Structure Shift of GaN Among Nanowall Network, Nanocolumn, and Compact Film Grown on Si (111) by MBE
© The Author(s). 2018
Received: 27 November 2017
Accepted: 28 January 2018
Published: 13 February 2018
Structure shift of GaN nanowall network, nanocolumn, and compact film were successfully obtained on Si (111) by plasma-assisted molecular beam epitaxy (MBE). As is expected, growth of the GaN nanocolumns was observed in N-rich condition on bare Si, and the growth shifted to compact film when the Ga flux was improved. Interestingly, if an aluminum (Al) pre-deposition for 40 s was carried out prior to the GaN growth, GaN grows in the form of the nanowall network. Results show that the pre-deposited Al exits in the form of droplets with typical diameter and height of ~ 80 and ~ 6.7 nm, respectively. A growth model for the nanowall network is proposed and the growth mechanism is discussed. GaN grows in the area without Al droplets while the growth above Al droplets is hindered, resulting in the formation of continuous GaN nanowall network that removes the obstacles of nano-device fabrication.
As direct wide band gap semiconductors, GaN and related compounds have achieved great success in light-emitting diodes [1–3], laser diodes , and high-electron-mobility transistors [5, 6]. The heteroepitaxy of GaN film on sapphire, silicon carbide, or single crystal silicon, however, induces a high density of dislocation. It is believed that their nanostructures have superior performance due to dislocation-free, strain-free, and large surface area-to-volume ratio [7, 8]. Researches on the GaN nanocolumns and nanowires have been intensively carried out [9–12]. The GaN nanocolumnar nucleation occurs spontaneously by Volmer-Weber growth mechanism , whereas nitrogen-rich (N-rich) condition prevents the nucleation sites from coalescing. Much attention has been paid to the fabrication of an electrical device on the GaN nanowires or on the nanocolumns. The GaN nanowires were mechanically dispersed on SiO2/Si substrate and ohmic contacts formed in two sides of an individual nanowire in random . In another case , one side of the nanowire was fixed to a stage connected to negative electrode while another side was aligned to positive electrode by means of scanning electron microscope (SEM), forming an electrical device for scientific research.
Alternatively, a special nanostructure namely the GaN nanowall network which is in-plane electrically conductive is promising since no complex process is needed for the nano-device fabrication. In 2007, growth of the GaN nanowall network was obtained by Kishino’s group using Ti layer patterned by electron-beam lithography as a mask . Several years ago, growth of the GaN nanowall network without any lithography was successfully obtained on sapphire and silicon substrates [17–19]. The band-edge emission intensity of the GaN nanowall network is similar to the GaN nanocolumns and the yellow luminescence is not obvious, indicating high quality of the GaN nanowall network. Different from the separated nanostructure such as the nanocolumns, the nanowall network is in-plane electrically conductive [18, 20, 21] that it could be fabricated into nano-device as easy as the film . Therefore, the obstacle of device fabrication on the separated nanocolumns could be removed by the in-plane electrical conduction of the nanowall network. It is crucial to study the growth mechanism of the nanowall network. Dislocation-induced spontaneous formation of nanowall network is regarded as the growth mechanism of GaN nanowall network on bare c-plane sapphire . Since the dislocation-induced formation of nanowall network is of low control, the nanowall network growth on Si (111) substrate with Al buffer layer  has been carried out. The growth mechanism of the nanowall on Si (111) is significantly different from that on bare sapphire substrate; however, no research is carried out though the growth mechanism on Si (111) is the key for the nanowall network growth.
In this work, growth of GaN in various structures including the nanowall network, the nanocolumns, and compact film are systematically studied. Various GaN structures mentioned above were grown on Si (111) using plasma-assisted molecular beam epitaxy (MBE). Results show that the structure shift of GaN growth can be achieved by adjusting the Ga/N ratio and by adding the pre-deposited Al droplets. The morphology and photoluminescence of the GaN nanowall network were measured by field emission scanning electron microscopy (FESEM) and photoluminescence spectrum analyzer with He-Cd laser (325 nm, 200 mW) as the excitation source. Atomic force microscope (AFM) was utilized for the characterization of the pre-deposited Al layer. The growth mechanism of GaN nanowall network on Si (111) with metallic Al droplets is proposed.
GaN structures were grown on the Si (111) substrates by Riber 32 MBE system equipped with a N2 RF plasma source (Veeco, RFS-N/TH). The pressure of the growth chamber was pumped to 3.0 × 10− 10 Torr prior to growth. The N2 gas, Ga, and Al with purity of 99.9999% were used in this experiment. Si (111) substrate (without doping, one side polished for growth, 380 ±20 μm, provided by Sigma-Aldrich) with resistivity > 5000 Ω cm was cleaned by standard RCA process, followed by dipping in HF:H2O = 1:50 for a few seconds to remove silicon oxide layer on the surface of Si substrate as well as forming a hydrogen-terminated surface.
For the growth of the GaN nanocolumns, the shutters of the N2 plasma and the Ga source were simultaneously opened and the bare Si (111) was heated at 973 K. The power and the pressure of the N2 plasma source used in all samples in this work were fixed at 400 W and 4.2 × 10− 5 Torr, respectively. Prior to the growth of the GaN nanowall network, the Al droplets with diameter of about 80 nm were deposited on the bare Si (111) heated at 973 K. The Al source was kept at 1323 K. The pre-deposition of the Al droplets resulted in a different nucleation and growth of GaN, leading to the growth of the nanowall network. The Ga flux for the growth of the nanowall network was the same with the nanocolumns (φGa = 1.2 × 10− 7 Torr at 1169 K). For the growth of GaN film, the Ga flux was increased to 5.3 × 10− 7 Torr while the N flux was kept at constant.
Results and Discussion
Summarization of samples studied in this work
Growth temperature (K)
Growth time (min)
1.2 × 10−7
1.2 × 10−7
5.3 × 10−7
1.2 × 10−7
1.2 × 10−7
Since the atomically flat nanocolumn sidewalls provide few adsorption sites, it is assumed that the Gaab diffusion length L on the m-plane of sidewalls is much higher than that on the c-plane, resulting in the vertical growth of GaN to nanocolumns. If this assumption was true, the strong growth rate anisotropy would be changed when the Ga/N ratio is improved. Indeed, the GaN (S3) structure changed from the nanocolumn to the compact film (Fig. 1e) when the Ga flux was increased to 5.3 × 10− 7 Torr. Therefore, GaN growth in the form of the nanocolumn or the compact film can be controlled by adjusting the Ш/V ratio.
Though the GaN nanocolumns exhibit superior performance than the film, the fabrication of electrical device is of high difficulty because the separated nanocolumn needs alignment prior to the electrical contact fabrication. An in-plane electrically conductive nanostructure, therefore, is favored. For the growth of sample S2, metallic Al pre-deposition was carried out in the MBE growth chamber for 40 s. Then, the N2 plasma and the Ga source were simultaneously opened. The Ga flux for the S2 growth is summarized in Table 1, the same with that of S1. Figure 1c shows the top-view FESEM image of the sample S2. It is quite interesting that the GaN grows in the form of the nanowall network on the Al/Si (111). The nanowalls with diameter of 50~100 nm overlap and interlace with one another, forming an in-plane continuous network, namely nanowall network. Two classes of holes are observable, named class A and class B. The diameters of the class A and the class B holes are typically, 50~100 and 10~ 49 nm, respectively. The in-plane continuous characteristic makes the nanowall network in-pane electrically conductive , removing the obstacles of nano-device fabrication to some extent. The top surface of the nanowalls is relatively flat, different from the faceted GaN matrix reported in Ref. . It is observable that the holes shown in the top-view image extend to near the substrate, as indicated by the rectangle in Fig. 1d.
One may wonder how the holes mentioned above are generated. We grew a sample S5 at a lower growth temperature of 900 K. The other growth parameters are the same with the sample S2, as shown in the Table 1. From Fig. 1g, we observe that the sample S5 also grew in the form of the nanowall network with smaller holes. Figure 1h is the cross-sectional image of S5, showing a more compact layer than S2. In order to see the beginning growth of the GaN nanowall network, we grew another sample S4 in a short time with Al pre-deposition. All the growth parameters of S4 are the same with that of sample S2 except for the growth time (20 vs 120 min). The thickness of S4 is about 50 nm and its top-view image is shown in Fig. 1f. It is observed that holes have been formed at this stage and the as-gown GaN is an in-plane continuous network, rather than the GaN nanowires or islands. From the study of samples S1, S2, S4, and S5, it is clear that the pre-deposition of the Al layer changes the growth behavior of GaN at the beginning, from the nanocolumn to the in-plane continuous nanowall network.
In our case, the growth mechanism of the GaN nanowall network should be different since the nanowalls grow with the requirement of the metallic Al pre-deposition. Of course, to our knowledge, all GaN nanowall networks including in our experiment are grown under the N-rich atmosphere. N rich is required to reduce the coalescence of the nanowalls. Now, let us focus on the role of the Al droplets in the formation of the nanowall network. Similar to the Au droplets acting as a catalyst , if the Al droplets acted as a catalyst, the GaN should grow to the nanocolumns rather than the nanowall network. The Al droplets’ role, therefore, is not a catalyst in our study. The melt temperature of the Al metal is 933 K while the substrate temperature is maintained at 973 K during growth. At the beginning of the GaN growth, thus, the Al droplets are liquid droplets. According to previous report, in the case of GaN on Si (111) with Ga droplets , the Ga droplets act as reservoirs that supply Ga atoms to their close vicinity. The Ga droplets themselves, however, hinder the GaN growth on them since the original Ga droplet sites are hollow circles. In our case, the diameter of the Al droplets is ~ 80 nm, similar to the size of the class A holes in Fig. 1a. Therefore, the Al droplets may hinder the growth of GaN on them, leading to the formation of the class A holes observed in the GaN nanowall network. Because of the same Ш/V ratio of samples S1 and S2, the Ga diffusion length L on Si for the nanowall network growth is expected to be the same with that for the nanocolumns. The typical size of the bare Si substrate (the area without Al droplets) is ~ 80 nm, within the value of the nanocolumn diameter in Fig. 1a. In other words, the Ga diffusion length L covers the size of the bare Si substrate, resulting in the continuous growth of GaN in the area without the Al droplets, i.e., GaN nanowall network.
In this work, structure shift of the GaN growth among the nanocolumn, the nanowall network, and the compact film was successfully achieved on Si (111) substrate using MBE. The GaN nanocolumns were grown on the bare Si substrate under N-rich condition while the compact film was grown with an improved Ga flux. By adding a pre-deposited Al layer, the growth of GaN shifts from the nanocolumns to the in-plane continuous nanowall network. The pre-deposited Al layer exists in the form of droplets with the typical height and diameter of 6.7 and 80 nm, respectively. The growth mechanism of the nanowall network is addressed. GaN continuously grows on the bare Si substrate while the GaN growth on the Al droplets is hindered, resulting in the formation of the nanowall network. Both Al droplets and N-rich condition are essential for the nanowall network growth.
The authors are grateful to thank Ms. W.T. Wang and Mr. W. Bo for their help in the electrical property measurement.
This work was supported by the National Natural Science Foundation of China (Grant No. 61504084), the Basical Research Program of Shenzhen (Grant No. JCYJ20160307144047526), and the Natural Science Foundation of SZU (Grant No. 201554, Grant No. 827-000187).
Availability of Data and Materials
The dataset supporting the conclusions of this article is included within the article.
AHZ and YZX drafted the manuscript and carried out the growth experiment. FL and YTZ carried out the measurement experiment. ZDP and JTL helped the development of growth mechanism. FP and KH helped the design of the study. All authors read and approved the final manuscript.
Aihua Zhong received the Dr.Eng. degree in Nano mechanics from Tohoku University, Sendai, Japan, in 2014. Since 2015, he has been an assistant professor with the College of Physics and Energy, Shenzhen University, China, where he is currently engaged in research and development of film growth and MEMS-based devices and sensors.
Ping Fan received the Ph.D. degree in Physics from Chinese Academy of Sciences, Shanghai, China, in 1985. Since 1985, he has been an assistant professor, associate professor, and professor with the College of Physics and Energy, Shenzhen University, China, where he is currently engaged in research and development of film growth and micro device.
Dongping Zhang received the Ph.D. degree from Chinese Academy of Sciences, Shanghai, China. Since 2007, he has been an assistant professor, associate professor, and professor with the College of Physics and Energy, Shenzhen University, China, where he is currently engaged in research and development of film growth.
Yuanting Zhong graduated from Changan University, Xian, China, in 2012. From 2012 to 2014, she was an engineer in SAIC MOTOR. Since 2015, she has been an assistant researcher in the department of Automotive Engineering, Foshan Polytechnic, Foshan, China.
Fu Li received the Dr.Eng. degree in Materials Science and Engineering from Tsinghua University, Beijing, China, in 2013, followed by postdoc at Tsinghua University. Since 2016, she has been an assistant professor with the College of Physics and Energy, Shenzhen University, China, where she is currently engaged in research and development of film growth and thermoelectric materials.
Jingting Luo received the Dr.Eng. degree in Materials Science and Engineering from Tsinghua University, Beijing, China, in 2011. Since 2012, he has been an assistant professor and associate professor with the College of Physics and Energy, Shenzhen University, China, where he is currently engaged in research and development of micro device and biosensors.
Yizhu Xie received the Ph.D. degree (2012) in condensed matter physics from Lanzhou University, China, followed by postdoc at The Hong Kong Polytechnic University. Since 2015, he has been an assistant professor with the College of Physics and Energy, Shenzhen University, China, where he is currently engaged in research and development of film growth and flexible electronic devices, including photodetectors, sensors, and flexible energy storage and conversion devices.
Kazuhiro Hane received the M.S. and Dr.Eng. degree from Nagoya University, Nagoya, Japan, in 1980 and 1983, respectively. From 1983 to 1994, he was in the Department of Electrical Engineering, Nagoya University. From 1985 to 1986, he was a visiting researcher with the National Research Council of Canada. Since 1994, he has been a professor in the Gradual School of Mechanical Engineering, Tohoku University, Sendai, Japan, where he is currently engaged in research and development of optical microsensors and optical microelectromechanical systems.
The authors declare that they have no competing interests.
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- Ponce FA, Bour DP (1997) Nitride-based semiconductors for blue and green light-emitting devices. Nature 386:351–359. https://doi.org/10.1038/386351a0.View ArticleGoogle Scholar
- Wang H-C, Chen M-C, Lin Y-S et al (2017) Optimal silicon doping layers of quantum barriers in the growth sequence forming soft confinement potential of eight-period In0.2Ga0.8N/GaN quantum wells of blue LEDs. Nanoscale Res Lett 12. https://doi.org/10.1186/s11671-017-2359-3.
- Zhou X, Lu T, Zhu Y et al (2017) Surface morphology evolution mechanisms of InGaN/GaN multiple quantum wells with mixture N2/H2-grown GaN barrier. Nanoscale Res Lett 12. https://doi.org/10.1186/s11671-017-2115-8.
- Nakamura S, Senoh M, Nagahama S et al (1996) InGaN-based multi-quantum-well-structure laser diodes. Jpn J Appl Phys 35:L74–L76. https://doi.org/10.1143/JJAP.35.L74.View ArticleGoogle Scholar
- Tzou A-J, Chu K-H, Lin I-F et al (2017) AlN surface passivation of GaN-based high electron mobility transistors by plasma-enhanced atomic layer deposition. Nanoscale Res Lett 12. https://doi.org/10.1186/s11671-017-2082-0.
- Chien C-Y, Wu W-H, You Y-H et al (2017) Breaking through the multi-mesa-channel width limited of normally off GaN HEMTs through modulation of the via-hole-length. Nanoscale Res Lett 12. https://doi.org/10.1186/s11671-017-2189-3.
- Mamand SM, Omar MS, Muhammad AJ (2012) Nanoscale size dependence parameters on lattice thermal conductivity of Wurtzite GaN nanowires. Mater Res Bull 47:1264–1272. https://doi.org/10.1016/j.materresbull.2011.12.025.View ArticleGoogle Scholar
- Hu FR, Ochi K, Zhao Y, Hane K (2006) High-efficiency light-emitting column-crystallized InGaN∕GaN quantum-well flower structure on micropillared Si substrate. Appl Phys Lett 89:171903. https://doi.org/10.1063/1.2364839.View ArticleGoogle Scholar
- Bertness KA, Roshko A, Mansfield LM et al (2008) Mechanism for spontaneous growth of GaN nanowires with molecular beam epitaxy. J Cryst Growth 310:3154–3158. https://doi.org/10.1016/j.jcrysgro.2008.03.033.View ArticleGoogle Scholar
- Debnath RK, Meijers R, Richter T et al (2007) Mechanism of molecular beam epitaxy growth of GaN nanowires on Si(111). Appl Phys Lett 90:12311. https://doi.org/10.1063/1.2715119.View ArticleGoogle Scholar
- Neplokh V, Messanvi A, Zhang H et al (2015) Substrate-free InGaN/GaN nanowire light-emitting diodes. Nanoscale Res Lett 10. https://doi.org/10.1186/s11671-015-1143-5.
- Hou W-C, Wu T-H, Tang W-C, Hong F (2012) Nucleation control for the growth of vertically aligned GaN nanowires. Nanoscale Res Lett 7:373. https://doi.org/10.1186/1556-276X-7-373.View ArticleGoogle Scholar
- Ristić J, Calleja E, Fernández-Garrido S et al (2008) On the mechanisms of spontaneous growth of III-nitride nanocolumns by plasma-assisted molecular beam epitaxy. J Cryst Growth 310:4035–4045. https://doi.org/10.1016/j.jcrysgro.2008.05.057.View ArticleGoogle Scholar
- González-Posada F, Songmuang R, Den Hertog M, Monroy E (2012) Room-temperature photodetection dynamics of single GaN nanowires. Nano Lett 12:172–176. https://doi.org/10.1021/nl2032684.View ArticleGoogle Scholar
- Wang X, Zhou J, Song J et al (2006) Piezoelectric field effect transistor and nanoforce sensor based on a single ZnO nanowire. Nano Lett 6:2768–2772. https://doi.org/10.1021/nl061802g.View ArticleGoogle Scholar
- Komatsu Y, Mitsui S, Kuroe H et al (2011) Raman scattering from a surface phonon in GaN nanowalls and regularly-arrayed GaN nanocolumns, pp 527–528.Google Scholar
- Kesaria M, Shetty S, Shivaprasad SM (2011) Evidence for dislocation induced spontaneous formation of GaN nanowalls and nanocolumns on bare C-plane sapphire. Cryst Growth Des 11:4900–4903. https://doi.org/10.1021/cg200749w.View ArticleGoogle Scholar
- Zhong A, Hane K (2012) Growth of GaN nanowall network on Si (111) substrate by molecular beam epitaxy. Nanoscale Res Lett 7:686. https://doi.org/10.1186/1556-276X-7-686.View ArticleGoogle Scholar
- Tamura Y, Hane K (2016) Optical characteristics of multiple layered InGaN quantum wells on GaN nanowalls grown on Si (111) substrate. Mater Res Bull 83:563–567. https://doi.org/10.1016/j.materresbull.2016.06.042.View ArticleGoogle Scholar
- Tamura Y, Hane K (2015) AlN nanowall structures grown on Si (111) substrate by molecular beam epitaxy. Nanoscale Res Lett 10. https://doi.org/10.1186/s11671-015-1178-7.
- Zhong A, Sasaki T, Hane K (2014) Platinum/porous GaN nanonetwork metal-semiconductor Schottky diode for room temperature hydrogen sensor. Sens Actuators Phys 209:52–56. https://doi.org/10.1016/j.sna.2014.01.014.View ArticleGoogle Scholar
- Zhong A, Sasaki T, Fan P et al (2018) Integrated H2 nano-sensor array on GaN honeycomb nanonetwork fabricated by MEMS-based technology. Sens Actuators B Chem 255:2886–2893. https://doi.org/10.1016/j.snb.2017.09.107.View ArticleGoogle Scholar
- Kesaria M, Shivaprasad SM (2011) Nitrogen flux induced GaN nanostructure nucleation at misfit dislocations on Al2O3(0001). Appl Phys Lett 99:143105. https://doi.org/10.1063/1.3646391.View ArticleGoogle Scholar
- Wang H, Wang W, Yang W et al (2017) Employing Al buffer layer with Al droplets-distributed surface to obtain high-quality and stress-free GaN epitaxial films on Si substrates. J Mater Sci 52:1318–1329. https://doi.org/10.1007/s10853-016-0427-1.View ArticleGoogle Scholar
- Poppitz D, Lotnyk A, Gerlach JW, Rauschenbach B (2014) Microstructure of porous gallium nitride nanowall networks. Acta Mater 65:98–105. https://doi.org/10.1016/j.actamat.2013.11.041.View ArticleGoogle Scholar
- Navamathavan R, Ra Y-H, Song K-Y et al (2011) Different growth behaviors of GaN nanowires grown with Au catalyst and Au + Ga solid solution nano-droplets on Si(111) substrates by using MOCVD. Curr Appl Phys 11:77–81. https://doi.org/10.1016/j.cap.2010.06.022.View ArticleGoogle Scholar
- Kesaria M, Shetty S, Cohen PI, Shivaprasad SM (2011) Transformation of c-oriented nanowall network to a flat morphology in GaN films on c-plane sapphire. Mater Res Bull 46:1811–1813. https://doi.org/10.1016/j.materresbull.2011.07.043.View ArticleGoogle Scholar
- Reshchikov MA, Morkoç H (2005) Luminescence properties of defects in GaN. J Appl Phys 97:061301. https://doi.org/10.1063/1.1868059.View ArticleGoogle Scholar