CN103695999B - Nitride single crystal film prepared by a kind of alternately supply source and method - Google Patents
Nitride single crystal film prepared by a kind of alternately supply source and method Download PDFInfo
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- CN103695999B CN103695999B CN201310629287.XA CN201310629287A CN103695999B CN 103695999 B CN103695999 B CN 103695999B CN 201310629287 A CN201310629287 A CN 201310629287A CN 103695999 B CN103695999 B CN 103695999B
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Abstract
The present invention is the brilliant film of a kind of high quality nitride utilizing alternately supply source to prepare, and its structure is aluminium nitride AlN buffer layer in single crystalline substrate; Aluminium nitride AlN buffer layer is nitride single crystal film.Its preparation method, comprises following processing step: a) single crystalline substrate puts into reaction chamber, high bake; B) in single crystalline substrate, Al soakage layer is prepared; C) on soakage layer, prepare aluminium nitride AlN buffer layer; D) on aluminium nitride AlN buffer layer, nitride single crystal film is prepared; E) be down to room temperature, take out.Advantage: present method prepares on the basis of the aluminum nitride buffer layer of high-crystal quality in alternately supply source method, in conjunction with In atmosphere protection and Al soakage layer, can improve crystal and the surface quality of nitride single crystal film further, and reduce membrane stress; Have that structure is simple, technique is controlled; Surface topography is good; The features such as low cost.
Description
Technical field
What the present invention relates to is a kind of in single crystalline substrate, utilize In as protective atmosphere, with Al soakage layer with alternately pass into Al source, N source and prepare aluminum nitride buffer layer, thus improve nitride single crystal film quality replace nitride single crystal film and method prepared by supply source.Belong to wide bandgap semiconductor epitaxial material technical field.
Background technology
For want of high-quality monocrystal material is as homo-substrate, and nitride film is prepared in the hetero epitaxy mode of large mismatch substantially.Usual introducing two-step approach overcomes lattice mismatch between substrate and epitaxial film and coefficient of thermal expansion mismatch, can obtain the nitride epitaxial film of better quality.According to the difference of substrate kind, gan or aluminium nitride how can be adopted as buffer layer.Aluminum nitride buffer layer is because lattice parameter is less, and stable in properties, produces stress to the nitride film of growth on it, reduce the probability cracked, and in addition, because its insulativity is better, in multiple electronics and microwave device, obtains more application.
Conventional epitaxy method can prepare aluminum nitride buffer layer, but because the restriction on the low side of conventional epitaxial equipment growth temperature, its crystal mass can't be satisfactory.The method of growing aluminum nitride has growth continuously and replaces TongYuan's growth method.Continuous growth method keeps unremitting the continuing in Al source and N source to pass in aluminium nitride process of growth, prepares aluminium nitride by processing condition such as adjustment temperature, pressure, flows; Alternately TongYuan's growth method is that Al source and N source alternately pass into respectively in a pulsed fashion, mainly avoid pre-reaction, period is passed into there is no N source, relatively add the surface migration lengths of Al atom, can under the condition not improving growth temperature, by the quality of the improvement of terms aluminium nitride such as the time that passes into, flow, interval time in adjustment Al source and N source.The obstacle of continuous growth method is the growth temperature needing significantly to improve epitaxial device, faces the transformation difficult problems such as power supply, well heater, pilot circuit, reaction chamber.Alternately the advantage of TongYuan's method does not need to improve growth temperature, just can improve the preparation of aluminium nitride.Although alternately TongYuan's method is better than the effect of continuous growth method to a certain extent, the length surface of the just Al atom changed, does not improve the quality of aluminium nitride from this basic reason of change Al atomic surface travelling speed.
Summary of the invention
Nitride single crystal film prepared by a kind of alternately supply source that what the present invention proposed is and method, its object is intended to the above-mentioned defect overcome existing for prior art.Replacing supply source method increase Al atomic surface migration length, prepare on the basis of high quality aluminum nitride buffer layer, introduce the protection of In atmosphere on the one hand, effective raising Al atom is in the travelling speed of substrate surface, and continue to pass into certain hour after AlN synthesis terminates, impel the improvement of surface quality; When replacing TongYuan on the other hand, Al source is first passed into substrate surface, this step has two effects, it is the first step replacing TongYuan and prepare aluminium nitride, also can form soakage layer at substrate surface simultaneously, the surface energy of reduction substrate, passes into N source subsequently and Al soakage layer generates aluminium nitride, improves the crystal mass of aluminium nitride.In addition, after AlN synthesis terminates, In source also will continue to pass into for some time and closes, ensure that planeness and the slickness on surface.When not improving growth temperature, crystal mass and the surface topography of nitride single crystal film can be improved further, reducing stress, avoid continuous growing method and replace the deficiency of supply source legal system for AlN buffer layer.The advantages such as it is simple that the present invention has method, and technology difficulty is little, easy realization.
Technical solution of the present invention: a kind of utilization replaces the brilliant film of high quality nitride prepared by supply source, and its structure is aluminium nitride AlN buffer layer in single crystalline substrate; Aluminium nitride AlN buffer layer is nitride single crystal film.
Its preparation method, comprises following processing step:
A) single crystalline substrate puts into reaction chamber, high bake;
B) in single crystalline substrate, Al soakage layer is prepared;
C) on soakage layer, prepare aluminium nitride AlN buffer layer;
D) on aluminium nitride AlN buffer layer, nitride single crystal film is prepared;
E) be down to room temperature, take out.
Advantage of the present invention: 1) AlN buffer layer preparation process and preparation terminate all to adopt In atmosphere protection in rear for some time, effectively increases the travelling speed of Al atom, improves the crystal mass of aluminum nitride buffer layer and the smooth of surface.2) adopt Al soakage layer to reduce surface energy, improve stress and the crystal mass of aluminum nitride buffer layer.3) the AlN buffer layer of alternating growth contributes to realizing two-dimensional growth, and the stress of buffering nitride single crystal film, improves crystal and surface quality.4) structure is simple, and preparation technology is controlled.5) cost is low, is widely used, can growing nitride series monocrystal film and multilayered structure.
Accompanying drawing explanation
Accompanying drawing 1 is the structural representation preparing nitride single crystal film.
Accompanying drawing 2 is In sources in aluminum nitride buffer layer preparation process, Al source and N source pass into sequential schematic.
In figure 1 is single crystalline substrate, 2 are aluminium nitride (AlN) buffer layers, 3 is nitride single crystal films.
Embodiment
Contrast accompanying drawing 1,2, the brilliant film of high quality nitride, its structure is aluminium nitride AlN buffer layer 2 in single crystalline substrate 1; Aluminium nitride AlN buffer layer is nitride single crystal film 3.
Its preparation method, comprises following processing step:
A) single crystalline substrate puts into reaction chamber, high bake;
B) in single crystalline substrate, Al soakage layer is prepared;
C) on soakage layer, prepare aluminium nitride AlN buffer layer;
D) on aluminium nitride AlN buffer layer, nitride single crystal film is prepared;
E) be down to room temperature, take out.
Described single crystalline substrate is sapphire, silicon carbide (SiC), silicon (Si), gan, aluminium nitride, silicon-on-insulator (SOI) or lithium aluminate.
After terminating with preparation in described aluminium nitride AlN buffer layer preparation process at the appointed time, In source is passed into all the time.
The method preparation that described aluminium nitride AlN buffer layer adopts Al source and N source alternately to pass into, namely each unit of preparing first passes into Al source and stops after 5 ~ 30 seconds, then passes into N source and stop after 5 ~ 30 seconds, until AlN buffer layer thickness meets the demands.
The preparation temperature T of described aluminium nitride AlN buffer layer
lbe 500 DEG C≤T
l≤ 1300 DEG C, thickness t is 10nm≤t≤1000nm.
Described nitride single crystal film comprises gan, aluminium nitride, indium nitride binary single-crystal film, or consisting of polynary monocrystal thin films, and multilayered structure.
Its structure single crystalline substrate 1 is aluminium nitride (AlN) buffer layer 2; Aluminium nitride (AlN) buffer layer 2 is nitride single crystal films 3.
embodiment 1
1) select single crystal Si substrate, put into MOCVD reaction chamber;
2) be warming up to 1080 DEG C, hydrogen atmosphere toasts 10 minutes;
3) be cooled to 600 DEG C, 150torr, after trimethyl indium and trimethyl aluminium pass into 30 seconds, stop passing into trimethyl aluminium, form Al soakage layer, ammonia stops after passing into 30 seconds;
4) pass into trimethyl aluminium to stop after 30 seconds, ammonia stops after passing into 30 seconds, keeps alternately passing into trimethyl aluminium and ammonia, until aluminium nitride thickness reaches 100nm, closes trimethyl aluminium;
5) pass into ammonia, within 30 seconds, stop afterwards passing into trimethyl indium;
6) be warming up to 1060 DEG C, 100Torr, pass into trimethyl-gallium and grow 2 μm of thick GaN monocrystal thin films;
7) close trimethyl-gallium, drop to room temperature in protection of ammonia.
embodiment 2
1) select monocrystalline SOI substrate, put into MOCVD reaction chamber;
2) be warming up to 1060 DEG C, hydrogen atmosphere toasts 10 minutes;
3) be cooled to 1000 DEG C, 100torr, after trimethyl indium and trimethyl aluminium pass into 20 seconds, stop passing into trimethyl aluminium, form Al soakage layer, ammonia stops after passing into 20 seconds;
4) pass into trimethyl aluminium to stop after 20 seconds, ammonia stops after passing into 20 seconds, keeps alternately passing into trimethyl aluminium and ammonia, until aluminium nitride thickness reaches 500nm, closes trimethyl aluminium;
5) pass into ammonia, within 20 seconds, stop afterwards passing into trimethyl indium;
6) close trimethyl aluminium, be warming up to 1060 DEG C, 100Torr, pass into trimethyl-gallium and silane grows 3 μm of thick N-shaped GaN monocrystal thin films;
7) close trimethyl-gallium and silane, drop to room temperature in protection of ammonia.
Embodiment 3
1) select monocrystalline sapphire substrate, put into MOCVD reaction chamber;
2) be warming up to 1100 DEG C, hydrogen atmosphere toasts 10 minutes;
3) be cooled to 1080 DEG C, 80torr, after trimethyl indium and trimethyl aluminium pass into 10 seconds, stop passing into trimethyl aluminium, form Al soakage layer, ammonia stops after passing into 10 seconds;
4) pass into trimethyl aluminium to stop after 10 seconds, ammonia stops after passing into 10 seconds, keeps alternately passing into trimethyl aluminium and ammonia, until aluminium nitride thickness reaches 1000nm, closes trimethyl aluminium;
5) pass into ammonia, within 10 seconds, stop afterwards passing into trimethyl indium;
6) be warming up to 1060 DEG C, 100Torr, pass into trimethyl-gallium and trimethyl aluminium grows 1 μm of thick AlGaN monocrystal thin films;
7) close trimethyl-gallium and trimethyl aluminium, drop to room temperature in protection of ammonia.
Embodiment 4
1) select single crystal SiC substrate, put into MOCVD reaction chamber;
2) be warming up to 1100 DEG C, hydrogen atmosphere toasts 10 minutes;
3) be warming up to 1200 DEG C, 50torr, after trimethyl indium and trimethyl aluminium pass into 10 seconds, stop passing into trimethyl aluminium, form Al soakage layer, ammonia stops after passing into 20 seconds;
4) pass into trimethyl aluminium to stop after 10 seconds, ammonia stops after passing into 20 seconds, keeps alternately passing into trimethyl aluminium and ammonia, until aluminium nitride thickness reaches 200nm, closes trimethyl aluminium;
5) pass into ammonia, within 15 seconds, stop afterwards passing into trimethyl indium;
6) be cooled to 1060 DEG C, 100Torr, pass into trimethyl-gallium and trimethyl aluminium grows 1 μm of thick AlGaN monocrystal thin films;
7) close trimethyl-gallium and trimethyl aluminium, drop to room temperature in protection of ammonia.
Embodiment 5
1) select single crystal SiC substrate, put into MBE reaction chamber;
2) be warming up to 890 DEG C, toast 10 minutes;
3) be warming up to 910 DEG C, after indium source and aluminium source pass into 10 seconds, stop logical aluminium, form Al soakage layer, nitrogenous source stops after passing into 15 seconds;
4) pass into aluminium to stop after 5 seconds, N source stops after passing into 5 seconds, keeps alternately passing into aluminium source and nitrogenous source, until aluminium nitride thickness reaches 10nm, closes aluminium source;
5) pass into nitrogenous source, within 10 seconds, stop afterwards passing into indium source;
6) be cooled to 800 DEG C, pass into Ga source and grow 2 μm of thick GaN monocrystal thin films;
7) close Ga and N source, be down to room temperature.
The nitride single crystal film of low-dislocation-density not only can be grown according to aforesaid method, can also the various device architecture of continued growth thereon.
Preparation broad stopband monocrystal thin films structure involved in the present invention and method can utilize common as MOCVD(metalorganic chemical vapor deposition), CVD(chemical vapor deposition), MBE(molecular beam epitaxy), UHVCVD(high vacuum chemical gas deposition) etc. film preparing technology realize, according to technical characterstic, realization of the present invention includes but not limited to aforesaid method.
Claims (1)
1. utilize alternately supply source to prepare a method for gallium nitride single crystal film, it is characterized in that comprising following processing step:
1) select single crystal Si substrate, put into MOCVD reaction chamber;
2) be warming up to 1080 DEG C, hydrogen atmosphere toasts 10 minutes;
3) be cooled to 600 DEG C, 150torr, after trimethyl indium and trimethyl aluminium pass into 30 seconds, stop passing into trimethyl aluminium, form Al soakage layer, ammonia stops after passing into 30 seconds;
4) pass into trimethyl aluminium to stop after 30 seconds, ammonia stops after passing into 30 seconds, keeps alternately passing into trimethyl aluminium and ammonia, until aluminium nitride thickness reaches 100nm, closes trimethyl aluminium;
5) pass into ammonia, within 30 seconds, stop afterwards passing into trimethyl indium;
6) be warming up to 1060 DEG C, 100Torr, pass into trimethyl-gallium and grow 2 μm of thick GaN monocrystal thin films;
7) close trimethyl-gallium, drop to room temperature in protection of ammonia.
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| CN103710747B (en) * | 2013-12-02 | 2016-06-08 | 中国电子科技集团公司第五十五研究所 | Nitride single crystal film and method are prepared in the conveying of a kind of interval, N source |
| CN105543969B (en) * | 2016-01-25 | 2018-05-01 | 南通同方半导体有限公司 | A kind of growing method of improvement AlN film crystal quality |
| CN110224020A (en) * | 2019-05-28 | 2019-09-10 | 苏州汉骅半导体有限公司 | The method for manufacturing high quality and high uniformity group III-nitride epitaxial structure |
| CN111710592B (en) * | 2020-06-28 | 2022-08-12 | 中国科学院长春光学精密机械与物理研究所 | Ga 2 O 3 Film and preparation method thereof |
| CN111739791B (en) * | 2020-08-25 | 2020-12-18 | 中电化合物半导体有限公司 | Epitaxial structure of gallium nitride material and preparation method |
| CN112242463B (en) * | 2020-09-29 | 2022-05-20 | 苏州紫灿科技有限公司 | Deep ultraviolet LED with pulse doped electron blocking layer and preparation method thereof |
| CN113284986B (en) * | 2021-03-29 | 2023-03-24 | 华灿光电（浙江）有限公司 | Preparation method of light-emitting diode epitaxial wafer |
| CN113481593B (en) * | 2021-05-14 | 2022-12-13 | 华灿光电（浙江）有限公司 | Preparation method of light-emitting diode epitaxial wafer with AlN |
| CN114277443B (en) * | 2021-12-28 | 2022-12-30 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nitride single crystal film and preparation method and application thereof |
| CN117904719B (en) * | 2024-03-15 | 2024-07-30 | 浙江求是半导体设备有限公司 | N-type SiC epitaxial wafer and preparation method thereof |
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