition of InN nanostructures, focusing on how precursor choices, crystallographic orientation, and other growth parameters affect the deposition. The optical properties of InN nanostructures will also be assessed, with an eye towards the fabrication of optoelectronic devices such as light-emitting diodes, laser diodes, and photodetectors.

• Reference (91)

/