TW201625504A - 氧化物燒結體、濺鍍用靶、及使用其而得之氧化物半導體薄膜 - Google Patents
氧化物燒結體、濺鍍用靶、及使用其而得之氧化物半導體薄膜 Download PDFInfo
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- TW201625504A TW201625504A TW104137984A TW104137984A TW201625504A TW 201625504 A TW201625504 A TW 201625504A TW 104137984 A TW104137984 A TW 104137984A TW 104137984 A TW104137984 A TW 104137984A TW 201625504 A TW201625504 A TW 201625504A
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- Prior art keywords
- oxide
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- less
- sintered body
- oxide semiconductor
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 70
- 239000010409 thin film Substances 0.000 title claims abstract description 51
- 238000005477 sputtering target Methods 0.000 title claims abstract description 16
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 60
- 229910052738 indium Inorganic materials 0.000 claims abstract description 43
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000004544 sputter deposition Methods 0.000 claims abstract description 27
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010408 film Substances 0.000 claims description 74
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000012071 phase Substances 0.000 description 87
- 239000000843 powder Substances 0.000 description 31
- 238000005245 sintering Methods 0.000 description 31
- 239000013078 crystal Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002425 crystallisation Methods 0.000 description 13
- 230000008025 crystallization Effects 0.000 description 13
- 229910003437 indium oxide Inorganic materials 0.000 description 12
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 238000000137 annealing Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 238000010891 electric arc Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000001039 wet etching Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910001195 gallium oxide Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000004993 emission spectroscopy Methods 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 230000005355 Hall effect Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011011 black crystal Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- H01L21/34—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 not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
- H01L21/46—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428
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- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
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- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
- H01L29/78693—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate the semiconducting oxide being amorphous
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- C03C2218/00—Methods for coating glass
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- C03C2218/154—Deposition methods from the vapour phase by sputtering
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Abstract
本發明提供一種於藉由濺鍍法製成氧化物半導體薄膜之情形時可獲得低載體濃度、高載體遷移率之氧化物燒結體、及使用其之濺鍍用靶。
該氧化物燒結體以氧化物之形式含有銦、鎵及鋁。鎵之含量以Ga/(In+Ga)原子數比計為0.15以上且0.49以下,且鋁之含量以Al/(In+Ga+Al)原子數比計為0.0001以上且未達0.25。將該氧化物燒結體作為濺鍍用靶而形成之結晶質之氧化物半導體薄膜可獲得4.0×1018cm-3以下之載體濃度、10cm2V-1sec-1以上之載體遷移率。
Description
本發明係關於一種氧化物燒結體、靶、及使用其而得之氧化物半導體薄膜,更詳細而言,係關於一種藉由含有銦、鎵、及鋁而能夠降低非晶質之氧化物半導體薄膜之載體濃度之濺鍍用靶、對於獲得其而言最適合之含有銦、鎵、及鋁之氧化物燒結體、以及使用其而得之顯示出較低之載體濃度與較高之載體遷移率的非晶質之含有銦、鎵、及鋁之氧化物半導體薄膜。
薄膜電晶體(Thin Film Transistor,以下稱為TFT)為場效電晶體(Field Effect Transistor,以下稱為FET)之1種。TFT係具備閘極端子、源極端子、及汲極端子作為基本構成之3端子元件,且係使用成膜於基板上之半導體薄膜作為供電子或電洞進行遷移之通道層,具有對閘極端子施加電壓,控制通道層中所流動之電流,而對源極端子與汲極端子間之電流進行切換之功能的主動元件。TFT係目前最多地被實用化之電子裝置,作為其代表性用途有液晶驅動用元件。
作為TFT,目前被最廣泛地使用者係將多晶矽膜或非晶質矽膜作為通道層材料之金屬-絕緣體-半導體(Metal-Insulator-
Semiconductor)-FET(MIS-FET)。使用矽之MIS-FET由於對可見光為不透明,故而無法構成透明電路。因此,於將MIS-FET用作液晶顯示器之液晶驅動用開關元件之情形時,該裝置之顯示器像素之開口比會變小。
又,最近,隨著要求液晶之高清化,對液晶驅動用開關元件亦要求高速驅動。為了實現高速驅動,需要將作為載體之電子或電洞之遷移率至少高於非晶質矽之遷移率之半導體薄膜用於通道層。
對於此種情況,專利文獻1中提出有一種透明半絕緣性非晶質氧化物薄膜,其係藉由氣相成膜法成膜且由In、Ga、Zn及O元素所構成之透明非晶質氧化物薄膜,其特徵在於:關於該氧化物之組成,結晶化時之組成為InGaO3(ZnO)m(m為未達6之自然數),於不添加雜質離子之情況下為載體遷移率(亦稱為載體電子遷移率)超過1cm2V-1sec-1且載體濃度(亦稱為載體電子濃度)為1016cm-3以下之半絕緣性;以及提出有一種薄膜電晶體,其特徵在於:將該透明半絕緣性非晶質氧化物薄膜作為通道層。
然而,關於專利文獻1所提出之藉由濺鍍法、脈衝雷射蒸鍍法中之任一氣相成膜法成膜且由In、Ga、Zn及O元素所構成之透明非晶質氧化物薄膜(a-IGZO膜),業界指出其載體遷移率停留於大致1cm2V-1sec-1以上且10cm2V-1sec-1以下之範圍,對於顯示器之更加高清化而言載體遷移率不足。
又,於專利文獻2中揭示有一種濺鍍靶,其係目的在於形成專利文獻1所記載之非晶質氧化物薄膜者,即至少含有In、Zn、Ga之燒結體靶,其特徵在於:其組成中含有In、Zn、Ga,相對密度為75%以上並且電阻值ρ為50Ωcm以下。然而,由於專利文獻2之靶係顯示出同型相晶
體結構之多晶氧化物燒結體,故而由此而獲得之非晶質氧化物薄膜與專利文獻1相同,載體遷移率會停留於大致10cm2V-1sec-1左右。
作為實現較高之載體遷移率之材料,專利文獻3中提出有一種薄膜電晶體,其特徵在於:使用鎵固溶於氧化銦,原子數比Ga/(Ga+In)為0.001以上且0.12以下,銦與鎵相對於所有金屬原子之含有率為80原子%以上,且具有In2O3之方鐵錳礦結構之氧化物薄膜;作為其原料,提出有一種氧化物燒結體,其特徵在於:鎵固溶於氧化銦,原子比Ga/(Ga+In)為0.001以上且0.12以下,銦與鎵相對於所有金屬原子之含有率為80原子%以上,且具有In2O3之方鐵錳礦結構。
然而,於將如專利文獻3所提出之結晶質之氧化物半導體薄膜應用於TFT之情形時,由晶界所導致之TFT特性不均成為問題。尤其是極難以於第8代以上之大型玻璃基板上均勻地形成TFT。
於專利文獻4中記載有一種燒結體,其係具有方鐵錳礦結構且含有氧化銦、氧化鎵及正三價及/或正四價之金屬之氧化物燒結體,且正三價及/或正四價之金屬含量為100ppm以上且10000ppm以下,銦(In)與鎵(Ga)之組成量以原子%計處於滿足0.005<In/(In+Ga)<0.15之式之組成範圍;且揭示有TFT評價中,顯示出60cm2V-1sec-1左右之較高之遷移率之實施例。
然而,藉由專利文獻4之燒結體而獲得之氧化物半導體薄膜容易生成微晶等之方面成為問題,尤其難以於大型玻璃基板上良率較好地形成TFT。一般而言,氧化物半導體之薄膜電晶體之製造步驟中,暫時形成非晶質膜並藉由其後之退火處理而獲得非晶質或結晶質之氧化物半導體
薄膜。於非晶質膜形成步驟之後,為了圖案化加工成所需通道層之形狀,利用含有草酸或鹽酸等之水溶液等弱酸實施濕式蝕刻。然而,於使用專利文獻4之實質上僅由方鐵錳礦結構所構成之氧化物燒結體之情形時,會產生如下問題:所形成之非晶質膜之結晶化溫度降低,於成膜後之階段已生成微晶,而於蝕刻步驟中產生殘渣;或部分地進行結晶化而無法進行蝕刻。即,會引起如下等問題:難以利用光微影技術等並藉由濕式蝕刻法而形成所需TFT通道層之圖案,或即便形成了TFT亦不會穩定地動作。
[專利文獻1]日本特開2010-219538號公報
[專利文獻2]日本特開2007-073312號公報
[專利文獻3]WO2010/032422號公報
[專利文獻4]WO2011/152048號公報
本發明之目的在於提供一種可形成顯示出良好之濕式蝕刻性與較高之載體遷移率之非晶質的氧化物半導體薄膜之濺鍍用靶、對於獲得其而言最適合之氧化物燒結體、以及使用其而得之顯示出較低之載體濃度與較高之載體遷移率的氧化物半導體薄膜。
本發明人等新發現:於以氧化物之形式含有銦、鎵及鋁且鎵之含量以Ga/(In+Ga)原子數比計為0.15以上且0.49以下,並且鋁之含量以Al/(In+Ga+Al)之原子數比計為0.0001以上且未達0.25之氧化物燒結體由方鐵錳礦型結構之In2O3相與作為In2O3相以外之生成相之β-Ga2O3型結構之GaInO3相、或β-Ga2O3型結構之GaInO3相與(Ga,In)2O3相及InAlO3相所構成之情形時,使用上述氧化物燒結體所製作之非晶質之氧化物半導體薄膜顯示出良好之濕式蝕刻性、較低之載體濃度與較高之載體遷移率。
即,本發明之第一發明係一種氧化物燒結體,其以氧化物之形式含有銦、鎵及鋁,上述鎵之含量以Ga/(In+Ga)原子數比計為0.15以上且0.49以下,上述鋁之含量以Al/(In+Ga+Al)原子數比計為0.0001以上且未達0.25。
本發明之第二發明係如第一發明所記載之氧化物燒結體,其係方鐵錳礦型結構之In2O3相及In2O3相以外之生成相構成,該In2O3相以外之生成相為β-Ga2O3型結構之GaInO3相、或β-Ga2O3型結構之GaInO3相與(Ga,In)2O3相。
本發明之第三發明係如第一或第二發明所記載之氧化物燒結體,其中,上述鋁之含量以Al/(In+Ga+Al)原子數比計為0.01以上且0.20以下。
本發明之第四發明係如第一至第二發明所記載之氧化物燒結體,其中,上述鎵之含量以Ga/(In+Ga)原子數比計為0.20以上且0.45以下。
本發明之第五發明係一種濺鍍用靶,其係對第一至第二發明所記載之氧化物燒結體進行加工而獲得。
本發明之第六發明係一種氧化物半導體薄膜,其係使用第五發明所記載之濺鍍用靶並藉由濺鍍法形成於基板上之後,實施氧化性環境中之熱處理而成之非晶質之氧化物半導體薄膜。
本發明之第七發明係如第六發明所記載之氧化物半導體薄膜,其載體濃度未達4.0×1018cm-3,且載體遷移率為10cm2V-1sec-1以上。
本發明之第八發明係如第七發明所記載之氧化物半導體薄膜,其載體濃度為6.0×1017cm-3以下。
本發明之第九發明係如第七發明所記載之氧化物半導體薄膜,其載體遷移率為15cm2V-1sec-1以上。
關於本發明之以氧化物之形式含有銦、鎵及鋁且鎵之含量以Ga/(In+Ga)原子數比計為0.15以上且0.49以下,並且鋁之含量以Al/(In+Ga+Al)之原子數比計為0.0001以上且未達0.25,且含有方鐵錳礦型結構之In2O3相與作為In2O3相以外之生成相之β-Ga2O3型結構之GaInO3相、或β-Ga2O3型結構之GaInO3相及(Ga,In)2O3相之氧化物燒結體,例如於用作濺鍍用靶之情形時係藉由濺鍍成膜而形成,其後進行熱處理,藉此可獲得本發明之非晶質之氧化物半導體薄膜。上述藉由濺鍍成膜而形成之薄膜藉由含有特定量之鎵與鋁之效果而不會生成微晶等,具有充分之非晶質性,故而可藉由濕式蝕刻圖案化加工成所需形狀。又,藉由相同效果,本發明之非晶質之氧化物半導體薄膜顯示出較低之載體濃度與較高之載體
遷移率。因此,於將本發明之非晶質之氧化物半導體薄膜應用於TFT之情形時,能夠提高TFT之接通/斷開(on/off)。因此,本發明之氧化物燒結體、靶、及使用其而得之氧化物半導體薄膜於工業上極為有用。
圖1係表示實施例6之氧化物燒結體之X射線繞射測定結果光譜之圖。
圖2係表示實施例9之氧化物燒結體之X射線繞射測定結果光譜之圖。
圖3係使用掃描穿透式電子顯微鏡所拍攝之實施例9之氧化物燒結體之晶粒照片。
圖4係使用掃描穿透式電子顯微鏡所拍攝之實施例9之氧化物燒結體之白色晶粒的電子束繞射照片。
圖5係使用掃描穿透式電子顯微鏡所拍攝之實施例9之氧化物燒結體之黑色晶粒的電子束繞射照片。
以下,針對本發明之氧化物燒結體、濺鍍用靶、及使用其而得之氧化物半導體薄膜詳細地進行說明。
本發明之氧化物燒結體以氧化物之形式含有銦、鎵及鋁,其特徵在於:鎵之含量以Ga/(In+Ga)原子數比計為0.15以上且0.49以下,且鋁之含
量以Al/(In+Ga+Al)原子數比計為0.0001以上且未達0.25。
鎵之含量以Ga/(In+Ga)原子數比計為0.15以上且0.49以下,更佳為0.20以上且0.45以下。鎵具有提高本發明之非晶質之氧化物半導體薄膜之結晶化溫度的效果。又,鎵與氧之鍵結力較強,具有降低本發明之非晶質之氧化物半導體薄膜之氧空位量之效果。於鎵之含量以Ga/(In+Ga)原子數比計未達0.15之情形時,無法充分地獲得該等效果。另一方面,於超過0.49之情形時,無法獲得作為氧化物半導體薄膜而言足夠高之載體遷移率。
本發明之氧化物燒結體除了含有如上述般規定之組成範圍之銦與鎵以外亦含有鋁。鋁濃度以Al/(In+Ga+Al)之原子數比計為0.0001以上且未達0.25,較佳為0.01以上且0.20以下。鋁具有提高本發明之非晶質之氧化物半導體薄膜之結晶化溫度之效果。又,藉由添加鋁,可抑制本發明之非晶質之氧化物半導體薄膜之載體濃度,但於超過0.25之情形時,濺鍍靶之體電阻值變高,濺鍍時於成膜時因如電弧放電(弧光放電)之異常放電而無法獲得均質之膜。
藉由該效果,於將本發明之非晶質之氧化物半導體薄膜應用於TFT之情形時,能夠提高TFT之接通/斷開。
本發明之氧化物燒結體係由方鐵錳礦型結構之In2O3相及β-Ga2O3型結構之GaInO3相所構成,除該等以外亦可略微含有(Ga,In)2O3相。
此處,鎵較佳為固溶於In2O3相、或構成GaInO3相。基本上作為正三價離子之鎵在固溶於In2O3相之情形時,同樣地會置換作為正三價
離子之銦之晶格位置。於構成GaInO3相以及(Ga,In)2O3相之情形時,基本上Ga佔據原本之晶格位置,亦可於In之晶格位置以缺陷之形式進行若干置換固溶。又,因燒結未進行等原因,鎵難以固溶於In2O3相、或難以生成β-Ga2O3型結構之GaInO3相以及(Ga,In)2O3相,作為其結果,形成β-Ga2O3型結構之Ga2O3相,故而欠佳。Ga2O3相由於缺乏導電性,故而會導致異常放電。
又,鋁較佳為固溶於In2O3相或GaInO3相。基本上作為正三價離子之鋁在固溶於In2O3相之情形時,同樣地會置換作為正三價離子之銦之晶格位置。於固溶於GaInO3相以及(Ga,In)2O3相之情形時,基本上會於In或Ga之晶格位置進行置換。
本發明之氧化物燒結體至少由In2O3相所構成,且存在含有β-Ga2O3型結構之GaInO3相以及(Ga,In)2O3相之情形,該等相之晶粒較佳為平均粒徑5μm以下。該等相之晶粒由於與方鐵錳礦型結構之In2O3相之晶粒相比更難以被濺鍍,故而存在因凹陷而產生節瘤,從而導致弧光放電之情形。
本發明之氧化物燒結體之製造中,將含有氧化銦粉末與氧化鎵粉末之氧化物粉末、以及氧化鋁粉末用作原料粉末。
本發明之氧化物燒結體之製造步驟中,於混合該等原料粉末之後進行成形,並藉由常壓燒結法對成形物進行燒結。本發明之氧化物燒結體組織之生成相較強地取決於氧化物燒結體之各步驟之製造條件,例如原料粉末之粒徑、混合條件及燒結條件。
本發明之氧化物燒結體之組織較佳為以InAlO3相、β-Ga2O3型結構之GaInO3相、進而(Ga,In)2O3相之各晶粒成為5.0μm以下之方式進行控制,為此,更佳為將上述原料粉末之平均粒徑設為3.0μm以下,進而較佳為設為1.0μm以下。
氧化銦粉末為ITO(添加有錫之銦氧化物)之原料,燒結性優異之微細之氧化銦粉末之開發係與ITO之改良一併進行。氧化銦粉末由於被被持續大量用作ITO用原料,故而最近可獲取平均粒徑1.0μm以下之原料粉末。
氧化鋁(alumina)粉末由於被廣泛用作陶瓷或藍寶石之原料,故而可獲取平均粒徑1.0μm以下之原料粉末。
然而,於氧化鎵粉末之情形時,由於使用量仍然少於氧化銦粉末,故而存在難以獲取平均粒徑1.0μm以下之原料粉末之情形。於僅可獲取粗大之氧化鎵粉末之情形時,需要粉碎至平均粒徑1.0μm以下。
本發明之氧化物燒結體之燒結步驟中,較佳為應用常壓燒結法。常壓燒結法係簡便且於工業上有利之方法,就低成本之觀點而言亦為較佳手段。
於使用常壓燒結法之情形時,如上所述,首先製作成形體。將原料粉末加入至樹脂製罐中,與黏合劑(例如PVA)等一併利用濕式球磨機等進行混合。本發明之氧化物燒結體係由InAlO3相、方鐵錳礦型結構之In2O3相及β-Ga2O3型結構之GaInO3相所構成,且存在進而含有(Ga,In)2O3相之情形,較佳為將該等相之晶粒控制為平均粒徑5μm以下而進行微細分散。又,較佳為儘量抑制(Ga,In)2O3相之生成。並且,必須不生成除
該等相以外之導致弧光放電之β-Ga2O3型結構之Ga2O3相。為了滿足該等必要條件,較佳為進行上述球磨機混合18小時以上。此時,作為混合用球,使用硬質ZrO2球即可。混合後,將漿料取出,並進行過濾、乾燥、造粒。其後,藉由冷均壓加壓施加9.8MPa(0.1ton/cm2)以上且294MPa(3ton/cm2)以下左右之壓力將所獲得之造粒物成形,而製作成形體。
常壓燒結法之燒結步驟中,較佳為設為存在氧之環境,更佳為環境中之氧體積分率超過20%。尤其是藉由使氧體積分率超過20%,使氧化物燒結體進一步高密度化。藉由環境中之過量之氧,而於燒結初期先進行成形體表面之燒結。繼而,進行成形體內部之還原狀態下之燒結,最終獲得高密度之氧化物燒結體。
於不存在氧之環境中,由於未先進行成形體表面之燒結,故而結果未進行燒結體之高密度化。若不存在氧,則尤其於900℃以上且1000℃以下左右,氧化銦會分解而生成金屬銦,故而較難獲得目標之氧化物燒結體。
常壓燒結之溫度範圍較佳為1200℃以上且1550℃以下,更佳為於向燒結爐內之大氣導入氧氣之環境中為1350℃以上且1450℃以下。燒結時間較佳為10小時以上且30小時以下,更佳為15小時以上且25小時以下。
藉由將燒結溫度設為上述範圍,並將上述調整為平均粒徑1.0μm以下之含有氧化銦粉末、氧化鎵粉末之氧化物粉末、以及氧化鋁粉末用作原料粉末,而主要由方鐵錳礦型結構之In2O3相與β-Ga2O3型結構之GaInO3相、或(Ga,In)2O3相所構成。
於燒結溫度未達1200℃之情形時,燒結反應未充分地進行。另一方面,若燒結溫度超過1550℃,則變得難以進行高密度化,另一方面,燒結爐之構件與氧化物燒結體會進行反應,而無法獲得目標之氧化物燒結體。尤其是本發明之氧化物燒結體由於鎵之含量以Ga/(In+Ga)原子數比計為0.15以上,故而較佳為將燒結溫度設為1450℃以下。其原因在於存在如下情況:於1500℃左右之溫度區域,(Ga,In)2O3相之生成變得明顯。若(Ga,In)2O3相為少量則無礙,但於大量之情形時,有引起成膜速度降低或弧光放電等之虞,故而欠佳。
關於至燒結溫度為止之升溫速度,為了防止燒結體之破裂,進行脫黏,較佳為將升溫速度設為0.2℃/min以上且5℃/min以下之範圍。若為該範圍,則亦可視需要將不同升溫速度組合而升溫至燒結溫度。於升溫過程中,為了進行脫黏或燒結,可於特定溫度下保持一定時間。燒結後進行冷卻時,較佳為停止導入氧氣,並以0.2℃/min以上且5℃/min以下、尤其是0.2℃/min以上且1℃/min以下之範圍之降溫速度降溫至1000℃。
本發明之靶可藉由將本發明之氧化物燒結體加工成特定大小而獲得。於用作靶之情形時,可進一步對表面進行研磨加工,並接著於背襯板(backing plate)而獲得。靶形狀較佳為平板形,但亦可為圓筒形。於使用圓筒形靶之情形時,較佳為抑制因靶旋轉而引起之微粒產生。又,可將上述氧化物燒結體例如加工成圓柱形狀而製作平板,並用於利用蒸鍍法或離子鍍覆法之成膜。
於用作濺鍍用靶之情形時,本發明之氧化物燒結體之密度較佳為6.3g/cm3以上,更佳為6.7g/cm3以上。於密度未達6.3g/cm3之情形時,會成為量產使用時產生節瘤之原因。又,於用作離子鍍覆用平板之情形時,較佳為未達6.3g/cm3,若為3.4g/cm3以上且5.5g/cm3以下則更佳。於此情形時,存在宜將燒結溫度設為未達1200℃之情形。
本發明之非晶質之氧化物半導體薄膜主要藉由如下方式而獲得:使用上述濺鍍用靶,藉由濺鍍法於基板上暫時形成非晶質之氧化物薄膜,繼而實施退火處理。
上述濺鍍用靶係利用本發明之氧化物燒結體而獲得,重要的是其氧化物燒結體組織、由方鐵錳礦型結構之In2O3相及β-Ga2O3型結構之GaInO3相或β-Ga2O3型結構之GaInO3相與(Ga,In)2O3相所基本構成之組織。為了獲得本發明之非晶質之氧化物半導體薄膜,重要的是非晶質之氧化物半導體薄膜之結晶化溫度較高,而其與氧化物燒結體組織相關。即,於如本發明之氧化物燒結體般不僅含有方鐵錳礦型結構之In2O3相,亦含有β-Ga2O3型結構之GaInO3相或β-Ga2O3型結構之GaInO3相與(Ga,In)2O3相之情形時,由此獲得之氧化物薄膜會顯示出較高之結晶化溫度、即300℃以上、更佳為350℃以上之結晶化溫度,成為穩定之非晶質。相對於此,於氧化物燒結體僅由方鐵錳礦型結構之In2O3相所構成之情形時,由此獲得之氧化物薄膜之結晶化溫度較低,為200℃左右,而未成為非晶質性。再者,於此情形時,於成膜後已生成微晶而未維持非晶質性,變得難以進行利用濕式蝕刻之圖案化加工。
本發明之非晶質之氧化物半導體薄膜之成膜步驟可使用普通之濺鍍法,尤其是若為直流(DC)濺鍍法,則由於成膜時之熱影響較少且可高速成膜,故而於工業上有利。於藉由直流濺鍍法形成本發明之氧化物半導體薄膜時,較佳為使用由非活性氣體與氧氣、尤其是氬氣與氧氣所構成之混合氣體作為濺鍍氣體。又,較佳為將濺鍍裝置之腔室內設為0.1Pa以上且1Pa以下、尤其是0.2Pa以上且0.8Pa以下之壓力而進行濺鍍。
關於基板,玻璃基板具有代表性,較佳為無鹼玻璃,樹脂板或樹脂膜之中只要可耐受上述製程條件者即可使用。
上述非晶質之氧化物薄膜形成步驟例如可於真空排氣至2×10-4Pa以下後,導入由氬氣與氧氣所構成之混合氣體,將氣壓設為0.2Pa以上且0.8Pa以下,以相對於靶之面積之直流電力、即直流電力密度成為1W/cm2以上且7W/cm2以下左右之範圍之方式施加直流電力而產生直流電漿,並實施預濺鍍。較佳為進行該預濺鍍5分鐘以上且30分鐘以下之後,視需要對基板位置進行修正,然後進行濺鍍。
於上述成膜步驟之濺鍍成膜中,為了提高成膜速度,可提高所輸入之直流電力。
本發明之非晶質之氧化物半導體薄膜可藉由成膜上述非晶質之氧化物薄膜之後對其進行退火處理而獲得。作為至退火處理為止之方法之一,例如於室溫附近等低溫下暫時形成非晶質之氧化物薄膜,其後於未達結晶化溫度下進行退火處理,而獲得仍維持非晶質之氧化物半導體薄膜。作為另一方法,將基板加熱至未達結晶化溫度之溫度、較佳為100℃以上且300℃以下,而成膜非晶質之氧化物半導體薄膜。繼而,可進一步進行
退火處理。該等兩個方法中之加熱溫度大致為600℃以下即可,可設為無鹼玻璃基板之應變點以下。
本發明之非晶質之氧化物半導體薄膜可藉由暫時形成非晶質之氧化物薄膜,然後進行退火處理而獲得。退火處理條件於氧化性環境中為未達結晶化溫度之溫度。作為氧化性環境,較佳為含有氧、臭氧、水蒸氣、或氮氧化物等之環境。退火溫度為200℃以上且600℃以下,較佳為300℃以上且500℃以下。關於退火時間,保持在退火溫度之時間為1分鐘以上且120分鐘以下,較佳為5分鐘以上且60分鐘以下。
上述非晶質之氧化物薄膜及非晶質之氧化物半導體薄膜之銦、鎵、及鋁之組成係與本發明之氧化物燒結體之組成大致相同。即,為以氧化物之形式含有銦及鎵且含有鋁之非晶質之氧化物半導體薄膜。鎵之含量以Ga/(In+Ga)原子數比計為0.15以上且0.49以下,上述鋁之含量以Al/(In+Ga+Al)原子數比計為0.0001以上且未達0.25。
本發明之非晶質之氧化物半導體薄膜係藉由將如上所述之組成及組織經控制之氧化物燒結體用於濺鍍靶等而進行成膜,並於上述適當之條件下進行退火處理,而使載體濃度降低至4.0×1018cm-3以下,並顯示出載體遷移率10cm2V-1sec-1以上。更佳為獲得15cm2V-1sec-1以上、尤佳為20cm2V-1sec-1以上之載體遷移率。
本發明之非晶質之氧化物半導體薄膜係藉由濕式蝕刻或乾式蝕刻,根據TFT等用途而實施所需之微細加工。通常,可自未達結晶化溫度之溫度例如室溫至300℃之範圍內選擇適當之基板溫度而暫時形成非晶質之氧化物薄膜,然後利用濕式蝕刻實施微細加工。作為蝕刻劑,只要
為弱酸則基本上可使用,較佳為以草酸或鹽酸為主成分之弱酸。例如可使用關東化學製造之ITO-06N等市售品。根據TFT之構成,亦可選擇乾式蝕刻。
本發明之非晶質之氧化物半導體薄膜之膜厚並無限定,為10nm以上且500nm以下,較佳為20nm以上且300nm以下,進而較佳為30nm以上且100nim以下。若未達10nm,則無法獲得充分之半導體特性,結果無法實現較高之載體遷移率。另一方面,若超過500nm,則會產生生產性之問題,故而欠佳。
以下,使用本發明之實施例更詳細地進行說明,但本發明並不受該等實施例所限定。
藉由ICP發光分光法調查所獲得之氧化物燒結體之金屬元素之組成。使用所獲得之氧化物燒結體之邊角材料,並使用X射線繞射裝置(PHILIPS製造)藉由粉末法進行生成相之鑑定。又,使用聚焦離子束裝置對所獲得之氧化物燒結體進行薄片化,利用掃描穿透式電子顯微鏡(Hitachi High-Technologies製造)進行晶粒之觀察及電子束繞射測定,而進行生成相之鑑定。進而,利用能量分散型X射線分析(Hitachi High-Technologies製造)調查各晶粒之組成。
藉由ICP發光分光法調查所獲得之氧化物薄膜之組成。氧化物薄膜之膜厚係利用表面粗糙度計(Tencor公司製造)進行測定。成膜速度係根據
膜厚與成膜時間而算出。氧化物薄膜之載體濃度及遷移率係藉由霍耳效應(Hall effect)測定裝置(TOYO Corporation製造)而求出。膜之生成相係藉由X射線繞射測定而進行鑑定。
以平均粒徑成為1.0μm以下之方式調整氧化銦粉末、氧化鎵粉末、以及氧化鋁粉末,而製作原料粉末。以成為如表1及表3之實施例及比較例之Ga/(In+Ga)原子數比、Al/(In+Ga+Al)原子數比之方式調製該等原料粉末,與水一併加入至樹脂製罐中,並利用濕式球磨機進行混合。此時,使用硬質ZrO2球,並將混合時間設為18小時。混合後,將漿料取出,並進行過濾、乾燥、造粒。藉由冷均壓加壓施加3ton/cm2之壓力將造粒物成形。
繼而,以如下方式對成形體進行燒結。於爐內容積每0.1m3以5公升/分鐘之比率向燒結爐內之大氣中導入氧氣之環境下,於1350℃以上且1450℃以下之燒結溫度下進行燒結20小時。此時,以1℃/min進行升溫,於燒結後進行冷卻時停止導入氧氣,並以1℃/min降溫至1000℃。
藉由ICP發光分光法進行所獲得之氧化物燒結體之組成分析,結果關於金屬元素,於任一實施例中均確認到與原料粉末之調配時之添加組成大致相同。
繼而,藉由X射線繞射測定(XRD,X-ray diffraction)進行氧化物燒結體之相鑑定、及利用掃描穿透式電子顯微鏡(STEM,Scanning transmission electron microscope)進行晶粒之觀察,藉由能量分散型X射線(EDX,Energy dispersive X-ray spectrometry)分析進行各晶粒之組成分析,
並將其結果示於表1。
又,將實施例6之X射線繞射測定結果與相鑑定之結果示於圖1,將實施例9之X射線繞射測定結果及相鑑定之結果示於圖2,將實施例9之掃描穿透式電子顯微鏡之觀察結果示於圖3。藉由掃描穿透式電子顯微鏡之觀察,確認到存在看起來發白之晶粒與看起來發黑之晶粒之2種晶粒。進而,將圖3中看起來發白之晶粒之電子束繞射照片示於圖4,將看起來發黑之晶粒之電子束繞射照片示於圖5。再者,於圖4、圖5中,係以「○」表示穿透點及所分析之繞射點之位置,以白線連接穿透點與繞射點。根據圖4、圖5,針對各晶粒求出晶面間距及晶面角度,與JCPDS卡之文獻值進行比較,並將所得之結果示於表2。根據與JCPDS卡之比較得知:看起來發白之晶粒為In2O3相(JCPDS卡編號:00-006-0416),看起來發黑之晶粒為GaInO3相(JCPDS卡編號:04-017-1567)。進而,根據X射線繞射測定及能量分散型X射線分析之結果亦得知:看起來發白之晶粒為In2O3相,看起來發黑之晶粒為GaInO3相。
將氧化物燒結體加工成直徑152mm、厚度5mm之大小,並利用杯形磨石以最大高度Rz成為3.0μm以下之方式對濺鍍面進行研磨。使用金屬銦將所加工之氧化物燒結體接合於無氧銅製之背襯板,而製成濺鍍用靶。
使用實施例及比較例之濺鍍用靶以及無鹼之玻璃基板(Corning EagleXG),於表3所記載之基板溫度下藉由直流濺鍍進行成膜。於裝備有無弧光放電抑制功能之直流電源之直流磁控濺鍍裝置(Tokki製造)之陰極,安裝上述濺鍍靶。此時,將靶-基板(保持器)間距離固定為60mm。
於真空排氣至2×10-4Pa以下之後,根據各靶之鎵量以及鋁量,以成為適當之氧之比率之方式導入氬氣與氧氣之混合氣體,將氣壓調整為0.6Pa。施加直流電力300W(1.64W/cm2)而產生直流電漿。於10分鐘之預濺鍍後,於濺鍍靶之正上方、即靜止對向位置配置基板,而形成膜厚50nm之氧化物半導體薄膜。此時,對有無產生弧光放電進行確認。確認到所獲得之氧化物半導體薄膜之組成與靶大致相同。
如表3所記載般對所成膜之氧化物半導體薄膜於氧氣中,於300℃以上且500℃以下實施30分鐘以上且60分鐘以下之熱處理,並藉由X射線繞射測定調查熱處理後之氧化物半導體薄膜之結晶性。其結果為,比較例1及2之氧化物半導體薄膜發生結晶化,並生成方鐵錳礦型結構之In2O3相,除此以外之實施例及比較例維持非晶質。又,針對結晶化之氧化物半導體薄膜,對構成氧化物半導體薄膜之結晶相進行鑑定。針對除比較例1及2以外之實施例及比較例進行氧化物半導體薄膜之霍耳效應測定,並求出載體濃度及載體遷移率。將所獲得之評價結果彙總記載於表3。
根據表1之結果,實施例1~17之氧化物燒結體於鎵含量以Ga/(In+Ga)原子數比計為0.15以上且0.49以下,且鋁之含量以Al/(In+Ga+Al)原子數比計為0.0001以上且未達0.25之情形時,係由方鐵錳礦型結構之In2O3相及β-Ga2O3型結構之GaInO3相或β-Ga2O3型結構之GaInO3相與(Ga,In)2O3相所構成。相對於此,比較例1~3中,氧化物燒結體之鎵或鋁含量少於本發明之範圍。因此,比較例1中,成為僅由方鐵錳礦型結構之In2O3相所構成之氧化物燒結體。又,比較例4~8中,由於鋁含量過量,故
而於濺鍍成膜時會產生弧光放電,無法獲得均質之膜,而未獲得本發明之目標之氧化物燒結體。
又,根據表3之結果顯示出如下氧化物半導體薄膜之特性:該氧化物半導體薄膜係含有銦、鎵及鋁之非晶質之氧化物半導體薄膜,且鎵含量以Ga/(In+Ga)原子數比計被控制為0.15以上且0.49以下,鋁含量以Al/(In+Ga+Al)原子數比計被控制為0.0001以上且未達0.25。
得知實施例之氧化物半導體薄膜之任一者均為非晶質。又,得知實施例之氧化物半導體薄膜之載體濃度為4.0×1018cm-3以下,及載體遷移率為10cm2V-1sec-1以上,尤其是鎵含量以Ga/(In+Ga)原子數比計為0.20以上且0.45以下,且鋁含量以Al/(In+Ga+Al)原子數比計為0.01以上且0.20以下之實施例6、7、9、11、12之氧化物半導體薄膜顯示出載體濃度為6.0×1017cm-3以下、載體遷移率為15cm2V-1sec-1以上之優異特性。
相對於此,比較例1及2中,退火後之氧化物半導體薄膜發生結晶化,生成方鐵錳礦型結構之In2O3相而不為非晶質。又,得知,比較例3中,Al/(In+Ga+Al)原子數比所表示之鋁之含量不滿足本發明之範圍,結果其載體濃度超過4.0×1018cm-3。又,比較例4~8之氧化物半導體薄膜由於上述鋁含量之結果為產生弧光放電而未獲得均質之膜,故而未進行載體濃度、載體遷移率之評價。得知比較例9之氧化物半導體由於上述Ga/(In+Ga)超過上限,故而其載體遷移率未達10cm2V-1sec-1。
Claims (9)
- 一種氧化物燒結體,其以氧化物之形式含有銦、鎵及鋁,上述鎵之含量以Ga/(In+Ga)原子數比計為0.15以上且0.49以下,上述鋁之含量以Al/(In+Ga+Al)原子數比計為0.0001以上且未達0.25。
- 如申請專利範圍第1項之氧化物燒結體,其係方鐵錳礦型結構之In2O3相及In2O3相以外之生成相構成,該In2O3相以外之生成相為β-Ga2O3型結構之GaInO3相、或β-Ga2O3型結構之GaInO3相與(Ga,In)2O3相。
- 如申請專利範圍第1或2項之氧化物燒結體,其中,上述鋁之含量以Al/(In+Ga+Al)原子數比計為0.01以上且0.20以下。
- 如申請專利範圍第1或2項之氧化物燒結體,其中,上述鎵之含量以Ga/(In+Ga)原子數比計為0.20以上且0.45以下。
- 一種濺鍍用靶,其係對申請專利範圍第1或2項之氧化物燒結體進行加工而獲得。
- 一種氧化物半導體薄膜,其係於使用申請專利範圍第5項之濺鍍用靶並藉由濺鍍法形成於基板上之後,實施氧化性環境中之熱處理而成之非晶質之氧化物半導體薄膜。
- 如申請專利範圍第6項之氧化物半導體薄膜,其載體濃度未達4.0×1018cm-3,且載體遷移率為10cm2V-1sec-1以上。
- 如申請專利範圍第7項之氧化物半導體薄膜,其載體濃度為6.0×1017cm-3以下。
- 如申請專利範圍第7項之氧化物半導體薄膜,其載體遷移率為15cm2V-1sec-1以上。
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- 2015-11-18 TW TW104137984A patent/TWI574935B/zh not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI820861B (zh) * | 2018-08-01 | 2023-11-01 | 日本商出光興產股份有限公司 | 結晶構造化合物、氧化物燒結體、濺鍍靶材、結晶質氧化物薄膜、非晶質氧化物薄膜、薄膜電晶體、及電子機器 |
Also Published As
Publication number | Publication date |
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JPWO2016084636A1 (ja) | 2017-10-12 |
CN107001144A (zh) | 2017-08-01 |
TWI574935B (zh) | 2017-03-21 |
WO2016084636A1 (ja) | 2016-06-02 |
US20170345653A1 (en) | 2017-11-30 |
KR20170086473A (ko) | 2017-07-26 |
US10128108B2 (en) | 2018-11-13 |
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