TWI496195B - 形成於基材上之金屬氧化物層及其製造方法 - Google Patents
形成於基材上之金屬氧化物層及其製造方法 Download PDFInfo
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- TWI496195B TWI496195B TW094137315A TW94137315A TWI496195B TW I496195 B TWI496195 B TW I496195B TW 094137315 A TW094137315 A TW 094137315A TW 94137315 A TW94137315 A TW 94137315A TW I496195 B TWI496195 B TW I496195B
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- 239000000758 substrate Substances 0.000 title claims description 71
- 238000000034 method Methods 0.000 title claims description 31
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 20
- 150000004706 metal oxides Chemical class 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 45
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000004065 semiconductor Substances 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 14
- 239000011733 molybdenum Substances 0.000 claims description 14
- 229910002601 GaN Inorganic materials 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910005540 GaP Inorganic materials 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 3
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 3
- 238000004140 cleaning Methods 0.000 claims 2
- 239000000463 material Substances 0.000 description 37
- 239000010410 layer Substances 0.000 description 19
- 239000013078 crystal Substances 0.000 description 12
- 239000010453 quartz Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 229910052715 tantalum Inorganic materials 0.000 description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052594 sapphire Inorganic materials 0.000 description 5
- 239000010980 sapphire Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229910003468 tantalcarbide Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000000441 X-ray spectroscopy Methods 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
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- 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
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- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
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- C23C8/10—Oxidising
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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- 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
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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Description
本發明係有關由形成於基材上具有大能量間隙的金屬氧化物所製成的新穎半導體薄膜。
該新穎半導體薄膜用在電子和光子裝置中非常有用。
本發明也有關一種已常用於電子和光子裝置中的材料所製成的基材上形成該半導體薄膜之新穎方法。
最近，所謂的功率裝置例如二極電晶體、場效電晶體、和閘流體用於多種領域例如家庭電子物件、汽車、機械工具、及照明等之中。隨著應用的增加，對於功率裝置要求具有高效率及高速度之電力轉換與控制。雖然長久以來都是使用矽(Si)來製造功率裝置，不過對矽裝置預料有限制。該等限制係來自矽的能量間隙為小，約1電子伏特(eV)之事實。對於用有大的能量間隙之半導體，亦即，所謂的寬間隙半導體來製造功率裝置以期實現克服該等限制之研究業經廣泛地進行過。特別者，使用能量間隙為約3.43 eV的氮化鎵(GaN)或能量間隙為約3.2 eV的碳化矽(SiC)之功率裝置的開發已廣泛地進行過。
另一方面，來自宇宙射線或汽車和熱的雜訊所致電子裝置的誤差或故障已變成嚴重的問題。已經清楚者，所謂的可對抗有雜訊或熱的嚴厲環境之敵意環境裝置應該用有大能量間隙的半導體來製造。使用GaN或SiC的電子裝置之開發係從此等觀點而著手。不過，為實現GaN或SiC製的電子裝置仍有許多問題待解決。
最嚴重的問題在於因為氮的平衡蒸氣壓相對於鎵係相當高者，所以仍未能得到大型GaN晶體。所以，乃使用藍寶石或碳化矽(SiC)製成的基材。GaN不能在藍寶石基材上直接形成，因為在藍寶石與GaN之間有16%的晶格誤配率之故。所以在生長GaN之前，要在藍寶石基材上先形成一氮化鋁(AlN)緩衝層。由於難以將雜質摻入AlN，所以AlN有電阻。在包括多層半導體的裝置例如雙極電晶體和閘流體中使用藍寶石基材對於彼等的結構和製程係非常不利者。另一方面，因為大型SiC晶體只能在2200~2400℃的非常高溫度下形成，所以SiC基材非常昂貴。使用SiC基材的GaN裝置或SiC裝置都是很貴者。
第二項嚴重問題在於要在比形成GaN或SiC所用者較低的溫度生長新的裝置。需要在高於1000℃的溫度下形成GaN或SiC層。在高溫下形成半導體層需要用到大能量。此外，會有原子在層間移動以及組成受干擾或摻雜劑移動到靠近層間介面處等可能性。
上述諸問題可以使用此等裝置所用氧化鉬來解決。本發明之發明人發現高品質的氧化鉬晶體具有大於3.2 eV的大能量間隙且用在光子和電子裝置中非常有用(美國專利申請第10/848,145號和第10/863,288號)。
不過，於上述諸專利申請案中，氧化鉬晶體係經由將金屬鉬板予以氧化而形成。因為鉬板不是晶體，所以不能使用某些製造技術例如解理(cleavage)。此外，也不能將氧化鉬形成的裝置與矽形成者整合起來。更進一步者，在經由鉬板氧化形成氧化鉬層時，難以精確控制其厚度。
所以，有需要在一般裝置所用材料所製成的基材上形成能量間隙大於3.2 eV的半導體晶體層。該半導體層應該在相當低溫下形成使得在形成層之中不損及裝置結構。具有高耐電壓的電子裝置及光子和電子敵意環境裝置將在目前裝置所用基材上於相當低溫下製成。
本發明係有關一種在基材上長成的金屬氧化物所構成的新穎半導體薄膜。
該金屬氧化物係由具有大3.2 eV的能量間隙之氧化鉬所構成且非常有用於製造有高耐受電壓的電子裝置以及光子和電子敵意環境裝置。氧化鉬也可用來製造可發出波長短於387奈米(nm)的光之發光二極體或雷射二極體。
本發明的一重要方面為氧化鉬薄膜係在已用於一般電子和光子裝置中的材料所製成的基材上形成的。最普遍的材料為矽。
本發明的另一重要方面為提供一種於基材上形成氧化鉬薄膜之新穎方法。此方法包括下面步驟：於第一步驟中將一基材與源材料固定在一沈積室內。典型的源材料為鉬板及典型的基材為矽。於第二步驟中，在該生長室內形成一溫度曲線使得源材料的溫度高於基材溫度。於第三步驟中，在形成該溫度曲線之後，流入氧氣持續一段時間，其決定於形成特定裝置所需的氧化鉬的厚度。
現在要更詳細地參照本發明較佳具體實例。
圖1示意地顯示出根據本發明方法形成高品質氧化鉬所用設備之一例子。形成氧化鉬所用設備(100)包括一石英管(101)，於其中沈積氧化鉬；一源材料固持器(104)；一基材固持器(105)；一爐子(102)；及一加熱器(103)，其可在該爐子(102)之內形成溫度曲線。此外也包括一監測源材料溫度的溫度計(106)和一監測基材溫度的溫度計(107)。於此例中，該溫度計(106)和(107)都是熱電偶。雖然於此圖中沒有顯示出來，不過也包括導入及控制氧氣(108)和氮氣所用之工具。於石英管(101)內部，可用真空泵(圖中未顯示出)予以抽真空。源材料固持器(104)和基材固持器(105)都是用石英製成者，因為其在形成氧化鉬所用溫度下不會變化且其不會與基材、氧氣和氧化鉬起反應之故。雖然在典型具體實例中係使用由圖1中所示設備，不過對設備並沒有限制，只要可以在包括源材料區和基材區中形成較佳溫度曲線，及沈積層內部可作成氧氣體環境即可。
本發明形成氧化鉬之新穎方法可參照圖2所示流程圖予以說明。於此例中使用鉬(Mo)板作為源材料且使用矽(Si)基材。首先，依序用丙酮、甲醇和高純度水清洗鉬板和矽基材(步驟201)。若需要時，在步驟201之後用酸和高純度水清洗鉬板。若需要時，用氫氟酸或其他用氫或氫自由基的方法移除在矽基材上自然長出的氧化物。
於下一步驟(步驟202)，將預處理過的源鉬板或其表面已事先氧化過的鉬板(10毫米×10毫米×0.1毫米)固定在源材料固持器(104)之上，及將矽基材(10毫米×10毫米×0.1毫米)固定在基材固持器(105)之上，該基材固持器(105)係經設定在距該源材料固持器(104)下游20厘米之位置。
於下一步驟(步驟203)，使用旋轉泵將石英管內部抽真空到10－ 3
托(Torr)，及用氮氣(或惰性氣體例如氬氣)塡充。
於石英管內部的空氣用氮氣或惰性氣體置換之後，將爐子加熱以形成圖3中所示的溫度曲線(步驟204)。於該溫度曲線中，在源材料區的溫度為650℃，及在基材區為450℃。該溫度曲線係經由在溫度控制器(圖中未示出)的控制下加熱約45分鐘而形成。於本發明具體實例中，源材料區的溫度為550－850℃，較佳者650℃，及基材區的溫度為350－650℃，較佳者450℃。從源材料區到基材區形成一溫度斜度。在源材料區超過850℃的溫度係非較佳者，因為氧可能離開氧化鉬且可能形成氮化鉬。重要的是基材區溫度要低於源材料區溫度。
在爐子(102)中形成所欲之溫度曲線之後，將氧氣(108)導到石英管(101)之內(步驟206)。氧氣(108)係沿著從源材料固持器(104)到基材固持器(105)的方向流動。氧氣(108)的流速為50至450 SCCM，較佳地為250 SCCM。雖然使用氧氣流使石英管內部成為氧氣體環境，不過除了該氧氣體環境之外也可以使用氧自由基或氧電漿，只要鉬板在所欲之溫度下被氧化，及氧化鉬分子從源材料脫吸附即可。
將上示溫度曲線和氧氣流保持6小時(步驟207)。其後，於保持氧氣流之下將爐子冷卻到室溫(步驟208)。其結果為在矽基材上沈積一層高品單晶氧化鉬到6微米之厚度，如圖5中所示者。雖然在此具體實例中，氧化鉬的成長速率為約1微米/小時，不過此速率可經由選擇鉬源大小、氧氣流速和溫度曲線而改變。此外，沈積速率也決定於許多因素例如石英管的直徑，源材料與基材之間的距離以及基材的尺寸。所以，宜於事先針對某些長晶參數組合測量長晶速率。層的厚度可用光學方法或直接測量法予以測量。
嚴格來說，在矽基材(501)與氧化鉬層(502)之間可能形成一氧化矽薄層。這是因為在氧化鉬的成長早期階段中矽基材表面被氧化之故。若想要使氧化矽不形成，可藉由於圖2所示流程圖中的步驟(204)與(206)之間增加流入氫氣之一步驟(步驟205)且持續5分鐘來抑制氧化矽的生長(其他步驟皆類似於上面對第一具體實例所示者)。雖然於第二具體實例中係經由流入氫氣來阻止氧化矽的生長，不過也可以用使用還原劑的其他方法予以防止。
如圖3中所示的在爐子中的溫度曲線為簡單者。不過，較佳者為在基材區中的溫度係平直者，因為可讓更多基材調定在相同溫度之故。
於本發明諸具體實例中，係使用有多種表面取向例如(100)和(111)的矽基材。於任何此等基材上可以形成高品質的氧化鉬結晶層。可以應用本發明沈積高品質金屬氧化物膜之方法在矽以外的基材上形成高品質金屬氧化物膜，例如在鍺、砷化鎵、磷化銦、磷化鎵、氮化鎵、碳化矽、有機半導體或彼等的衍生物、塑膠基材、聚醯亞胺和絕緣體例如玻璃等之上。類似地，可以應用本發明方法使用諸如鋅、鈦、鉭、鋁、釕、銦、錫、銥、鈀、鎢、銅和鉻等金屬作為彼等的來源而形成金屬氧化物膜。使用X－射線和拉曼光譜術分析顯示，由本發明方法所形成氧化鉬膜具有優良的晶體品質且相對於以已知的CVD法或濺鍍法所形成者有更一致的組成。其理由經認為是氧化鉬分子係在沒有打斷彼等的化學鍵之下從源鉬板脫吸附以及氧化鉬係沈積在保持相對較低溫的石英管之內。從使用X－射線和拉曼光譜術的分析明白，本發明方法所形成的氧化鉬膜之主要組成為MoO3
。已知MoO3
的晶體構造具有取決於晶格方向的不同晶格常數。此事實經認為有利於減低在不同材料的基材上沈積氧化鉬時因不同的晶格常數所導致的問題。本發明方法所形成的氧化鉬的能量間隙的特點為從反射光譜測量出大於約3.2 eV。經由改變長晶條件例如源材料溫度、基材溫度和氧氣流速，源板或基材的預處理程序或生長室的前處理，可能製成具有大於3.2 eV能量間隙之氧化鉬。氧化鉬具有大於3.2 eV能量間隙的事實意味著該材料具有可能取代GaN或SiC用於裝置中的可能性。由本發明方法所形成的氧化鉬為n－型，及當在源材料區溫度650℃和750℃時，其電阻率分別為1.5×107
Ω．cm和2.0×105
Ω．cm。
由本發明方法製成的氧化鉬可按其他半導體材料用於半導體工業中的一般方式來使用。由本發明方法製成的氧化鉬在沒有蓄意摻雜下製造且源材料區溫度為低於650℃之時，具有高電阻。不過，經由摻雜施體(例如，P、As、Sb、Se、等)或受體(例如Zn、Ga、Mg等)來改變氧化鉬的電子性質是可能的。在沒有蓄意摻雜下以本發明方法形成氧化鉬之時，可以經由改變源材料區溫度而改變其電阻率是可能的。例如，經由將源材料區溫度設定在750℃所長成的氧化鉬之電阻率遠低於經由設定源材料區溫度在650℃所長成的氧化鉬之電阻率。其理由經認為是氧化鉬中的氧空位具有施體的角色且其在經由將源材料區溫度設定在較高值所形成的氧化鉬中之濃度係大於其經由將源材料區溫度設定在較低值所形成的氧化鉬中之濃度。此事實為本發明的顯著點。此外，藉由將施體或受體以，例如，離子植入法引導到局部區內而控制以本發明方法形成的氧化鉬的局部電子性質是可能的。
以本發明方法經由，例如，將源材料區溫度調定在較低溫度所形成的具有高電阻率之金屬氧化物膜可以用來分隔基材上的裝置。再者，本發明的形成金屬氧化物膜之方法可用來形成要用在現有裝置中作為絕緣體之此等金屬氧化物膜。
100．．．設備
101．．．石英管
102．．．爐子
103．．．加熱器
104．．．源材料固持器
105．．．基材固持器
106，107．．．溫度計
108．．．氧氣
501．．．矽基材
502．．．氧化鉬層
圖1為用於根據本發明方法形成金屬氧化物層之設備之一實例的示意圖。
圖2為一流程圖，其顯示出根據本發明經由在基材上沈積以形成金屬氧化物層之步驟。
圖3顯示出在根據本發明方法形成金屬氧化物層期間，在爐子內和基材位置的溫度曲線的一實例。
圖4顯示出在一爐子內及目標基材區內的更佳溫度曲線的一實例。
圖5為在由目前常用裝置中所用材料製成的基材上所形成的金屬氧化物層之示意圖。
100．．．設備
101．．．石英管
102．．．爐子
103．．．加熱器
104．．．源材料固持器
105．．．基材固持器
106．．．溫度計
107．．．溫度計
108．．．氧氣
Claims (6)
- 一種製造半導體層之方法，該方法包括下列步驟：提供源金屬板和基材；清潔該源金屬板和該基材的表面；將該源金屬板和該基材固定在沈積室內；在惰性氣體環境中，將該源金屬板加熱到介於500℃與850℃之間的溫度及將該基材加熱到介於350℃與650℃之間的溫度，其中該源溫度高於基材溫度；及經由將該氣體環境從惰性氣體改變成為氧化性氣體環境及維持該源金屬板和該基材在該沈積室內的溫度一段足以形成具有所欲的厚度之該金屬氧化物層的時間，而在該基材上形成金屬氧化物層，其中該基材係用矽、砷化鎵、磷化鎵、磷化銦、氮化鎵、碳化鎵、有機半導體或其衍生物，或玻璃製成，且該源金屬板係由鉬、氧化鉬或彼等的衍生物製成。
- 一種製造半導體層之方法，該方法包括下列步驟：提供基材和其表面業經事先氧化過的源金屬板；清潔該基材和其表面業經事先氧化過的源金屬板之表面；將該基材和該源金屬板固定在沈積室內；在惰性氣體環境中，將該其表面業經事先氧化過的源金屬板加熱到介於500℃與850℃之間的溫度及將該基材加 熱到350℃與650℃之間的溫度，其中該源溫度高於基材溫度；及經由將該氣體環境從惰性氣體改變成為氧化性氣體環境及維持該源金屬板和該基材在該沈積室內的溫度一段足以形成具有所欲的厚度之該金屬氧化物層的時間，而在該基材上形成金屬氧化物層，其中該基材係用矽、砷化鎵、磷化鎵、磷化銦、氮化鎵、碳化鎵、有機半導體或其衍生物，或玻璃製成，且該源金屬板係由鉬、氧化鉬或彼等的衍生物製成。
- 如申請專利範圍第1項之方法，其中該氧化性氣體環境係經由使氧氣流以50-450SCCM的流速沿著從該源金屬板到該基材的方向流入該沈積室內而提供的。
- 如申請專利範圍第1或2項之方法，其進一步包含下述步驟：在加熱該源金屬板與該基材的步驟之後且於形成該金屬氧化物層的該步驟之前流入氫氣持續5分鐘。
- 如申請專利範圍第1或2項之方法，其中形成該金屬氧化物層的該步驟包括同時摻雜施體和受體之步驟。
- 一種如申請專利範圍第1-5項中任一項之方法製造成的半導體層。
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| JP5826094B2 (ja) * | 2012-03-30 | 2015-12-02 | 株式会社半導体エネルギー研究所 | ｐ型半導体材料、および光電変換装置の作製方法 |
| US8647943B2 (en) * | 2012-06-12 | 2014-02-11 | Intermolecular, Inc. | Enhanced non-noble electrode layers for DRAM capacitor cell |
| CN109643660B (zh) * | 2016-08-31 | 2024-03-05 | 株式会社Flosfia | p-型氧化物半导体及其制造方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61158900A (ja) * | 1984-12-28 | 1986-07-18 | Alps Electric Co Ltd | 金属酸化物ウイスカ−の製造装置 |
| JPS6287498A (ja) * | 1985-10-14 | 1987-04-21 | Alps Electric Co Ltd | 酸化モリブデンウイスカ−の製造方法 |
| FR2612946B1 (fr) * | 1987-03-27 | 1993-02-19 | Chimie Metal | Procede et installation pour le depot chimique de revetements ultradurs a temperature moderee |
| JPH0541285A (ja) * | 1991-08-07 | 1993-02-19 | Ricoh Co Ltd | 電界発光素子 |
| JPH0897159A (ja) * | 1994-09-29 | 1996-04-12 | Handotai Process Kenkyusho:Kk | エピタキシャル成長方法および成長装置 |
| JPH09213818A (ja) * | 1996-01-29 | 1997-08-15 | Oki Electric Ind Co Ltd | 強誘電体ゲートメモリ、これに用いる強誘電体薄膜の形成方法およびこの形成方法に用いる前駆体溶液 |
| JPH11298021A (ja) * | 1998-04-10 | 1999-10-29 | Canon Inc | 光起電力素子用基板、これを用いた光起電力素子及び集積型光起電力素子並びに集積型光起電力素子の製造方法 |
| US6214712B1 (en) | 1999-09-16 | 2001-04-10 | Ut-Battelle, Llc | Method of physical vapor deposition of metal oxides on semiconductors |
| US6624441B2 (en) * | 2002-02-07 | 2003-09-23 | Eagle-Picher Technologies, Llc | Homoepitaxial layers of p-type zinc oxide and the fabrication thereof |
| JP4519423B2 (ja) | 2003-05-30 | 2010-08-04 | 創世理工株式会社 | 半導体を用いた光デバイス |
| JP4351869B2 (ja) * | 2003-06-10 | 2009-10-28 | 隆 河東田 | 半導体を用いた電子デバイス |
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| V. Guidi et al., "Novel Gas Sensor Device Based on Thin MoO3 Film and Low Power-Consumption Micromachined Si-Based Structure", 1997 International conference on Solid-State Sensors and Actuators, 1997, pages 943~946. 赤木敏和，酸化モリブデンの評価，高知工科大學大學院，2003年01月27日 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006128154A (ja) | 2006-05-18 |
| KR20060049322A (ko) | 2006-05-18 |
| CN1779912A (zh) | 2006-05-31 |
| DE05023406T1 (de) | 2006-08-31 |
| US20060089006A1 (en) | 2006-04-27 |
| EP1652957A3 (en) | 2006-12-06 |
| EP1652957A2 (en) | 2006-05-03 |
| JP4576201B2 (ja) | 2010-11-04 |
| EP1983070A2 (en) | 2008-10-22 |
| EP1983070B1 (en) | 2014-08-13 |
| DE08014153T1 (de) | 2009-05-20 |
| US7476628B2 (en) | 2009-01-13 |
| EP1983070A3 (en) | 2009-04-15 |
| TW200629382A (en) | 2006-08-16 |
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