CN110504343B - 基于蓝宝石衬底的氧化镓薄膜及其生长方法和应用 - Google Patents
基于蓝宝石衬底的氧化镓薄膜及其生长方法和应用 Download PDFInfo
- Publication number
- CN110504343B CN110504343B CN201810479225.8A CN201810479225A CN110504343B CN 110504343 B CN110504343 B CN 110504343B CN 201810479225 A CN201810479225 A CN 201810479225A CN 110504343 B CN110504343 B CN 110504343B
- Authority
- CN
- China
- Prior art keywords
- source
- gallium
- alpha
- sapphire substrate
- time period
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052594 sapphire Inorganic materials 0.000 title claims abstract description 43
- 239000010980 sapphire Substances 0.000 title claims abstract description 36
- 239000000758 substrate Substances 0.000 title claims abstract description 36
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 31
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052733 gallium Inorganic materials 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims description 4
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000001272 nitrous oxide Substances 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 abstract description 30
- 239000010408 film Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 18
- 239000013078 crystal Substances 0.000 abstract description 12
- 239000010409 thin film Substances 0.000 abstract description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 12
- 238000000407 epitaxy Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000231 atomic layer deposition Methods 0.000 description 5
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 5
- 238000001451 molecular beam epitaxy Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/0242—Crystalline insulating materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/16—Controlling or regulating
- C30B25/165—Controlling or regulating the flow of the reactive gases
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/183—Epitaxial-layer growth characterised by the substrate being provided with a buffer layer, e.g. a lattice matching layer
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- 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
- C30B29/16—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
- H01L21/02483—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02494—Structure
- H01L21/02496—Layer structure
- H01L21/02505—Layer structure consisting of more than two layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02494—Structure
- H01L21/02496—Layer structure
- H01L21/0251—Graded layers
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
本发明公开了一种基于蓝宝石衬底的氧化镓薄膜及其生长方法和应用。所述的基于蓝宝石衬底的氧化镓薄膜的制备方法包括:以脉冲外延生长方式在蓝宝石衬底上形成一个以上α‑(AlxGa1‑x)2O3应变缓冲层,其中0.99≥x≥0.01;以及,在所述α‑(AlxGa1‑x)2O3应变缓冲层上形成氧化镓外延层。采用本发明实施例提供的生长方法,不仅可以避免α‑Ga2O3和α‑Al2O3外延温度相矛盾的技术难点,还可以有效降低α‑Ga2O3外延薄膜的缺陷密度,进而提高α‑Ga2O3外延薄膜材料的晶体质量。
Description
技术领域
本发明涉及一种半导体材料的生长方法,特别涉及一种基于蓝宝石衬底的氧化镓薄膜及其生长方法,属于半导体技术与电子技术领域。
背景技术
半导体材料在现代信息工业化社会中发挥着不可替代的作用,是现代半导体工业及微电子工业的基石。随着各种先进技术的不断发展,对高耐压、大功率、抗辐射等高性能电子器件以及深紫外光电子器件需求越来越迫切,尤其是在高耐压及深紫外领域,传统的半导体材料已难以满足使用要求。
超宽带隙氧化物半导体-氧化镓(Ga2O3),相较于第三代半导体材料,如氮化镓(GaN)和碳化硅(SiC),具有更大禁带宽度、更高的击穿场强、透明导电、可以通过熔体法生长、成本更低等优点,而成为半导体材料及器件等领域的研究热点。
Ga2O3材料共有α,β,γ,δ,ε五种已知的晶相,其中β-Ga2O3(Eg=4.7~4.9eV)结构最为稳定并能和其他四种氧化镓之间互相转化。然而α-Ga2O3禁带宽度达到5.3eV,可有效提高器件耐压性能,α-Ga2O3材料的迁移率也高于β-Ga2O3,因此器件性能优于β-Ga2O3。而且α-Ga2O3具有优良的化学稳定性、热稳定性和击穿场强大等优点,在深紫外透明导电薄膜、紫外探测器、半导体功率器件、自旋电子器件、气敏传感器等领域有广阔的应用前景。
目前,α-Ga2O3材料常见的制备方法有各种化学气相沉积(chemical vapordeposition,CVD)如MOCVD、LPCVD、Mist-CVD等,分子束外延(molecular beam epitaxy,MBE),卤化物气相外延(HVPE)、原子层沉积(ALD)等。
α-Ga2O3属于三方晶系,空间群,(晶格常数为α=β=90°,γ=120°,热膨胀系数α=5.23×10-6/℃)。c面蓝宝石(α-Al2O3, α=β=90°,γ=120°,α=5.22×10-6/℃)与α-Ga2O3晶体结构相同,都是刚玉结构,适合做α-Ga2O3异质外延衬底。目前已经有研究报道使用雾化学气相沉积法(Mist-CVD)可以在蓝宝石(Sapphire)衬底上生长高质量的α-Ga2O3,且制备的肖特基二极管(SBD)性能优于SiCSBD。因此,通过使用廉价的Sapphire衬底和CVD生长技术,可以低成本、大规模制备α-Ga2O3材料与器件。
虽然α-Ga2O3与α-Al2O3晶体结构相同,但晶格常数差异和热导率的不同造成外延时存在一定程度的失配,从而导致α-Ga2O3位错增大,薄膜开裂,这就严重影响了材料的应用与器件的发展。
发明内容
本发明的主要目的在于提供一种基于蓝宝石衬底的氧化镓薄膜及其生长方法和应用,以克服现有技术的不足。
为实现前述发明目的,本发明采用的技术方案包括:
本发明实施例提供了一种基于蓝宝石衬底的氧化镓薄膜的制备方法,其包括:
以脉冲外延生长方式在蓝宝石衬底上形成一个以上α-(AlxGa1-x)2O3应变缓冲层,其中0.99≥x≥0.01;以及
在所述α-(AlxGa1-x)2O3应变缓冲层上形成氧化镓外延层。
本发明实施例还提供了由所述的制备方法制备的基于蓝宝石衬底的氧化镓薄膜。
本发明实施例还提供一种基于蓝宝石衬底的氧化镓薄膜,包括蓝宝石衬底和氧化镓外延层,所述蓝宝石衬底和氧化镓外延层之间还形成有一个以上α-(AlxGa1-x)2O3应变缓冲层,其中0.99≥x≥0.01。
本发明实施例还提供了所述的基于蓝宝石衬底的氧化镓薄膜于制作半导体功率器件和半导体光电子器件领域的用途。
与现有技术相比,基于本发明实施例提供的生长方法形成α-(AlxGa1-x)2O3应变缓冲层,不仅可以避免α-Ga2O3和α-Al2O3外延中温度相矛盾的技术难点,还可以有效降低α-Ga2O3外延薄膜的缺陷密度,进而提高α-Ga2O3外延薄膜材料的晶体质量。
附图说明
图1是本发明一典型实施案例中一种基于蓝宝石衬底的氧化镓薄膜的结构示意图;
图2是本发明一典型实施案例中脉冲式外延生长中氧源和铝/镓源的流量示意图;
图3是本发明一典型实施案例中α-(AlxGa1-x)2O3应变缓冲层的外延生长示意图。
具体实施方式
鉴于现有技术中的不足,本案发明人曾尝试采用脉冲式外延方法低温生长不同Al组分的α-(AlxGa1-x)2O3应变缓冲层结构,以缓解α-Ga2O3薄膜应力,降低外延薄膜位错密度,提高α-Ga2O3晶体质量。然而,一方面,Al2O3相比于Ga2O3有更小的键长和更高的分解温度,因此外延α-Al2O3也需要更高的温度。Al原子在外延层表面的物理和化学吸附能力、迁移能力、并入晶格的能力以及解吸附温度等影响着α-(AlxGa1-x)2O3的晶体质量。另一方面,α-Ga2O3外延需要低温度,在高于550℃时会发生相变,这就导致在低于此温度下生长高Al组分的α-(AlxGa1-x)2O3应变缓冲层存在困难。亦即,若采用本案发明人曾经尝试过的前述方案,则不可避免α-Ga2O3和α-Al2O3外延温度相矛盾的问题。
为此,本案发明人又进行了长期研究和大量实践,才得以提出本发明的技术方案,其主要是通过采用脉冲式外延法低温生长α-(AlxGa1-x)2O3复合应变缓冲结构解决现有技术的问题。
本发明实施例提供了一种基于蓝宝石衬底的氧化镓薄膜的制备方法,其包括:
以脉冲外延生长方式在蓝宝石衬底上形成一个以上α-(AlxGa1-x)2O3应变缓冲层,其中0.99≥x≥0.01;以及
在所述α-(AlxGa1-x)2O3应变缓冲层上形成氧化镓外延层。
进一步的,所述的制备方法包括:将蓝宝石衬底置入反应室内,之后采用脉冲方式将氧源、镓源和/或铝源在不同时间单独输入反应室,以形成所述的一个以上α-(AlxGa1-x)2O3应变缓冲层。
更进一步的,所述的制备方法具体包括:在每一个生长循环周期内,先在第一时间段内将氧源、镓源和/或铝源中的任一者持续输入反应室,再间隔一第二时间段,之后在第三时间段内将氧源、镓源和/或铝源中的另一者持续输入反应室,再间隔一第四时间段。
进一步的,所述第一时间段、第二时间段、第三时间段、第四时间段的时长为0.1-99s。
进一步的,所述氧源选自能够提供氧元素的含氧物质。
优选的,所述含氧物质包括氧气、水、一氧化二氮、一氧化氮、二氧化碳和一氧化碳中的任意一种或两种以上的组合,但不限于此。
进一步的,所述镓源选自含镓的有机化合物。
优选的,所述镓源包括三甲基镓和/或三乙基镓,但不限于此。
进一步的,所述铝源选自含铝的有机化合物。
优选的,所述铝源包括三甲基铝和/或三乙基铝,但不限于此。
进一步的,所述α-(AlxGa1-x)2O3应变缓冲层的生长压力为10~760Torr,生长温度为100~1000℃。
更进一步的,所述的制备方法包括:在蓝宝石衬底上依次形成1-99个所述α-(AlxGa1-x)2O3应变缓冲层。
更进一步的,一个所述α-(AlxGa1-x)2O3应变缓冲层的厚度为1-1000nm。
进一步的,其中至少两个α-(AlxGa1-x)2O3层中Al元素的含量不相同。
进一步的,所述氧化镓外延层的生长压力为10~760Torr,生长温度为100~600℃。
进一步的,所述氧化镓外延层的材质为α-Ga2O3。
本发明实施例还提供了由所述的制备方法制备的基于蓝宝石衬底的氧化镓薄膜。
本发明实施例还提供一种基于蓝宝石衬底的氧化镓薄膜,包括蓝宝石衬底和氧化镓外延层,所述蓝宝石衬底和氧化镓外延层之间还形成有一个以上α-(AlxGa1-x)2O3应变缓冲层,其中0.99≥x≥0.01。
进一步的,每一α-(AlxGa1-x)2O3层的厚度为1-1000nm。
进一步的,所述氧化镓薄膜包括1-99个α-(AlxGa1-x)2O3层。
进一步的,其中至少两个α-(AlxGa1-x)2O3层的A1元素的含量不相同。
本发明通过采用脉冲式外延方法低温生长不同A1组分的α-(AlxGa1-x)2O3应变缓冲层结构,不仅可以避免α-Ga2O3和α-Al2O3外延中温度相矛盾的难题,还可以有效降低α-Ga2O3外延薄膜的缺陷密度,缓解α-Ga2O3薄膜应力,进而提高α-Ga2O3外延薄膜材料的晶体质量。
本发明实施例还提供了所述的基于蓝宝石衬底的氧化镓薄膜于制作半导体功率器件或半导体光电子器件中的用途。
如下将结合实施例及附图对本发明实施例的技术方案、其实施过程及原理等作进一步的解释说明。
请参阅图1,图1示出了本发明一典型实施例中一种基于蓝宝石衬底的氧化镓薄膜的结构示意图,其包括蓝宝石衬底,以及依次在蓝宝石衬底上设置的多个α-(AlxGa1-x)2O3应变缓冲层和一个或更多α-Ga2O3外延层。
本实施例中基于蓝宝石衬底的氧化镓薄膜可以包括如下步骤:
1)在蓝宝石衬底上采用脉冲式外延法低温生长α-(AlxGa1-x)2O3应变缓冲层。该外延生长的方法可以选自化学气相沉积(chemical vapor deposition,CVD),特别是MOCVD(金属有机化学气相沉积)等,适用的设备包括CVD(化学气相沉积设备),LPCVD(低压化学气相沉积设备),MOCVD(金属有机化学气相沉积设备),MBE(分子束外延设备),LMBE(激光分子束外延设备),ALD(单原子层沉积设备)、PEALD(等离子体增强原子层沉积设备),HVPE(氢化物气相外延设备)等。
具体而言,请参阅图2和图3,氧源(可以是氧气)和镓/铝源(例如三乙基镓/三甲基镓)以脉冲分离的方式,周期性的进行外延生长,即在一个脉冲循环周期内(t1、t2、t3、t4脉冲宽度分是代表氧源通入反应室的时间、间歇时间、镓/铝源通入反应室的时间、间歇时间四个变量,它们间隔交替,其中0.1s≤t1/t2/t3/t4≤99s)通过脉冲循环次数、脉冲宽度(对应氧源,镓/铝源进入反应室的时间)和脉冲个数(对应氧源,镓/铝源进入反应室的次数)的灵活调控和设计,进而实现较低温下高质量α-(AlxGa1-x)2O3薄膜材料(即所述应变缓冲层)的生长(即在较低温度下使原子迁移到最佳位置成键,进行高质量薄膜外延)。
采用脉冲式外延将氧源和镓/铝源在不同的时间单独通入反应室,可以降低O和Al/Ga到达衬底之前接触而发生预反应的机会,减少预反应产物淀积引起的材料缺陷,增加Al/Ga原子在生长表面的横向迁移率,使Al/Ga-O在生长面最佳格点反应成键,使(AlxGa1-x)2O3结合更规则,原子结合到晶体中时得以规则的排列,获得原子级光滑表面。
通过调整脉宽、间隔、周期和叠加时间等脉冲式生长的工艺参数来控制生长过程,提高结晶质量,在不同Al组分的缓冲层基础上,通过(AlxGa1-x)2O3(0.99≥x≥0.01)温度和厚度的控制,调节外延过程中的应变,释放应力。
该实施例中的氧源可以选自能产生O分子的各种含氧物质,如氧气,水,一氧化二氮,一氧化氮,二氧化碳,一氧化碳等。
该实施例中的镓源可以选自各种Ga的金属有机源,如三甲基镓TEG,三乙基镓TMG;含Ga的其他物质。
该实施例中的铝源可以选自各种Al的金属有机源,如三甲基铝TEA,三乙基铝TMA;含Al的其他物质。
该实施例中各α-(AlxGa1-x)2O3应变缓冲层外延生长时的压力优选控制为10Torr~760Torr或更高压力。
该实施例中各α-(AlxGa1-x)2O3应变缓冲层的外延生长温度优选为100℃~1000℃。
该实施例中各α-(AlxGa1-x)2O3应变缓冲层的外延生长温度优选为100℃~600℃。
该实施例中各α-(AlxGa1-x)2O3应变缓冲层中x的取值范围优选为0.99≥x≥0.01。
该实施例中α-(AlxGa1-x)2O3应变缓冲层的层数优选为99≥层数≥1。
该实施例中各α-(AlxGa1-x)2O3应变缓冲层的厚度优选为1nm≥厚度≥1000nm。
该实施例中前述脉冲式外延时各个时间(t1、t2、t3、t4)优选为99s≥t≥0.1s。
2)进行α-Ga2O3外延层的生长
该实施例中α-Ga2O3外延层的生长设备亦可以是MOCVD(金属有机化学气相沉积)等,适用的设备包括适用的设备包括CVD(化学气相沉积设备),LPCVD(低压力化学气相沉积设备),MOCVD(金属有机化学气相沉积设备),MBE(LMBE)(分子束外延设备),ALD(PEALD)(单原子层沉积设备),HVPE(氢化物气相外延设备)等。
该实施例的步骤2)所采用的外延生长压力优选为10Torr~760Torr或更高压力。
该实施例中α-Ga2O3外延层的生长温度优选为100℃~600℃。
采用本发明实施例提供的方法,不仅可以避免α-Ga2O3和α-Al2O3外延中温度相矛盾的技术难点,还可以有效降低α-Ga2O3外延薄膜的缺陷密度,获得具有较为理想的质量的α-Ga2O3外延薄膜材料。
应当理解,上述实施例仅为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (9)
1.一种基于蓝宝石衬底的氧化镓薄膜的制备方法,其特征在于包括:
将蓝宝石衬底置入反应室内,于10~760Torr、100~1000℃条件下,采用脉冲方式将氧源、镓源和/或铝源在不同时间单独输入反应室,以形成一个以上应变缓冲层,0.99≥x≥0.01,其中,至少两个层中Al元素的含量不相同;
在每一个生长循环周期内,先在第一时间段内将氧源、镓源和/或铝源中的任一者持续输入反应室,再间隔一第二时间段,之后在第三时间段内将氧源、镓源和/或铝源中的另一者持续输入反应室,再间隔一第四时间段,所述第一时间段、第二时间段、第三时间段、第四时间段的时长为0.1-99s;以及
2.根据权利要求1所述的制备方法,其特征在于:所述氧源选自含氧物质。
3.根据权利要求2所述的制备方法,其特征在于:所述含氧物质包括氧气、水、一氧化二氮、一氧化氮、二氧化碳和一氧化碳中的任意一种或两种以上的组合。
4.根据权利要求1所述的制备方法,其特征在于:所述镓源选自含镓的有机化合物。
5.根据权利要求4所述的制备方法,其特征在于:所述镓源包括三甲基镓和/或三乙基镓。
6.根据权利要求1所述的制备方法,其特征在于:所述铝源选自含铝的有机化合物。
7.根据权利要求6所述的制备方法,其特征在于:所述铝源包括三甲基铝和/或三乙基铝。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810479225.8A CN110504343B (zh) | 2018-05-18 | 2018-05-18 | 基于蓝宝石衬底的氧化镓薄膜及其生长方法和应用 |
PCT/CN2018/109317 WO2019218581A1 (zh) | 2018-05-18 | 2018-10-08 | 基于蓝宝石衬底的氧化镓薄膜及其生长方法和应用 |
US17/051,779 US11996288B2 (en) | 2018-05-18 | 2018-10-08 | Gallium oxide film based on sapphire substrate as well as growth method and application thereof |
JP2020564615A JP7173621B2 (ja) | 2018-05-18 | 2018-10-08 | サファイア基板を含む酸化ガリウム薄膜の製造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810479225.8A CN110504343B (zh) | 2018-05-18 | 2018-05-18 | 基于蓝宝石衬底的氧化镓薄膜及其生长方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110504343A CN110504343A (zh) | 2019-11-26 |
CN110504343B true CN110504343B (zh) | 2021-02-23 |
Family
ID=68539382
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810479225.8A Active CN110504343B (zh) | 2018-05-18 | 2018-05-18 | 基于蓝宝石衬底的氧化镓薄膜及其生长方法和应用 |
Country Status (4)
Country | Link |
---|---|
US (1) | US11996288B2 (zh) |
JP (1) | JP7173621B2 (zh) |
CN (1) | CN110504343B (zh) |
WO (1) | WO2019218581A1 (zh) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111524995B (zh) * | 2020-04-21 | 2022-02-15 | 昌吉学院 | β-Ga2O3/GaN异质结日盲/可见盲双色紫外探测器及其制备方法 |
JP7061214B2 (ja) * | 2020-08-06 | 2022-04-27 | 信越化学工業株式会社 | 半導体積層体、半導体素子および半導体素子の製造方法 |
CN116157550A (zh) * | 2020-08-06 | 2023-05-23 | 信越化学工业株式会社 | 半导体层叠体、半导体元件及半导体元件的制造方法 |
CN112359417B (zh) * | 2020-09-27 | 2022-11-01 | 南京新澳半导体科技有限公司 | 一种无掩模原位横向外延α相氧化镓薄膜的方法 |
TR202019031A2 (tr) * | 2020-11-25 | 2021-02-22 | Univ Yildiz Teknik | Yüksek kalitede hetero epitaksiyel monoklinik galyum oksit kristali büyütme metodu |
KR102537070B1 (ko) * | 2020-11-30 | 2023-05-26 | 서울대학교산학협력단 | 알파-산화알루미늄갈륨을 활용한 알파-산화갈륨 박막의 제조방법 |
CN113571404B (zh) * | 2021-06-07 | 2024-07-12 | 西安电子科技大学 | 一种β-Ga2O3薄膜的生长方法 |
CN114141910B (zh) * | 2021-11-27 | 2023-09-15 | 北京铭镓半导体有限公司 | 一种蓝宝石衬底生长纯相Ga2O3薄膜的方法及日盲紫外探测器 |
US20230167548A1 (en) * | 2021-11-30 | 2023-06-01 | Illinois Institute Of Technology | Thermal atomic layer deposition of ternary gallium oxide thin films |
CN114525585A (zh) * | 2022-01-05 | 2022-05-24 | 西安电子科技大学 | 采用预铺Ga层在金刚石上外延β-Ga2O3薄膜的制备方法及结构 |
CN114725234B (zh) * | 2022-03-23 | 2024-03-22 | 电子科技大学 | 基于非晶Ga2O3薄膜的日盲紫外探测器及其制备方法 |
KR102557905B1 (ko) * | 2022-09-14 | 2023-07-20 | 한국세라믹기술원 | 고품질의 대면적 초박형 산화갈륨 박막 제조 방법 |
JP2024042611A (ja) * | 2022-09-15 | 2024-03-28 | 株式会社Flosfia | 電力変換回路および制御システム |
CN115821378A (zh) * | 2022-11-29 | 2023-03-21 | 厦门大学 | 一种等离子体热氧化制备氧化镓薄膜的方法 |
CN115838971B (zh) * | 2023-02-14 | 2023-06-13 | 楚赟精工科技(上海)有限公司 | 氧化镓薄膜及其制备方法 |
CN116314278B (zh) * | 2023-05-22 | 2023-08-15 | 江西兆驰半导体有限公司 | 高电子迁移率晶体管外延结构及制备方法、hemt器件 |
CN116377582A (zh) * | 2023-05-30 | 2023-07-04 | 北京青禾晶元半导体科技有限责任公司 | 一种氧化镓薄膜及其生长方法和应用 |
KR102675782B1 (ko) * | 2023-06-30 | 2024-06-18 | 삼성전자주식회사 | 커패시터 및 이를 포함하는 반도체 장치 |
CN116936631B (zh) * | 2023-09-15 | 2023-12-12 | 江西兆驰半导体有限公司 | 一种氮化镓基晶体管的外延结构及制备方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020084455A1 (en) * | 1999-03-30 | 2002-07-04 | Jeffery T. Cheung | Transparent and conductive zinc oxide film with low growth temperature |
JP4888857B2 (ja) * | 2006-03-20 | 2012-02-29 | 国立大学法人徳島大学 | Iii族窒化物半導体薄膜およびiii族窒化物半導体発光素子 |
US8338273B2 (en) * | 2006-12-15 | 2012-12-25 | University Of South Carolina | Pulsed selective area lateral epitaxy for growth of III-nitride materials over non-polar and semi-polar substrates |
JP2009155672A (ja) * | 2007-12-25 | 2009-07-16 | Showa Denko Kk | Iii族窒化物半導体の製造方法、iii族窒化物半導体発光素子の製造方法、iii族窒化物半導体製造装置、iii族窒化物半導体及びiii族窒化物半導体発光素子、並びにランプ |
CN101921994B (zh) * | 2010-07-30 | 2011-12-21 | 北京印刷学院 | 一种原子层沉积超薄氧化铝薄膜的装置及方法 |
KR102094568B1 (ko) * | 2012-10-17 | 2020-03-27 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 반도체 장치 및 그의 제작 방법 |
CN103489967B (zh) * | 2013-09-05 | 2016-07-13 | 大连理工大学 | 一种氧化镓外延膜的制备方法及氧化镓外延膜 |
CN103456603B (zh) * | 2013-09-05 | 2016-04-13 | 大连理工大学 | 在镓系异质半导体衬底上制备氧化镓膜的方法及氧化镓膜 |
CN104988579A (zh) * | 2015-07-08 | 2015-10-21 | 西安电子科技大学 | 基于蓝宝石衬底的氧化镓薄膜及其生长方法 |
WO2017152620A1 (zh) * | 2016-03-08 | 2017-09-14 | 西安电子科技大学 | 基于石墨烯与磁控溅射氮化铝的氮化镓生长方法 |
-
2018
- 2018-05-18 CN CN201810479225.8A patent/CN110504343B/zh active Active
- 2018-10-08 US US17/051,779 patent/US11996288B2/en active Active
- 2018-10-08 WO PCT/CN2018/109317 patent/WO2019218581A1/zh active Application Filing
- 2018-10-08 JP JP2020564615A patent/JP7173621B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
US20210327703A1 (en) | 2021-10-21 |
US11996288B2 (en) | 2024-05-28 |
WO2019218581A1 (zh) | 2019-11-21 |
JP2021527610A (ja) | 2021-10-14 |
CN110504343A (zh) | 2019-11-26 |
JP7173621B2 (ja) | 2022-11-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110504343B (zh) | 基于蓝宝石衬底的氧化镓薄膜及其生长方法和应用 | |
US10192737B2 (en) | Method for heteroepitaxial growth of III metal-face polarity III-nitrides on substrates with diamond crystal structure and III-nitride semiconductors | |
CN109346400B (zh) | 一种高质量Ga2O3薄膜及其异质外延制备方法 | |
EP1298709B1 (en) | Method for producing a iii nitride element comprising a iii nitride epitaxial substrate | |
US6648966B2 (en) | Wafer produced thereby, and associated methods and devices using the wafer | |
WO2023231566A1 (zh) | 半导体外延结构及其制备方法、半导体器件 | |
CN114664642B (zh) | 基于iii族氮化物同质外延的hemt结构、其制备方法及应用 | |
CN107808916B (zh) | Led晶元及其制备方法和led灯 | |
WO2023087543A1 (zh) | N极性GaN/AlGaN异质结外延结构及其制备方法 | |
EP2575161A2 (en) | Method of growing semiconductor crystal | |
CN112490112A (zh) | 氧化镓薄膜及其异质外延生长方法与应用 | |
US9396936B2 (en) | Method for growing aluminum indium nitride films on silicon substrate | |
CN116682910B (zh) | 一种氮化镓外延片结构及其制备方法 | |
CN116666196A (zh) | 无旋转畴的κ-Ga2O3薄膜及κ-(AlxGa1-x)2O3/κ-Ga2O3异质结的制备方法 | |
CN111863945A (zh) | 一种高阻氮化镓及其异质结构的制备方法 | |
KR20200057698A (ko) | 고 전자 이동도 트랜지스터를 위한 이종구조체 및 이를 제조하는 방법 | |
KR20100104997A (ko) | 전위 차단층을 구비하는 질화물 반도체 기판 및 그 제조 방법 | |
Twigg et al. | Nucleation layer microstructure, grain size, and electrical properties in GaN grown on a-plane sapphire | |
CN111312585B (zh) | 一种低位错密度氮化物的外延层生长方法 | |
JP7120598B2 (ja) | 窒化アルミニウム単結晶膜及び半導体素子の製造方法 | |
CN110670138A (zh) | 用于氮化铝单晶生长的复合籽晶及其制备方法 | |
Li et al. | Epitaxial of III-Nitride LED Materials | |
KR100975835B1 (ko) | 인듐을 이용한 저온에서의 나노 구조체 제조방법 | |
CN106601787B (zh) | 一种InxAlyGa1-x-yN/GaN异质结构及其外延方法 | |
CN114293249A (zh) | Iii族氮化物半导体材料的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |