Atomic layer deposition and application of group III nitrides semiconductor and their alloys

Qiu Peng; Liu Heng; Zhu Xiao-Li; Tian Feng; Du Meng-Chao; Qiu Hong-Yu; Chen Guan-Liang; Hu Yu-Yu; Kong De-Lin; Yang Jin; Wei Hui-Yun; Peng Ming-Zeng; Zheng Xin-He

doi:10.7498/aps.73.20230832

Abstract

Group III nitride semiconductors, such as GaN, AlN, and InN, are an important class of compound semiconductor material, and have attracted much attention, because of their unique physicochemical properties. These semiconductors possess excellent characteristics, such as wide direct bandgap, high breakdown field strength, high electron mobility, and good stability, and thus are called third-generation semiconductors. Their alloy materials can adjust their bandgaps by changing the type or proportion of group III elements, covering a wide wavelength range from near-ultraviolet to infrared, thereby achieving wavelength selectivity in optoelectronic devices. Atomic layer deposition (ALD) is a unique technique that produces high-quality group III nitride films at low temperatures. The ALD has become an important method of preparing group III nitrides and their alloys. The alloy composition can be easily controlled by adjusting the ALD cycle ratio. This review highlights recent work on the growth and application of group III nitride semiconductors and their alloys by using ALD. The work is summarized according to similarities so as to make it easier to understand the progress and focus of related research. Firstly, this review summarizes binary nitrides with a focus on their mechanism and application. In the section on mechanism investigation, the review categorizes and summarizes the effects of ALD precursor material, substrate, temperature, ALD type, and other conditions on film quality. This demonstrates the effects of different conditions on film growth behavior and quality. The section on application exploration primarily introduces the use of group III nitride films in various devices through ALD, analyzes the enhancing effects of group III nitrides on these devices, and explores the underlying mechanisms. Additionally, this section discusses the growth of group III nitride alloys through ALD, summarizing different deposition methods and conditions. Regarding the ALD growth of group III nitride semiconductors, there is more research on the ALD growth of AlN and GaN, and less research on InN and its alloys. Additionally, there is less research on the ALD growth of GaN for applications, as it is still in the exploratory stage, while there is more research on the ALD growth of AlN for applications. Finally, this review points out the prospects and challenges of ALD in preparation of group III nitride semiconductors and their alloys.

Keywords:

Authors and contacts

School of Mathematics and Physics, Beijing Key Laboratory for Magneto-Photoelectrical Composite and Interface Science, University of Science and Technology Beijing, Beijing 100083, China

Corresponding author: Zheng Xin-He, xinhezheng@ustb.edu.cn

Funds: Project supported by the National Key Research and Development Program of China (Grant No. 2018YFA0703700), the National Natural Science Foundation of China (Grant No. 52002021), and the Fundamental Research Funds for the Central Universities, China (Grant No. FRF-IDRY-GD22-001).

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图 1 等离子体增强原子层沉积沉积GaN的示意图

Figure 1. Schematic diagram of GaN deposited by plasma-enhanced atomic layer deposition.

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图 2 (a)未经预处理的氮化镓薄膜的GIXRD曲线; (b) 预处理样品的XRD曲线; (c) (002) GaN峰的XRD ω扫描摇摆曲线; (d), (e)未经预处理和预处理的GaN/蓝宝石界面的HRTEM图像; (f) 预处理和未预处理的氮化镓的初始生长示意图; (g) 预处理的GaN薄膜的选区电子衍射图. 氮化镓是外延的, 存在$\left[ {1\bar 10} \right]$_氮化镓//[100]_蓝宝石平面排列; (h) 图(b)中黄色矩形所包围的GaN/蓝宝石界面区域的放大图^[34]

Figure 2. (a) GIXRD patterns of the non-pretreated GaN thin film; (b) XRD patterns and (c) XRD ω-scan rocking curve of the (002) GaN peak of the pretreated sample; (d), (e) HRTEM images of the non-pretreated and pretreated GaN/sapphire interfaces, respectively; (f) the schematic diagram of the initial growth of pretreated and non-pretreated GaN; (g) selected area electron diffraction of the pretreated GaN thin film, GaN is epitaxial, with a $\left[ {1\bar 10} \right]$_GaN//[100]_sapphire plane alignment; (h) magnification of the GaN/sapphire interface region enclosed by the yellow rectangle in panel (b)^[34].

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图 3 实时测量的和平均原位椭圆光度法薄膜厚度数据显示, 即在衬底温度为(a) 120 , (b) 160, (c) 200和(d) 240 ℃时, TMG化学吸附和N₂/H₂/Ar等离子体辅助配体去除反应的等离子体射频功率相关性^[37]

Figure 3. Real-time measured and averaged in situ ellipsometric film thickness data showing the plasma rf-power dependence of TMG chemisorption and N₂/H₂/Ar plasma-assisted ligand removal reactions at substrate temperatures of (a) 120, (b) 160, (c) 200 and (d) 240 ℃^[37].

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图 4 (a) H₂O和(b) NH₃预处理后的成核示意图. 蓝色区域、红色区域和a^*分别代表完全羟基化状态、较高能量状态和反应性部位, 如离解的NH₃^[67]

Figure 4. Schematics of nucleation after (a) H₂O and (b) NH₃ pretreatment. The blue region, the red region and a^* represent the fully hydroxylated state, a higher energy state, and a reactive site such as dissociated NH₃, respectively^[67].

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图 5 (a) 用于InN的ALD研究的三种六价In(III)前体1—3; (b)前体3的改进的表面化学示意图, 显示与(c)前体2相比, 其iPr基团的立体和表面排斥力下降^[85]

Figure 5. (a) Hexacoordinated In(III) precursors 1–3 used for the ALD study of InN; schematics of the suggested improved surface chemistry for (b) precursor 3, showing the decrease in steric and surface repulsion of its iPr groups in comparison to (c) precursor 2^[85].

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图 6 数字合金化的示意图

Figure 6. Schematic diagram of digital alloying.

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表 1 使用ALD沉积III族二元氮化物薄膜的生长条件概述, 包括薄膜生长和器件应用

Table 1. Overview of growth conditions for the deposition of group III binary nitride films using ALD, including film growth and device applications.

材料	金属前驱体	氮前驱体	沉积温度/ ℃	沉积衬底	应用	ALD类型	等离子体功率/W	参考文献
GaN	TEG	Ar/N₂/H₂ (1∶3∶6)	350	Si (100)	薄膜生长	PE-ALD	60	[32]
GaN	TEG	Ar/N₂/H₂ (1∶3∶6)	350	Si (100)	薄膜生长	PE-ALD	60	[33]
GaN	TEG	Ar/N₂/H₂ (1∶3∶6)	350	c-sapphire	薄膜生长	PE-ALD	60	[34]
GaN	TEG	N₂/H₂	200	Si (100)	薄膜生长	HCPA-ALD	300	[36]
GaN	TMG	N₂/H₂	120—240	Si (100)	薄膜生长	HCP-ALD	50—250	[37]
GaN	TEG	N₂/H₂	200	sapphire	薄膜生长	HCPA-ALD	300	[38]
GaN	TEG	NH₃/Ar	160—350	Si (100)	薄膜生长	PE-ALD	2000	[39]
GaN	TEG	N₂/H₂	300	sapphire (0001)	薄膜生长	PE-ALD	50和 300	[40]
GaN	Ga(NMe₂)₃	NH₃/Ar	130—250	Si (100) 4H-SiC (0002)	薄膜生长	PE-ALD	2800	[41]
GaN	Ga(NMe₂)₃	NH₃/Ar	130—250	Si (100), 4H-SiC (0002)	薄膜生长	PE-ALD	2800	[42]
GaN	TEG	Ar/N₂/H₂ (1∶3∶6)	350	multilayer graphene	薄膜生长	PE-ALD	60	[43]
GaN	TEG	Ar/N₂/H₂ (1∶3∶6)	300	graphene	薄膜生长	PE-ALD	60	[44]
GaN	TEG	Ar/N₂/H₂ (1∶3∶6)	≤290	stainless steel	薄膜生长	PE-ALD	60	[45]
GaN	TEG	Ar/N₂/H₂ (1∶3∶6)	200—300	Kapton	薄膜生长	PE-ALD	60	[46]
GaN	TEG	Ar/N₂/H₂ (1∶3∶6)	260	MoS₂	薄膜生长	PE-ALD	60	[47]
GaN	TEG	Ar/N₂/H₂ (1∶3∶6)	260, 320	MoS₂	薄膜生长	PE-ALD	60	[48]
GaN	TEG	Ar/N₂/H₂ (1∶3∶6)	280	FTO	薄膜生长	PE-ALD	60	[49]
GaN	TEG	Ar/N₂/H₂ (1∶3∶6)	280	FTO	钙钛矿太阳能电池	PE-ALD	60	[50]
GaN	TEG	Ar/N₂/H₂ (1∶3∶6)	200—280	—	量子点太阳能电池	PE-ALD	60	[51]
AlN	AlCl₃	NH₃/Ar/H₂	350	p-Si (100)	薄膜生长	PE-ALD	150	[52]
AlN	TMA	Ar/N₂/H₂ (1∶3∶6)	350—300	Si (100)	薄膜生长	PE-ALD	60	[53]
AlN	TMA	Ar/N₂/H₂ (1∶3∶6)	250	Si (100), Si (111) sapphire	薄膜生长	PE-ALD	60	[54]
AlN	TMA	NH₃	200—300	Si, sapphire	薄膜生长	PE-ALD	2500	[55]
AlN	TMA	NH₃	300	GaN	薄膜生长	PE-ALD	200	[56]
AlN	TMA	N₂/H₂	200	Si (100)	薄膜生长	PE-ALD	300	[57]
AlN	TMA	Ar/N₂	300	(Homemade substrates)	MEMS	PE-ALD	975	[58]
AlN	TMA	H₂ plasma, NH₃	325—350	SiC	薄膜生长	PE-ALD	1800	[59]
	TMA	NH₃	325—400	SiC		T-ALD	—
AlN	TMA	N₂/H₂	300	4H-SiC	薄膜生长	PE-ALD	50—300	[60]
AlN	TMA	NH₃ (Ar)	300	Si (100), Si (111)	薄膜生长	PE-ALD	100, 200	[61]
AlN	TMA	NH₃	350	Si	薄膜生长	PE-ALD(ICP)	200 600	[62]
AlN	TMA	NH₃	350	Si	薄膜生长	PE-ALD(CCP)	200	[62]
AlN	Al(C₄H₉)₃	N₂H₅Cl	200—350	—	薄膜生长	T-ALD	—	[63]
AlN	TMA	N₂/H₂	300	Si (100)	薄膜生长, 电容器	PE-ALD	300	[64]
AlN	TMA	Ar/N₂/H₂	100—250	Si (100)	薄膜生长	HCPA-ALD	25—200	[65]
AlN	TMA	Ar/N₂/H₂	100—250	Si (100)	薄膜生长	HCPA-ALD	25—200	[66]
AlN	TMA	NH₃	295—342	Si, TiN	薄膜生长	T-ALD	—	[67]
AlN	TMA	N₂H₄	175—350	p-Si	薄膜生长	T-ALD	—	[68]
AlN	TMA	Monomethylhydrazine(MMH)	375—475	Si (100)	薄膜生长	T-ALD	—	[69]
AlN	三(二甲氨基)铝	NH₃	300	p-Si	薄膜生长	T-ALD	—	[70]
AlN	TMA	NH₃	400	GaN/AlGaN	MIS-HEMT	T-ALD	—	[71]
AlN	TMA	NH₃	360	GaN	MIS-HEMT	T-ALD	—	[72]
AlN	TMA	N₂ & NH₃	300, 350	AlGaN	HEMT	PE-ALD	2800	[73]
AlN	TMA	NH₃	400	AlGaN	HEMT	T-ALD	—	[74]
AlN	TMA	N₂/H₂	300	p-GaN	LED	PE-ALD	—	[75]
AlN	TMA	N₂	350	AlGaN	Schottky diodes	PE-ALD	2800	[76]
AlN	TMA	NH₃	340	GaN	异质结	T-ALD	—	[77]
AlN	TMA	NH₃	300	GaN	薄膜生长, 异质结	PE-ALD	200	[78]
AlN	TMA	NH₃	335	c-sapphire	异质结	T-ALD	—	[79]
InN	TMI	Ar/N₂	250 ± 20	sapphire	薄膜生长	PE-ALD	300	[80]
InN	TMI	N₂/H₂	200	sapphire	薄膜生长	HCPA-ALD	300	[81]
InN	TMI	NH₃	240—320	Si (100)	薄膜生长	PE-ALD	2400—2800	[82]
InN	TMI	N₂, Ar/N₂, Ar/N₂/H₂	120—240	Si (100)	薄膜生长	HCP-ALD	50—200	[83]
InN	TMI	N₂/Ar	250	GaN (0001)	薄膜生长	PE-ALD	300	[84]
InN	Tris (N, N-dimethyl-N', N''-diisopropylguanidinato) indium (III), Tris (N, N'-diisopropylamidinato) indium (III), Tris(N, N'-diisopropylformamidinato) indium (III)	Ar/NH₃	200—280	Si (100)	薄膜生长	PE-ALD	2800	[85]
InN	Tris(1,3-diisopropyltriazenide) indium (III)	NH₃(Ar/NH₃)	200—400	Si, 4H-SiC	薄膜生长	PE-ALD	2800	[86]
InN	TMI	N₂	190—310	Si (100), Al₂O₃ (0001), ZnO (0001)	薄膜生长	PE-ALD	100—200	[87]
InN	TMI	N₂(Ar)	150—300	glass, polyimide	薄膜生长	PE-ALD	200	[88]
InN	TMI	N₂	180—320	GaN (0001)	薄膜生长	PE-ALD	300	[89]
InN	TMI	NH₃/Ar	320	4H-SiC	薄膜生长	PE-ALD	2800	[90]
InN	TMI	Ar/N₂/H₂(1∶3∶6)	200—300	Si (100)	薄膜生长	PE-ALD	60	[91]

DownLoad: CSV

表 2 使用ALD沉积III族氮化物合金薄膜的生长条件概述, 包括薄膜生长和器件应用.

Table 2. Overview of growth conditions for the deposition of group III nitride alloy films using ALD, including film growth and device applications.

材料	金属前驱体	氮前驱体	沉积温度/ ℃	沉积衬底	应用	ALD类型	等离子体功率/W	参考文献
InGaN	TMI, TEG	N₂/H₂, N₂	200	Si, quartz	薄膜生长	HCPA-ALD	300	[95]
InGaN	Ga(III) and In(III) triazenides	NH₃/Ar	350	Si (100) 4H-SiC (0001)	薄膜生长	PE-ALD	2800	[96]
AlGaN	TMA, TMG	NH₃/N₂/H₂	200	Si (100), Si (111), c-sapphire	薄膜生长	HCPA-ALD	300	[97]
AlGaN	TMA, TMI, TMG	N₂/Ar	350—450	Si (100), a-sapphire, GaN/a-sapphire	薄膜生长	PE-ALD	300	[98]
InAlN			340—300
InGaN			340—300
AlGaN InGaN	TMG, TMA, TMI	N₂/H₂	220—300	Si	薄膜生长	PE-ALD	280	[99]
AlGaN	TMA&TEG	NH₃ & N₂	342	p-Si (100), TiN/SiO₂/Si	薄膜生长	T-ALD	—	[100]
AlGaN	TMA, TEG	NH₃	335	c-GaN	异质结	ALD	—	[101]
AlGaN	TMA. TEG	NH₃	335	c-GaN	异质结	T-ALD	—	[102]
AlGaN	TEG	NH₃	335 ℃	GaN	异质结	T-ALD	—	[103]

DownLoad: CSV

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Vol. 73, Issue 3 - 2024-02-05

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