TW201248903A - Sputtering target for forming transparent film for solar cells, and process for production thereof - Google Patents
Sputtering target for forming transparent film for solar cells, and process for production thereof Download PDFInfo
- Publication number
- TW201248903A TW201248903A TW101104037A TW101104037A TW201248903A TW 201248903 A TW201248903 A TW 201248903A TW 101104037 A TW101104037 A TW 101104037A TW 101104037 A TW101104037 A TW 101104037A TW 201248903 A TW201248903 A TW 201248903A
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- Prior art keywords
- powder
- sputtering target
- transparent film
- sputtering
- zno
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000000843 powder Substances 0.000 claims abstract description 39
- 238000004544 sputter deposition Methods 0.000 claims abstract description 39
- 239000011812 mixed powder Substances 0.000 claims abstract description 16
- 229910052844 willemite Inorganic materials 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052593 corundum Inorganic materials 0.000 abstract description 17
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 17
- 229910052681 coesite Inorganic materials 0.000 abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 abstract description 16
- 239000000377 silicon dioxide Substances 0.000 abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract 2
- 239000010408 film Substances 0.000 description 80
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 65
- 239000011787 zinc oxide Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 18
- 230000002159 abnormal effect Effects 0.000 description 11
- 238000010304 firing Methods 0.000 description 11
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- -1 polyethylene Polymers 0.000 description 6
- 238000007731 hot pressing Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- CZEPEKPAPYAXPU-UHFFFAOYSA-N [O-2].[Ce+3].[O-2].[Zn+2] Chemical compound [O-2].[Ce+3].[O-2].[Zn+2] CZEPEKPAPYAXPU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- QYHNIMDZIYANJH-UHFFFAOYSA-N diindium Chemical group [In]#[In] QYHNIMDZIYANJH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
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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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
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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
- 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
- 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
- C23C14/081—Oxides of aluminium, magnesium or beryllium
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- 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
- 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
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- H—ELECTRICITY
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- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F77/00—Constructional details of devices covered by this subclass
- H10F77/30—Coatings
- H10F77/306—Coatings for devices having potential barriers
- H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
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- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Photovoltaic Devices (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
Description
201248903 六、發明說明: 【發明所屬之技術領域】 本發明有關很適合作爲薄膜太陽電池(thin film solar cell)用之低折射率的透明膜之Zn0-Si02-Al203(氧化鋅-二 氧化矽-三氧化二鋁)膜的成膜之太陽電池用透明膜形成用 灘鍍靶(sputtering target)及其製造方法。 【先前技術】 近年來,薄膜太陽電池已開始提供爲實用。此種薄膜 太陽電池,具有形成有 AZ0(Al-Zn-0: Aluminium doped Zinc Oxide:摻雜有鋁之氧化鋅)等的透明電極層(transparent electrode layer)、再於該透明電極層上形成有爲防止反射 用之低折射率的透明膜之基本構造。 上述低折射率的透明膜,係配置於透明導電膜( transparent conductive film)的上面藉以緩和與大氣之間的 折射率的變化而防止反射之用所設置者。 在來,例如專利文獻1中所記載,透明導電層上之低 折射率透明膜,係由MgF2(氟化鎂)所形成者。 又,例如專利文獻2中所記載,爲抑制各層的折射率 差爲小,抑制在界面的反射以增大到達受光面(light reception surface)之光量起見、爲連續性增大折射率起見,形成有 多層的防反射塗膜(anti-reflection coating)。 [先前技術文獻] [專利文獻] -5- 201248903 [專利文獻1]日本專利特開2001-257374號公報 [專利文獻2]日本專利特開平7-235684號公報 【發明內容】 [發明所欲解決之課題] 上述在來技術中’尙留存有下述的課題。 亦即’低折射率的透明膜而言,在來,在採用折射率 1·37(對波長550nm的光)的MgF2膜,惟由於該MgF2膜下 的透明導電層之AZO膜的折射率爲1.8(對波長5 50nm的 光)之故,因兩者的折射率差而有發生相當不少程度之光 反射之問題。因此,希望開發一種使具有較AZO膜爲低 ,而接近MgF2膜之折射率之透明膜介在兩者之間,以使 階段性變化折射率,藉以抑制光的反射之作法。又,希望 開發一種能將此種太陽電池用透明膜,利用生產性優異的 DC (直流)濺鍍進行成膜之濺鍍靶。 本發明乃係鑑於前述之課題所開發者,其目的在於提 供一種能將較AZO膜之折射率爲低的Zn0-Si02-Al203膜 進行DC濺鍍之太陽電池用透明膜形成用濺鍍靶及其製造 方法。 [用以解決課題之手段] 本發明人等根據,如使AZ0膜中含有Si〇2則折射率會降 低之事贲,爲製造能作爲太陽電池用透明膜之Zn〇_Si〇2_Al2〇3 膜之成膜之濺鍍靶起見,進行硏究。於此硏究中’如將 -6- 201248903
Al2〇3粉末與Si〇2粉末與ZnO粉末之混合粉末在大氣中燒 成或氮氣氣氛中燒成以製作濺鍍靶之情形,發生Si02與 ZnO進行反應而成爲複合氧化物(compound oxide),並且 電阻升高爲1x1 〇6Ω /cm2以上而發生異常放電,以致不能 進行DC濺鍍之問題。又,如將Si02的含量設定爲少量時 ,雖然依上述製法仍能製得低電阻的濺鍍靶,惟利用該濺 鍍靶之成膜時,則不能獲得作爲太陽電池用透明膜所要求 之低折射率。於是,本發明人等再進行硏究之結果發現, 如成分組成控制爲既定範圍以實施熱壓(hot pressing)時, 則可製得低電阻且能進行良好的DC濺鍍之濺鍍靶,如使 用該濺鍍靶以進行濺鍍成膜時則可製得一種低折射率之 Zn0-Si02-Al203 膜之事實。 因而,本發明係根據上述心得所開發者,爲解決前述 課題起見,採用如下述之構成。亦即,本發明之濺鍍靶, 係由具有對全金屬成分量含有A1: 0.3至4.0 wt(重量)%、 Si : 6.0至14.5 wt%、餘部爲由Zn以及不可避免之不純物 所成之成分組成之氧化物燒結體所成者,其特徵爲:該燒 結體的組織中存在有複合氧化物Zn2 Si 04及ZnO。 由於此種太陽電池用透明膜形成用濺鍍靶,係由具有 對全金屬成分量含有 A1 : 0.3至 4.0wt%、Si : 6.0至 1 4.5 wt %、餘部爲由Zn以及不可避免之不純物所成之成分 組成之氧化物燒結體所成,而於該燒結體的組織中存在有 複合氧化物Zn2Si04及ZnO之故,複合氧化物Zn2Si04與 ZnO共存於組織中而藉以獲得導電性,除能進行良好的 201248903 DC濺鍍之同時,尙可製得較AZO膜爲低折射率且適合於 太陽電池用透明膜之Zn0-Si02-Al203膜。 在此,將上述A1的含量作成0.3至4.0wt°/〇之理由’ 係如在0.3 wt%以下時,則由於不能獲得足夠的導電性而 發生異常放電,以致不能實施DC濺鍍之故’如在4.0wt% 以上時,則由於將發生起因於所產生之Al2〇3與ZnO的複 合氧化物ZnAl204之異常放電’以致不能實施DC濺鍍之 故。 又,將上述Si的含量作成6.0至14.5wt%之理由,係 如在6.Owt%以下時,則由於不能獲得降低折射率之充分 的效果而發生異常放電,以致不能實施DC濺鍍之故,如 在14.5 wt%以上時,則由於不能獲得足夠的導電性而發生 異常放電,以致不能實施DC濺鍍之故》 又,本發明之太陽電池用透明膜形成用濺鍍靶之特徵 爲:前述燒結體的密度,係以理論密度比(theoretical density ratio)計,爲 100 至 108%。 由於該太陽電池用透明膜形成用濺鍍靶,係燒結體的 密度爲理論密度的100至108%之故,除能實施DC濺鑪之 同時,尙可抑制靶龜裂。 亦即,將上述燒結體的密度以理論密度比計,作成 100至108%之理由,係如在100%以下時,則由於會發生 靶龜裂等問題之故,如在1 〇 8 %以上時,則由於殆全部將 成爲複合氧化物Zn2Si04的組織,以致不能實施藉由DC 濺鍍之放電之故。 -8- 201248903 在此,爲理論密度的計算上,採用ZnO: 5.61g/Cm3、 Si02 : 2·20 g/cm3、Al2〇3 : 3.99 g/cm3 之値進行計算。 又’本發明之太陽電池用透明膜形成用濺鍍靶之特徵 爲:體電阻(bulk resistance),爲 1Ω · cm 以下。 亦即,由於該太陽電池用透明膜形成用濺鍍靶,係體 電阻在1 Ω · cm以下之故,能穩定進行良好的DC濺鍍。 本發明之太陽電池用透明膜形成用濺鍍靶之製造方法 ,係製作上述太陽電池用透明膜形成用濺鍍靶之方法,其 特徵爲:包含;將Al2〇3粉末與Si02粉末與ZnO粉末, 按能成爲由 Al2〇3: 0.5 至 5.0wt%、Si02: 10 至 22wt%、 餘部·· ZnO以及不可避免之不純物所成之方式混合以作成 混合粉末之過程、及將前述混合粉末在真空中使用熱壓機 (hot press)以進行燒結之過程。 亦即,於該太陽電池用透明膜形成用濺鍍靶之製造方 法中,由於依上述的範圍混合ai2o3粉末與Si02粉末與 ZnO粉末以作成混合粉末之過程後,將前述混合粉末在真 空中使用熱壓機以進行燒結之故,能穩定地實施良好的 DC濺鎪,且可製作能進行低折射率透明膜之成膜之濺鍍 耙。 [發明之效果] 如採用本發明,則可發揮如下述之效果。 亦即,如採用有關本發明之太陽電池用透明膜形成用 濺鍍靶,則由於由具有對全金屬成分量含有:A1: 0.3至 -9- 201248903 4.0wt%、Si: 6.0至14.5wt%、餘部爲由Zn以及不可避免 之不純物所成之成分組成之氧化物燒結體所成,而於該燒 結體的組織中存在有複合氧化物Zn2Si04及ZnO之故,可 製得一種除能進行良好的DC濺鍍之同時,尙較AZO膜之 折射率爲低且適合於太陽電池用透明膜之Zn0-Si02-Al203 膜。如採用本發明之濺鍍靶之製造方法,而將經依上述的 範圍混合Al2〇3粉末與Si02粉末與ZnO粉末之混合粉末 ,在真空中使用熱壓機進行燒結後,則可製作上述濺鍍靶 〇 因而,在經採用本發明之濺鍍靶並藉由DC濺鍍所成膜 之太陽電池用透明膜,可獲得作爲薄膜太陽電池的AZO膜( 透明電極層)上所形成之防止反射用之透明膜所要求之低折 射率,且能以低成本製作轉換效率(convertion efficiency) 良好的薄膜太陽電池。 [發明之最佳K施形態] 以下,在參考第1圖及第2圖之下,將有關本發明之 太陽電池用透明膜形成用濺鍍靶及其製造方法之一實施形 態加以說明。 本實施形態之太陽電池用透明膜形成用濺鍍靶,係由 具有對全金屬成分量含有:A1: 0.3至4.0wt%、Si : 6.0 至14.5 wt%、餘部爲由Zn以及不可避免之不純物所成之 成分組成之氧化物燒結體所成,於該燒結體之組織中存在 有複合氧化物Zn2Si04及ZnO之靶。 -10- 201248903 又,該濺鍍靶,係燒結體的密度爲理論密度之100至 108 %者。再者,該濺鍍靶,係體電阻爲IQ· cin以下者 〇 製作本實施形態之太陽電池用透明膜形成用濺鍍靶之 方法,包含;將Ah〇3粉末與Si02粉末與ZnO粉末,按 能成爲由 Al2〇3: 〇.5 至 5_0wt%、S丨02: 10 至 22wt%、餘 部:ZnO以及不可避免之不純物所成之方式混合以作成混 合粉末之過程、及將前述混合粉末在真空中使用熱壓機以 進行燒結之過程。 如就上述製法之一例加以詳述時,則例如,第1圖所 不般’首先將Al2〇3粉末與Si〇2粉末與ZnO粉末按能成 爲上述含量範圍之方式進行稱量,使用濕式球磨機加以粉 碎·混合以製作混合粉末。例如,將經稱量所得之各粉末 及氧化鉻球置入聚乙烯容器(聚乙烯製壺)中,使用球磨機 裝置進fr濕式混合既定時間,以作成混合粉末。在此,爲 溶劑,則例如,採用乙醇。 · 其次’將所得之混合粉末乾燥後,過篩例如,篩孔: 250μηι的篩子並造粒、再在真空乾燥後,例如在】2〇(rCT 5小時,以200kgf(千克力)/Cm2的壓力、在真空中進行熱 壓以作成燒結體。在此,熱壓溫度,較佳爲11〇〇至1250 C的範圍’壓力較佳爲150至350kgf/cm2之範圍》 經如此方式熱壓之燒結體,通常採用放電加工、切削 或磨削技法機械加工爲耙的指定形狀,將加工後的耙以 In(銦)作爲銲劑’並黏合(bonding)於由Cu(銅)或SUS(不鏽 -11 - 201248903 鋼)或者其他金屬(例如’ Mo(鉬))所成之背板(backing plate)以供爲濺鍍之用。 在此,其他的製造方法而言,亦可爲將上述製造方法 所採用之濕式球磨機之粉碎、混合,以純水作爲溶劑並使 用內容積300L(公升)的球磨機裝置替代實施,然後,經由 噴霧乾燥所乾燥造粒者,再使用乾式球磨機加以撕碎,並 將該撕碎粉末按與上述同樣方式進行熱壓之方法。又,亦 可爲經省略使用上述乾式球磨機之撕碎過程。 經使用該本實施形態之濺鍍靶實施DC濺鎞之太陽電 池用透明膜,具有含有Αΐ2〇3: 〇·5至5.0wt%、Si〇2: 10 至22wt%、餘部爲由ZnO以及不可避免之不純物所成之成 分組成。 經採用此種太陽電池用透明膜之薄膜太陽電池,例如 第2圖所示,係於驗石灰玻璃基板(soda lime glass board)l上 依序層合:Mo(鉬)後面電極(rear-face electrode)2、CIGS(銅 銦鎵硒)吸收層3、屬於η型半導體層之ZnO(氧化鋅), ZnS(硫化鋅),ZnOH(氫氧化鋅),CdS(硫化鎘)等的緩衝層 (buffer layer)4、屬於高電阻層之i(異)ZnO緩衝層5、屬 於上部透明電極層之AZO電極6、防反射膜7a、7b、以 及表面電極8、所構成,其中,屬於M gF2(氟化鎂)膜之防 反射膜7b與AZO電極6之間的防反射膜7a,即爲本责施 形態之太陽電池用透明膜。 於如此之本實施形態之太陽電池用透明膜形成用濺鍍 靶中,由於由具有對全金厕成分量含有A1: 0.3至4.0wt% -12- 201248903 ' Si: 6.0至14.5wt%、餘部爲由Zn以及不可 物所成之成分組成之氧化物燒結體所成、而於 組織中存在有複合氧化物Zn2Si04及ZnO之故 中共存有複合氧化物Zn2Si04與ZnO之結果獲 而可製得除能進行良好的DC濺鍍之同時,尙| 折射率爲低且適合於太陽電池用透明膜之ZnO 膜。 又,由於該太陽電池用透明膜形成用濺鍍 密度,係理論密度的100至108%之故,除能進 之同時,尙可抑制靶的龜裂。 再者,由於該太陽電池用透明膜形成用濺 阻,係1 Ω · cm以下之故,能穩定進行良好的 又,由於本實施形態之太陽電池用透明膜 靶之製造方法,係將ai2o3粉末與Si〇2粉末劈 ,依上述的範圍進行混合以作成混合粉末之過 混合粉末在真空中使用熱壓機進行燒結之故, 良好的DC濺鍍,而可製作能進行低折射率透 之上述濺鍍靶。 再者’由於採用該濺鍍靶以進行DC濺鍍 射用透明膜,係依上述含有範圍含有ai2o3、S 餘部爲由ZnO以及不可避免之不純物所成之成 ’可獲得作爲將形成於薄膜太陽電池的透明電 反射用透明膜所需要之低折射率,如採用該膜 太陽電池而獲得高的轉換效率。 避免之不純 該燒結體的 ,藉由組織 得導電性, 交AZO膜之 -Si〇2'Al2〇3 靶的燒結體 行DC濺鍍 鑛靶的體電 DC濺鎪。 形成用濺鍍 ! ZnO粉末 程後,將此 能穩定進行 明膜之成膜 所得之防反 iO,並具有 分組成之故 極層上之防 ,則可作爲 -13- 201248903 【實施方式】 將就根據上述本實施形態實際所製作之太陽電池用透 明膜形成用濺鍍靶之實施例所評價之結果,加以說明如下 〇 本實施例之製造,係依下列條件所實施者。 首先,將Al2〇3粉末及Si02粉末及ZnO粉末,依表1 中所示之各比例加以稱fi後,將所得之粉末及其4倍量( 重量比)的氧化錐球(將直徑5mm的球及直徑10mm的球各 一半)置入10公升的聚乙烯容器(聚乙烯製壺)中,使用球 磨機裝置進行濕式混合48小時,作成混合粉末。在此, 爲溶劑,則例如,採用乙醇。 其次,將所得之混合粉末乾燥後,過篩例如,篩孔: 2 5 Ομηι的篩子並造粒,再在真空乾燥後,在1 2〇〇 °c下5小 時’以200kgf/cm2的壓力,在真空中進行熱壓以作成燒結 體。 將經如此方式熱壓之燒結體,機械加工爲靶的指定形 狀(直徑125mm、厚度10mm),並將經加工者黏合於由無 氧銅所成之背板以製作本實施例之濺鍍靶。 再者’作爲比較例1至1 1,將Al2〇3粉末及Si02粉 末及ZnO粉末依表丨所示之各比例稱量,並將所得之各粉 末混合’以0.6t(噸)/cm2加壓,再使用CIP(冷間等靜水壓 壓機)依175MPa(兆帕斯卡)進行成型,將此在14〇(rc下實 施大氣燒成以製作濺鍍靶。又,作爲比較例12至14,按 -14 - 201248903 本發明之成分組成的範圍外而依表1中所示之各比例稱量 ,按與本實施例同樣條件進行真空熱壓以製作濺鍍靶。 再者,將此等濺鍍靶裝附於磁控式濺鍍裝置(magnetron sputtering device)上,依電源:DC(直流)、施加電力: 200W(瓦特)、到達真空度:lxl(T4pa(帕)、濺鍍氣體:Ar( 氬)' 濺鍍壓力:〇_67Pa之條件,於經加熱爲200°C之玻璃 基板(康寧社 1737#縱:20x橫:20、厚度:0.7mm)上,嘗 試具有膜厚:300nm之透明膜之形成。 就如此所製作之本發明之實施例及比較例,分別測定: 燒結體的密度(理論密度比),藉由X射線繞射法(XRD)之 ZnO(lOl)及Zn2SiO4(410)的繞射峰値之有無、DC濺鏟之可否 、體電阻、60分鐘之DC濺鑛時的異常放電(extraordinary discharge)次數、經DC濺鍍之透明膜的折射率(對波長 3 8 0nm、5 5 0nm、7 5 0nm的光),並加以評價。將其結果表 示於表1中。 -15- 201248903
【SJ 折射率 750 nm 1 1 U7 1.74 1M 1 1 1.73 1 1 I U2 1 I 5 CO (Ο 1.63 I 1.62 P 1.63 1.65 ΰ 550 nm 1 1 1.Θ5 1M «a 1 1 1.83 1 1 I 1.$3 1 I <〇 s <s «η $ <〇 1.54 Ε i cn 1 1 2.15 Ν 2.07 1 1 1.98 1 1 I s •m: 1 I ir> a> to s ε 1.66 卜· (0 U> 異常放 電次數 (6吩鐘) 1380 變 严 rg ΙΩ 89t 1470 2042 1 1 I o 1 762 04 - ο 严 o η 電阻値 (Ω _cnr〇 4.6X10"* 1.8 X10'3 2.3X10'5 6ΛΧ10*4 7*2X10— 8.6 X10-4 9.1 ΧΙΟ"4 8.8X10"* OV.RG OV.RG OV.RG voxuT3 丨 OV.RG 6.9 x I O'3 1.5X10_, xi O'5 3^x10 3 4.8 X10"3 52X10^ 9.1 xIO"3 9.3 XIO'3 3.3^10^ DC可否 1? t? 1? 1? 1? t? 不可1 1不可I i不可| t? 不可 t? 1? t? tH1 I? t? XRD峰値 Zn,Si〇4 (410) 摧 雔 摧 摧 摧 壊 w 擗 耻 up 2nO (ton 聛 W- w 揲 裢 戡 聛 m 耻 擗 理論. 密度比 σ> a Ο) I 9> σ> ίΛ β> aft 〇> η ο 〇 s η ο S O o Ϊ Ο 姿 o g o % ο 〇 ο s o 〇 理論 密度 g/cm3 S in w ΙΟ 5.59 | 5.54 J ΙΑ ΙΟ 5.43 5.39 6.15 4.81 4.52 4爻6 5.15 1 s in 454 4.15 4£4 4.17 4^8 Ml 製法 燒成 燒成 燒成 燒成 燒成 燒成 燒成 燒成 燒成 燒成 燒成 % ϊ a. X 1 X ϊ 僅靶金屬成分之重量% •5 餘部 餘部 餘部 餘部 餘部 餘部 餘部 餘部 餘部 餘部 I餘部I 餘部 m 錐 餘部 餘部 餘部 餘部 餘部 餘部 餘部 餘部 餘部 (7) ο 〇 〇 〇 〇 〇 ο 〇 5 G〇 〇 A 12.79 14.98 12.99 寸 5 12^4 14·26 g <£> 14.15 12.72 12.94 < 0.07 0.13 0.66 CM 3.35 5.42 6.82 2.04 2·08 1-½ 1.Λ5 2.04 j 4.41 S 2.13 2.18 CsJ 0.69 0.73 0.36 3.66 原料混合組成 ZnO 餘部 餘部 餘部 餘部 餘部 餘部 餘部 餘部 餘部 I餘部I l餘部I 餘部 餘部 餘部 餘部 餘部 餘部 餘部 餘部 餘部 餘部 餘部 o ΪΛ I 1 1 1 1 1 I 5wt% 10wt% I 15w% 20wt% 5wt% 23wt% 20vwtt 10wt% 15wt% i I 10wt\ 22wtX 20wt% 20wt% ai2o3 O.lwt% 0.2wrt Iwtt 1 Qwt% 10wtX 3wtt 3wtt 2wtt 2wt% 3wrt I 6wt% 1 3w« 3wt% i iw« \wt% 0.5wtX I «Μ co 寸 \〇 卜 00 9> o 二 — CO \n c〇 卜 00 比較例 實施例 -16- 201248903 由此結果可知,採用大氣燒成之比較例之中,在 Al2〇3的含量少而不含Si〇2之比較例1、2,貝IJ異常放電次 數多以致不能實施穩定的DC濺鍍、在雖然有某程度之 Ah〇3的含量惟不含Si02之比較例3至5,貝IJ未倉g獲得低 折射率。又,採用大氣燒成之比較例之中,A1203的含量 多而不含Si02之比較例6、7,則異常放電次數多以致不 能實施穩定的DC濺鍍,在含有A1203及Si02之比較例8 至11,則異常放電次數多或靶不具有導電性以致不能實施 DC濺鍍。在此,比較例1至7中,密度均在理論密度之 1 0 0 %以下者。 再者,採用熱壓機之比較例之中,Si02的含量較本發 明之範圍爲少的比較例1 2中,則未能獲得低的折射率而 Si 〇2的含量較本發明之範圍爲多之比較例13中,則靶不 具有導電性以致未能實施DC濺鍍。又,Al2〇3的含量較 本發明之範圍爲多之比較例1 4中,則異常放電次數多以 致未能實施穩定的DC濺鍍。再者,在比較例8,12,14 ,則雖於XRD時觀察有ZnO(lOl)及Zn2Si〇4(410)的兩峰 値,然而由於A1或Si的含量係本發明之範圍外之故,發 生有上述之缺點。 相對於此,本實施例中,均於XRD觀察有ZnO(lOl) 及Zn2SiO4(410)的兩峰値,因異常放電次數非常少之故能 穩定實施有良好的DC濺鍍、就折射率而言,亦均獲得有 較AZO膜爲低的折射率。又,就密度而言,於本實施例 中,均在理論密度的1〇〇至108 %之範圍內。 -17- 201248903 其次,就表1中所示實施例3(Si02 : 20wt%),將藉由 X射線繞射(XRD)所觀察之結果,表示於第3圖中。在此 施例3中,均以高的強度觀察有複合氧化物Zn2Si04的 (410)的繞射峰値及ΖηΟ的(101)的繞射峰値。相對於此, 經按與ΪΪ施例3同樣成分組成但依大氣燒成所製作之比較 例中,則如第4圖所示,未能獲得ΖηΟ的(1 01)的繞射峰 値。因而,如欲獲得導電性時,則如本實施例般,需要在 組織中共存複合氧化物Zn2Si04及ΖηΟ之情況。 再者,本發明之技術範圍並不因上述實施形態及上述 贲施例而有所限定,可於不脫離本發明之要旨之範圍內加 以種種變更。 【圖式簡單說明】 [第1圖]於有關本發明之太陽電池用透明膜形成用濺 鍍靶及其製造方法之實施形態中,表示濺鍍靶之製造過程 之'流程圖。 [第2圖]表示經採用本實施形態之太陽電池用透明膜 之薄膜太陽電池之槪略剖面圖。 [第3圖]於有關本發明之太陽電池用透明膜形成用濺 鍍靶及其製造方法之實施例中,表示濺鍍靶之X射線繞射 (XRD)的分析結果之圖。 [第4圖]於有關本發明之太陽電池用透明膜形成用濺 鍍靶及其製造方法之比較例(大氣燒成)中,表示濺鍍靶的 X射線繞射(XRD)的分析結果之圖。 -18- 201248903 【主要元件符號說明】 1 :鹼石灰玻璃基板 2 : Mo後面電極 3 : CIG S吸收層 4 :緩衝層 5 : i-ZnO緩衝層 6 : AZO電極 7a :防反射膜(太陽電池用透明膜) 7b :防反射膜(MgF2膜) 8 :表面電極 -19-
Claims (1)
- 201248903 七、申請專利範圍: 1. 一種太陽電池用透明膜形成用濺鍍靶,其特徵爲: 由具有對全金屬成分量含有A1: 0.3至4.Owt%、Si : 6.0 至14.5wt%、餘部爲由Zn以及不可避免之不純物所成之 成分組成之氧化物燒結體所成者, 該燒結體的組織中存在有複合氧化物Zn2Si04及ZnO 〇 2. 如申請專利範圍第1項之太陽電池用透明膜形成用 濺鍍靶,其中, 該燒結體的密度,係以理論密度比計,爲1 00至 10 8%° 3 .如申請專利範圍第1項之太陽電池用透明膜形成用 濺鑛靶,其中, 體電阻,爲1Ω· cm以下》 4· 一種太陽電池用透明膜形成用濺鍍靶之製造方法, 係製作如申請專利範圍第1項之太陽電池用透明膜形成用 濺鍍靶之方法,其特徵爲: 包含有:將Ah〇3粉末與Si〇2粉末與Zn0粉末,按 由 Al2〇3 : 0.5 至 5.0wt°/〇、Si02 : 10 至 22wt%、餘部: ZnO以及不可避免之不純物所成之方式混合作成混合粉末 之步驟、及 將前述混合粉末在真空中使用熱壓機以進行燒結之步 驟。 -20-
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| JP5892016B2 (ja) * | 2012-09-19 | 2016-03-23 | 住友金属鉱山株式会社 | 酸化亜鉛スパッタリングターゲットとその製造方法 |
| WO2014069367A1 (ja) * | 2012-10-30 | 2014-05-08 | Jx日鉱日石金属株式会社 | 導電性酸化物焼結体及び該導電性酸化物を用いた低屈折率膜 |
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| JP6537715B2 (ja) * | 2017-03-15 | 2019-07-03 | Jx金属株式会社 | Al2O3スパッタリングターゲット及びその製造方法 |
| CN107522484A (zh) * | 2017-06-26 | 2017-12-29 | 广西新未来信息产业股份有限公司 | 一种氧化锌铝靶材的制备方法 |
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| JP5943226B2 (ja) | 2016-06-29 |
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