TWI427828B - 氮化物類化合物半導體及其製法 - Google Patents
氮化物類化合物半導體及其製法 Download PDFInfo
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- TWI427828B TWI427828B TW094125495A TW94125495A TWI427828B TW I427828 B TWI427828 B TW I427828B TW 094125495 A TW094125495 A TW 094125495A TW 94125495 A TW94125495 A TW 94125495A TW I427828 B TWI427828 B TW I427828B
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- layer
- nitride
- compound semiconductor
- based compound
- light
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- 239000004065 semiconductor Substances 0.000 title claims description 72
- 238000000034 method Methods 0.000 title claims description 30
- -1 Nitride compound Chemical class 0.000 title description 7
- 150000004767 nitrides Chemical class 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 49
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 21
- 239000013078 crystal Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 17
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 239000002019 doping agent Substances 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910052738 indium Inorganic materials 0.000 description 7
- 229910052594 sapphire Inorganic materials 0.000 description 7
- 239000010980 sapphire Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 3
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- USZGMDQWECZTIQ-UHFFFAOYSA-N [Mg](C1C=CC=C1)C1C=CC=C1 Chemical compound [Mg](C1C=CC=C1)C1C=CC=C1 USZGMDQWECZTIQ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- WCZKTXKOKMXREO-UHFFFAOYSA-N triethylsulfanium Chemical compound CC[S+](CC)CC WCZKTXKOKMXREO-UHFFFAOYSA-N 0.000 description 2
- QDLFVXRWLQSBTF-UHFFFAOYSA-N 1,1,2-triethylhydrazine Chemical compound CCNN(CC)CC QDLFVXRWLQSBTF-UHFFFAOYSA-N 0.000 description 1
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- VNWSGLAFGBBSAA-UHFFFAOYSA-N C(C)C1(C=CC=C1)[Ca]C1(C=CC=C1)CC Chemical compound C(C)C1(C=CC=C1)[Ca]C1(C=CC=C1)CC VNWSGLAFGBBSAA-UHFFFAOYSA-N 0.000 description 1
- MLKKSFBXZUQIKU-UHFFFAOYSA-N CC1(C=CC=C1)[Ca]C1(C=CC=C1)C Chemical compound CC1(C=CC=C1)[Ca]C1(C=CC=C1)C MLKKSFBXZUQIKU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UVYFNBNJLFERLL-UHFFFAOYSA-N FC(F)=CC#C[Ca]C#CC=C(F)F Chemical compound FC(F)=CC#C[Ca]C#CC=C(F)F UVYFNBNJLFERLL-UHFFFAOYSA-N 0.000 description 1
- XWTOLKZWCPVUJJ-UHFFFAOYSA-N FC1=C(F)C(F)([Ca]C2(F)C(F)=C(F)C(F)=C2F)C(F)=C1F Chemical compound FC1=C(F)C(F)([Ca]C2(F)C(F)=C(F)C(F)=C2F)C(F)=C1F XWTOLKZWCPVUJJ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 1
- HVBGBVXHGSELCT-UHFFFAOYSA-N [Ca](C1C=CC=C1)C1C=CC=C1 Chemical compound [Ca](C1C=CC=C1)C1C=CC=C1 HVBGBVXHGSELCT-UHFFFAOYSA-N 0.000 description 1
- LZNROSKSIPUXML-UHFFFAOYSA-N [Ca](c1cccc2ccccc12)c1cccc2ccccc12 Chemical compound [Ca](c1cccc2ccccc12)c1cccc2ccccc12 LZNROSKSIPUXML-UHFFFAOYSA-N 0.000 description 1
- IPOANIITHDTHQG-UHFFFAOYSA-N [Ca]C#CC1=CC=CC=C1 Chemical compound [Ca]C#CC1=CC=CC=C1 IPOANIITHDTHQG-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- UIXRSLJINYRGFQ-UHFFFAOYSA-N calcium carbide Chemical compound [Ca+2].[C-]#[C-] UIXRSLJINYRGFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- PNZJBDPBPVHSKL-UHFFFAOYSA-M chloro(diethyl)indigane Chemical compound [Cl-].CC[In+]CC PNZJBDPBPVHSKL-UHFFFAOYSA-M 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007786 electrostatic charging Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- JFDAACUVRQBXJO-UHFFFAOYSA-N ethylcyclopentane;magnesium Chemical compound [Mg].CC[C]1[CH][CH][CH][CH]1.CC[C]1[CH][CH][CH][CH]1 JFDAACUVRQBXJO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- PPWWEWQTQCZLMW-UHFFFAOYSA-N magnesium 5-methylcyclopenta-1,3-diene Chemical compound [Mg+2].C[C-]1C=CC=C1.C[C-]1C=CC=C1 PPWWEWQTQCZLMW-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BXYHVFRRNNWPMB-UHFFFAOYSA-N tetramethylphosphanium Chemical compound C[P+](C)(C)C BXYHVFRRNNWPMB-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- OTRPZROOJRIMKW-UHFFFAOYSA-N triethylindigane Chemical compound CC[In](CC)CC OTRPZROOJRIMKW-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- NRZWQKGABZFFKE-UHFFFAOYSA-N trimethylsulfonium Chemical compound C[S+](C)C NRZWQKGABZFFKE-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- 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
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
-
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- 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
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- 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
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- 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
- H01L21/02455—Group 13/15 materials
- H01L21/02458—Nitrides
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- 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
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/0254—Nitrides
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- 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
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
- H01L21/02576—N-type
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- 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
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
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- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
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- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
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- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
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- 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
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- Condensed Matter Physics & Semiconductors (AREA)
- Chemical & Material Sciences (AREA)
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- Crystallography & Structural Chemistry (AREA)
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- Crystals, And After-Treatments Of Crystals (AREA)
- Led Device Packages (AREA)
Description
本發明係關於以通式Inx
Gay
Alz
N(其中x+y+z=1,0x1,0y1,且0z1)表示的氮化物類化合物半導體,以及彼之製法。
近年來,使用以通式Inx
Gay
Alz
N(其中x+y+z=1,0x1,0y1,且0z1)表示之氮化物類化合物半導體的發光元件已具體化並商業化為藍光、綠光或白光發光裝置的光源。在此類發光元件中,氮化物類化合物半導體層係於基材(例如藍寶石基材)上形成。
在製造發光裝置(包含有如上所述的發光元件)的方法中,或者當操作發光裝置時,如果因為靜電而使得大電流瞬間流入氮化物類化合物半導體中,會發生化合物半導體被破壞的問題。
為了解決此問題,在組成半導體發光元件的氮化物類化合物半導體中,有人提出以下方法:其中p-型多層膜被層壓至由多量子井所組成的發光層上,且未摻雜層係於溫度1050℃下在p-型多層膜與p-型接觸層間形成之方法(例如,參考專利文件1);其中n-型多層膜、多量子井及p-型多層膜被施以層壓之方法(例如,參考專利文件2);及其中電子濃度低於n-型接觸層的n-型層係於溫度1150℃下在發光層與n-型接觸層間形成之方法(例如,參考專利文件3)等。
[專利文件1]JP-A-2001-148507[專利文件2]JP-A-2000-244072[專利文件3]JP-A-9-92880
但是,上述之在溫度1050℃下形成未摻雜層的方法及用以層壓n-型多層膜、多量子井及p-型多層膜的方法中,抗靜電崩解性無法得到令人滿意的結果;在具有低電子濃度之n-型層係於溫度1150℃下形成的方法中,正向的靜電耐受電壓雖然得到改善,但是逆向的靜電耐受電壓卻無法充分地改善。
本發明之目的係解決習知技藝的上述問題,並提供能夠製得具有高抗靜電崩解性的元件之氮化物類化合物半導體,以及彼之製法。
為解決上述問題,本發明人深入研究發現靜電耐受電壓可以藉由在p-型接觸層與n-型接觸層間形成特定的氮化物類半導體層而得到顯著的改善,本發明亦因此而得以完成。
具體而言,本發明提供:(1)以通式Inx
Gay
Alz
N(其中x+y+z=1,0x1,0y1,且0z1)表示的氮化物類化合物半導體之製法,其特徵為以通式Ina
Gab
Alc
N(其中a+b+c=1,0a1,0b1,且0c1)表示且厚度為50至500 nm的未經摻雜之氮化物類化合物半導體(A)係於550至850℃之溫度範圍內在p-型接觸層與n-型接觸層之間形成;(2)如上述(1)之方法,其中以通式Ind
Gae
Alf
N(其中d+e+f=1,0d1,0e1,且0f1)表示且厚度為20至600 nm的未經摻雜之氮化物類化合物半導體(B)係於900至1200℃之溫度範圍內在氮化物類化合物半導體(A)與n-型接觸層之間形成;及(3)一種氮化物類化合物半導體,其係利用如上述(1)或(2)之方法製得。
本發明亦提供具有以上氮化物類化合物半導體之發光元件。
此處,本發明中之名詞"未經摻雜"係指未故意加入雜質。
以下參考附圖對本發明之實施例的實例做說明。
作為本發明之主題的氮化物類化合物半導體是以通式Inx
Gay
Alz
N(其中x+y+z=1,0x1,0y1,且0z1)表示的化合物半導體。
至於用以成長氮化物類化合物半導體之基材,以氮化物類化合物半導體基材、藍寶石基材、SiC基材、Si基材、ZrB2
基材等為較佳。此處,如果氮化物類化合物半導體係於除氮化物類化合物半導體基材外的上述基材上直接成長,可能會因晶格不匹配之問題而無法製得品質足夠高的晶體。在此案例中,熟知高品質晶體可藉兩階段成長法製得,其中GaN、AlN、SiC或類似物的層係先在基材上長成並作為緩衝層,然後再長成氮化物類化合物半導體。
圖1是顯示適用本發明之氮化物類化合物半導體結構之架構形式的剖面圖。
雖然氮化物類化合物半導體之製法包含多種習知的方法,但以使用金屬有機蒸汽相外延成長法(MOVPE法)為較佳。以下說明使用MOVPE法的製造方法。
GaN緩衝層(低溫緩衝層)2係於藍寶石基材1上形成,且n-型接觸層3係於GaN緩衝層上形成。GaN緩衝層2的厚度以10至100 nm為較佳。以通式Gay
Al1 - y
N(其中0<y<1)表示的AlN與GaN之混合晶體亦可以作為緩衝層。
以不提高發光元件的操作電壓為宜,n-型接觸層3中的n-型載體(carrier)濃度為1x101 8
cm- 3
或以上至1x102 1
cm- 3
或以下。此n-型接觸層可藉熟知的方法容易地製得,其中適量的n-型摻雜氣體或有機金屬材料係於Inx
Gay
Alz
N(其中x+y+z=1,0x1,0y1,且0z1)晶體在900至1100℃之溫度範圍內成長時加入。至於n-型摻雜物之材料,以使用矽烷、二矽烷、鍺、四甲基鍺或類似物為較佳。n-型載體濃度不宜高於1x102 1
cm- 3
,因為結晶性質會變差,且發光元件的特性會受到不利的影響。
此外,當混合晶體中之In與Al的混合比率高時,晶體的品質會降低且載體濃度會提高(特別是在低溫下);因此,In組成以5%或以下為較佳,並以1%或以下為更佳。Al組成以5%或以下為較佳,並以1%或以下為更佳。n-型接觸層3由GaN組成為最佳。
以通式Ina
Gab
Alc
N(其中a+b+c=1,0a1,0b1,且0c1)表示的未經摻雜之氮化物類化合物半導體4係於上述n-型接觸層3上形成。半導體層4係於550至850℃之溫度範圍內成長,溫度並以700至800℃為較佳。例如,成長溫度設定為775℃,使用氨氣作為第V族材料並以三乙基鍺作為第III族材料以成長晶體。此時必須注意為了營造未摻雜之條件,未故意加入有n-型摻雜氣體及p-型摻雜氣體。在這些晶體成長條件下形成的氮化物類化合物半導體層4之n-型載體濃度可為1x101 7
至1x101 8
cm- 3
。
在氮化物類化合物半導體4中,因為當In與Al的混合晶體比率高時,晶體的品質會降低且載體濃度會提高(特別是在低溫下),In組成以5%或以下為較佳,並以1%或以下為更佳。Al組成以5%或以下為較佳,並以1%或以下為更佳。氮化物類化合物半導體4以GaN為最佳。
如果氮化物類化合物半導體層4的膜厚過薄,則改善靜電耐受電壓的效果會有降低的傾向;如果其過厚,則元件特性會受到不利的影響,例如,當發光元件動作時,漏電會增加。因此,氮化物類化合物半導體層4的膜厚通常在50至500 nm的範圍內,並以70至250 nm為較佳。
雖然氮化物類化合物半導體層4係作為與井層(其為下述之發光層)之下表面接觸的阻擋層;但是其可在n-型接觸層與阻擋層之間形成。其亦可作為與井層之上表面接觸的阻擋層,或者可在p-型接觸層與阻擋層之間形成。
此外,以通式Ind
Gae
Alf
N(其中d+e+f=1,0d1,0e1,且0f1)表示的未經摻雜之氮化物類化合物半導體層7可在n-型接觸層3與氮化物類化合物半導體層4之間形成。此為較佳的狀況,因為可以得到較好的靜電耐受電壓特性、良好的LED發光特性及電氣特性。半導體層7係於900至1200℃之溫度範圍內成長,溫度並以1000至1150℃為較佳。例如,晶體係於成長溫度1100℃下以氨氣作為第V族材料並以三乙基鍺作為第III族材料成長。此時為了營造未摻雜之條件,未故意加入n-型摻雜氣體及p-型摻雜氣體。在這些晶體成長條件下形成的半導體層7之n-型載體濃度可以低於5x101 6
cm- 3
,並以1x101 6
cm- 3
或以下為較佳。
但是,如果此低載體濃度層過厚,其變為發光元件的串聯電阻組件;因此,半導體層7的膜厚以600 nm或以下為較佳,並以10至300 nm為更佳,以50至300 nm為最佳。
在氮化物類化合物半導體7中,當In與Al的混合晶體比率高時,晶體品質會降低(特別是在低溫下)且載體濃度會提高;因此,In組成以5%或以下為較佳,並以1%或以下為更佳。Al組成以5%或以下為較佳,並以1%或以下為更佳。未經摻雜之氮化物類化合物半導體層7以包含GaN為最佳。
發光層5係於上述的氮化物類化合物半導體層4上形成。示於圖1中的發光層5是多量子井結構,其包含作為阻擋層之GaN層5A至5E以及作為井層之Ing
Gah
N層(其中g+h=1,0<g<1,0<h<1)5F至5J。雖然井層由五層所組成,但是至少有一井層即足夠。GaN層5A至5E及Ing
Gah
N層5F至5J之膜厚及混合晶體比率可依標的發光元件之特性而適當地選定。例如,當放射波長為約470nm的藍色發光元件為標的時,GaN層的厚度為3至30nm,Ing
Gah
N層的厚度為1至5nm,且In平均組成可為約5至40%。
p-型接觸層6係於上述的發光層5上形成。在p-型接觸層6中,為了不增高發光元件的操作電壓,p-型載體濃度以5x1015
cm-3
或以上為較佳,並以1x1016
至5x1019
cm-3
為更佳。此p-型接觸層可以藉由熟知的方法容易地製得,其中當Ina
Gab
Alc
N(其中a+b+c=1,0a1,0b1,且0c1)晶體於800至1100℃的成長溫度下成長時,在混合適量的供摻雜物用之材料氣體以成長晶體後,即施以熱處理。
在p-型接觸層6中,當Al的混合晶體比率高時,接觸電阻會有昇高的傾向,Al組成通常為5%或以下,並以1%或以下為較佳。p-型接觸層6以InGaN或GaN為更佳,並以GaN為最佳。
當如上所述的各層係以MOVPE法成長時,以下材料可以適當的選擇及使用。
第III族鍺材料的實例包括以通式R1
R2
R3
Ga(其中R1
、R2
及R3
表示低碳烷基)表示的三烷基鍺,例如三甲基鍺(TMG)及三乙基鍺(TEG)。
鋁材料包括以通式R1
R2
R3
Al(其中R1
、R2
及R3
表示低碳烷基)表示的三烷基鋁,例如三甲基鋁(TMA)、三乙基鋁(TEA)及三異丁基鋁。
銦材料包括以通式R1
R2
R3
In(其中R1
、R2
及R3
表示低碳烷基)表示的三烷基銦,例如三甲基銦(TMI)及三乙基銦;其一至三個烷基被鹵原子取代的三烷基銦,例如氯化二乙基銦;及以通式InX(其中X是鹵原子)表示的鹵化銦,例如氯化銦。
第V族材料的實例包括氨、肼、甲基肼、1,1-二甲基肼、1,2-二甲基肼、第三-丁基胺及乙二胺。這些材料可以單獨使用或者任意的組合使用。在這些材料中,以氨及肼為較佳,因其分子中不含碳原子,並且不太會對半導體造成碳污染。
p-型摻雜物的實例包括Mg、Zn、Cd、Ca、Be等。其中以使用Mg及Ca為較佳。至於作為p-型摻雜物之Mg的材料,可以使用諸如雙(環戊二烯基)鎂((C5
H5
)2
Mg)、雙(甲基環戊二烯基)鎂((C5
H4
CH3
)2
Mg)、雙(乙基環戊二烯基)鎂((C5
H4
C2
H5
)2
Mg)或類似物。至於Ca之材料,可以使用諸如雙(環戊二烯基)鈣((C5
H5
)2
Ca)及其衍生物,例如雙(甲基環戊二烯基)鈣((C5
H4
CH3
)2
Ca)、雙(乙基環戊二烯基)鈣((C5
H4
C2
H5
)2
Ca)或雙(全氟環戊二烯基)鈣((C5
F5
)2
Ca)、二-1-萘基鈣及其衍生物,或乙炔化鈣及其衍生物,例如,雙(4,4-二氟-3-丁烯-1-炔基)鈣或雙(苯基乙炔基)鈣。這些材料可以單獨使用或者以其兩或多種的組合使用。
雖然其中使用MOVPE法的案例在此實施例中做說明,但是本發明不限於彼,亦可使用其他熟知之用於成長第III-V族化合物半導體之晶體的方法,例如分子束外延法(molecular beam epitaxy)。
本發明之發光元件的特徵在於其具有以上述製法製得的氮化物類化合物半導體。
例如,圖3是顯示發光元件之實例的剖面圖,此元件具有依據本發明之氮化物類化合物半導體。利用習知方法,在氮化物類化合物半導體上,p-電極係於p-型接觸層上形成且n-電極係於n-型接觸層上形成,然後再實施晶片製程。氮化物類化合物半導體在晶片製程之後,即固定在基座上,此基座係以整體方式在第一導線架34的內端形成。提供第二導線架36使與第一導線架34幾乎平行。發光元件32的n-電極係經由第一連接導線33電連至基座部份,且p-電極係經由第二連接導線35電連至第二導線架36。第一導線架34及第二導線架36的內端係以透明熱固性樹脂31密封。因此,在第一導線架與第二導線架間施加電壓即可使發光元件發光。發光元件係經由透明熱固性樹脂31向外放出光線。
以下說明本發明之實例,但是本發明不限於彼。
以藍寶石作為基材,其C表面經鏡面拋光。晶體成長方法係以MOVPE法實施,在兩步驟成長法中,以低溫下成長之GaN作為緩衝層。成長爐中的壓力設定為1大氣壓,基材溫度設定為550℃,以氫氣作為載氣,並供應TMG及氨以成長出厚度約為50 nm的GaN緩衝層。
將基材溫度提高至1120℃後,供以氫載氣、TMG、矽烷及氨以成長出厚度約為4微米的摻雜Si之n-型GaN層,停止矽烷的供應以成長出厚度約為300 nm的未經摻雜之GaN層。
再將基材溫度設定為780℃,成長爐中的壓力設定為50 kPa,以氮氣作為載氣,並分別供應610 sccm及40 slm的TEG及氨以成長出厚度為100 nm的未經摻雜之GaN層,其係作為本發明之氮化物類化合物半導體層A。
然後,分別供應610 sccm、1160 sccm及40 slm的TEG、TMI及氨以成長出厚度為3 nm的In0 . 1 2
Ga0 . 8 8
N層。再分別供應610 sccm及40 slm的TEG及氨以成長出厚度為15 nm的未經摻雜之GaN層。
將成長In0 . 1 2
Ga0 . 8 8
N井層(3 nm)及未經摻雜之GaN阻擋層(15 nm)的流程再重覆操作四次;但僅將最外層的未經摻雜之GaN阻擋層的膜厚改為18 nm。
基材溫度提高至940℃後,再分別供應600 sccm、200 sccm、3000 sccm及40 slm的TEG、TMA、雙(環戊二烯基)鎂(以下簡稱EtCp2
Mg)及氨以成長出厚度為30 nm之摻雜Mg的Al0 . 1
Ga0 . 9
N層。基材溫度提高至1000℃後,再供應EtCp2
Mg及氨以成長出厚度為150 nm之摻雜Mg的p-型GaN層,其係作為p-層。
將由是製得的氮化物類化合物半導體樣品自反應爐中取出,再於700℃下鍛燒20分鐘以將摻雜Mg的GaN層(頂層)轉換成低電阻p-型層。
利用習知方法在由是製得的樣品上形成電極以生成發光二極體(以下簡稱LED)。以Ni-Au合金作為p-電極,並以Al作為n-電極。當20毫安培之電流以正向流入此LED時,LED發出明亮的藍光。LED對靜電放電之抵抗的測試方法如下:圖2是用以測試LED之耐靜電放電性的電略圖式。此處,Vo表示可變直流電源,Rp及R表示電阻器,C表示電容器,且Sw表示切換開關。試驗係利用以下機械模式試驗實施。機械模式試驗是一種以靜電充電裝置或夾具在R=0Ω且C=200 pF之條件下對LED實施靜電放電的模式。在將圖2中之可變直流電源Vo的電壓設定為某一值,並將實線所示之切換開關Sw切換至經電阻器Rp對電容器C充電後,將切換開關Sw切換至對LED放電,如虛線所示。重覆此試驗三次之後,評估發光元件的電壓-電流特性。經由發光元件之電壓-電流特性的改變可以判斷元件是否損壞。總測試元件的50%損壞時的Vo值訂為靜電耐受電壓值。此實例中的靜電耐受電壓為417伏特。
LED係依據實例1製得,除了氮化物半導體層A的膜厚改為200 nm。當20毫安培之電流以正向流入此LED時,LED發出明亮的藍光。靜電耐受電壓為417伏特。
LED係依據實例1製得,除了氮化物半導體層B的膜厚改為150 nm。當20毫安培之電流以正向流入此LED時,LED發出明亮的藍光。靜電耐受電壓為200伏特。
LED係依據實例1製得,除了氮化物半導體層A成長時的基材溫度改為889℃。當20毫安培之電流以正向流入此LED時,LED發出明亮的藍光。靜電耐受電壓為75伏特。
LED係依據實例1製得,除了氮化物半導體層A的膜厚改為15 nm。當20毫安培之電流以正向流入此LED時,LED發出明亮的藍光。靜電耐受電壓為60伏特。
LED係依據實例1製得,除了氮化物半導體層A成長時的基材溫度改為1124℃且膜厚改為300 nm。當20毫安培之電流以正向流入此LED時,LED發出明亮的藍光。靜電耐受電壓為88伏特。
表1顯示氮化物半導體層A的成長條件及靜電耐受電壓。
氮化物半導體層A的載體濃度量測如下:低溫緩衝層係於藍寶石基材上長成,在此低溫緩衝層上有厚度為約3000 nm的GaN基層(先前已知其載體濃度為1x101 6
cm- 3
或以下)形成,氮化物半導體層A即以厚度為約200 nm成長於其上。將由是製得的樣品施以電洞量測法以得到氮化物半導體層A的載體濃度。
在比較例1至3的藍光發光二極體中,靜電耐受電壓低於100伏特。
另一方面,在實例1及2中,靜電耐受電壓為417伏特,在實例3中,其為200伏特。易言之,確認在以本發明之製法製得的LED中,靜電破壞的耐受電壓得到顯著的改善,具體而言,在實例1及2中,其改善約300伏特或以上。
利用和實例1的相同方式,除了氮化物半導體層A及B的成長溫度及厚度改為如下表2所示者,最後製得靜電耐受電壓極佳的氮化物類化合物半導體。
依據本發明,得以防止靜電破壞氮化物類化合物半導體,即使靜電引發的異常高電壓及大電流脈衝加至氮化物類化合物半導體時亦然。
1‧‧‧藍寶石基材
2‧‧‧GaN緩衝層
3‧‧‧n-型接觸層
4‧‧‧未經摻雜之氮化物類化合物半導體層
5‧‧‧發光層
5A‧‧‧GaN層
5B‧‧‧GaN層
5C‧‧‧GaN層
5D‧‧‧GaN層
5E‧‧‧GaN層
5F‧‧‧Ing
Gah
N層
5G‧‧‧Ing
Gah
N層
5H‧‧‧Ing
Gah
N層
5I‧‧‧Ing
Gah
N層
5J‧‧‧Ing
Gah
N層
6‧‧‧p-型接觸層
7‧‧‧未經摻雜之氮化物類化合物半導體層
Rp
‧‧‧電阻器
SW‧‧‧切換開關
R‧‧‧電阻器
V0
‧‧‧可變直流電流
C‧‧‧電容器
31‧‧‧透明熱固性樹脂
32‧‧‧發光元件
33‧‧‧第一連接導線
34‧‧‧第一導線架
35‧‧‧第二連接導線
36‧‧‧第二導線架
圖1是顯示依據本發明之製法製得的氮化物類化合物半導體之實例的剖面圖。
圖2是用以測試發光元件之抗靜電放電性的電路圖式。
圖3顯示本發明之發光元件的結構。
1‧‧‧藍寶石基材
2‧‧‧GaN緩衝層
3‧‧‧n-型接觸層
4‧‧‧未經摻雜之氮化物類化合物半導體層
5‧‧‧發光層
5A~5E‧‧‧GaN層
5F~5J‧‧‧Ing
Gah
N層
6‧‧‧p-型接觸層
7‧‧‧未經摻雜之氮化物類化合物半導體層
Claims (3)
- 一種氮化物類化合物半導體之製法,而該氮化物係如下式所示:Inx Gay Alz N(其中x+y+z=1,0x1,0y1,且0z1),其特徵為厚度70至250nm之以通式Ina Gab Alc N(其中a+b+c=1,0a1,0b1,且0c1)表示的未經摻雜之氮化物類化合物半導體(A)係於550至850℃之溫度範圍內在p-型接觸層與n-型接觸層之間形成。
- 如申請專利範圍第1項之方法,其中厚度200至6000埃之以通式Ind Gae Alf N(其中d+e+f=1,0d1,0e1,且0f1)表示的未經摻雜之氮化物類化合物半導體(B)係於900至1200℃之溫度範圍內在該氮化物類化合物半導體(A)與該n-型接觸層之間形成。
- 一種氮化物類化合物半導體,其係以如申請專利範圍第1或2項之方法製得。
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TWI398016B (zh) * | 2007-02-07 | 2013-06-01 | Advanced Optoelectronic Tech | 具三族氮化合物半導體緩衝層之光電半導體元件及其製造方法 |
WO2017132283A1 (en) * | 2016-01-25 | 2017-08-03 | The Regents Of The University Of California | Nano-scale pixelated filter-free color detector |
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JPH11340580A (ja) * | 1997-07-30 | 1999-12-10 | Fujitsu Ltd | 半導体レーザ、半導体発光素子、及び、その製造方法 |
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GB2432047B (en) | 2008-10-08 |
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CN1989626A (zh) | 2007-06-27 |
GB2432047A (en) | 2007-05-09 |
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