JP6307071B2 - 光起電力素子 - Google Patents
光起電力素子 Download PDFInfo
- Publication number
- JP6307071B2 JP6307071B2 JP2015517051A JP2015517051A JP6307071B2 JP 6307071 B2 JP6307071 B2 JP 6307071B2 JP 2015517051 A JP2015517051 A JP 2015517051A JP 2015517051 A JP2015517051 A JP 2015517051A JP 6307071 B2 JP6307071 B2 JP 6307071B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- zinc oxide
- photovoltaic
- type
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 371
- 239000011787 zinc oxide Substances 0.000 claims description 174
- 239000000758 substrate Substances 0.000 claims description 96
- 239000002245 particle Substances 0.000 claims description 61
- 239000013078 crystal Substances 0.000 claims description 53
- 239000010408 film Substances 0.000 claims description 32
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 23
- 239000002019 doping agent Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000010409 thin film Substances 0.000 claims description 8
- 229910007709 ZnTe Inorganic materials 0.000 claims description 7
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 180
- 238000000034 method Methods 0.000 description 44
- 239000004065 semiconductor Substances 0.000 description 24
- 239000002994 raw material Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 239000002243 precursor Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000443 aerosol Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 229910052984 zinc sulfide Inorganic materials 0.000 description 10
- -1 a-SiCON Inorganic materials 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000007790 solid phase Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 239000000470 constituent Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 239000002346 layers by function Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 150000003751 zinc Chemical class 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910003811 SiGeC Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 3
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 3
- 238000001451 molecular beam epitaxy Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052950 sphalerite Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910017875 a-SiN Inorganic materials 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
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- 150000007513 acids Chemical class 0.000 description 2
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- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
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- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 238000010248 power generation Methods 0.000 description 2
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
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- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
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- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
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Description
板状の配向多結晶酸化亜鉛焼結体から構成される基板と、
前記基板上に設けられる光起電力層と、
前記光起電力層上に設けられる電極と、
を備えた、光起電力素子が提供される。
本発明は光起電力素子に関する。光起電力素子とは、物質に光を照射することで起電力が発生する現象(すなわち光起電力効果)を利用する素子である。本発明における光起電力素子は、PIN型フォトダイオード、PN型フォトダイオード、ショットキーフォトダイオード等の種々の形態を有することができ、紫外線フォトダイオード/センサー、可視光フォトダイオード/センサー、赤外線フォトダイオード/センサー等の各種センサー、シリコン系太陽電池、CIGS系太陽電池等の各種太陽電池等の種々の用途を包含する。本発明の好ましい態様においては、光起電力素子はシリコン系太陽電池又はCIGS系太陽電池として用いられる。本発明の別の好ましい態様においては、光起電力素子は紫外線センサーとして用いられる。
基板12として用いる配向多結晶酸化亜鉛焼結体は、酸化亜鉛結晶粒子に磁場を印加して配向させる方法(例えば特許文献10(特許第4378535号公報)に開示される方法)の他、以下に説明するように、原料に板状酸化亜鉛粉末を用いて成形及び焼結を行うことにより製造することができる。
原料となる板状酸化亜鉛粉末は、後述する成形及び焼成工程によって配向焼結体が得られる限り、いかなる方法により製造されたものであってもよい。例えば(101)面配向焼結体を得るには、特許文献9(特許第3128861号公報)に記載される方法に従って製造した板状酸化亜鉛粉末を原料として用いればよい。
上記の方法で製造した板状酸化亜鉛粉末をせん断力を用いた手法により配向させ、配向成形体とする。このとき、板状酸化亜鉛粉末に、ドーパント用の金属酸化物粉末(例えばα−Al2O3粉末)等の他の元素又は成分を添加してもよい。せん断力を用いた手法の好ましい例としては、テープ成形、押出し成形、ドクターブレード法、及びこれらの任意の組合せが挙げられる。せん断力を用いた配向手法は、上記例示したいずれの手法においても、板状酸化亜鉛粉末にバインダー、可塑剤、分散剤、分散媒等の添加物を適宜加えてスラリー化し、このスラリーをスリット状の細い吐出口を通過させることにより、基板上にシート状に吐出及び成形するのが好ましい。吐出口のスリット幅は10〜400μmとするのが好ましい。なお、分散媒の量はスラリー粘度が5000〜100000cPとなるような量にするのが好ましく、より好ましくは20000〜60000cPである。シート状に成形した配向成形体の厚さは5〜500μmであるのが好ましく、より好ましくは10〜200μmである。このシート状に成形した配向成形体を多数枚積み重ねて、所望の厚さを有する前駆積層体とし、この前駆積層体にプレス成形を施すのが好ましい。このプレス成形は前駆積層体を真空パック等で包装して、50〜95℃の温水中で10〜2000kgf/cm2の圧力で静水圧プレスにより好ましく行うことができる。また、押出し成形を用いる場合には、金型内の流路の設計により、金型内で細い吐出口を通過した後、シート状の成形体が金型内で一体化され、積層された状態で成形体が排出されるようにしても良い。得られた成形体には公知の条件に従い脱脂を施すのが好ましい。
ノンドープZnO配向焼結体基板を用いて、p−i−n積層構造による光起電力機能層を備えた光起電力素子を以下のようにして作製した。
(1a)板状酸化亜鉛粉末の作製
ノンドープの(002)面配向ZnO粉末を次のようにして作製した。硫酸亜鉛七水和物(高純度化学研究所製)173重量部とグルコン酸ナトリウム(和光純薬工業製)0.45重量部をイオン交換水300重量部に溶解した。こうして得られた溶液をビーカーに入れ、マグネットスターラーで攪拌しながら90℃に加熱して溶解させた。この溶液を90℃に保持し、攪拌しながら25%アンモニウム水49重量部をマイクロチューブポンプで滴下した。滴下終了後、90℃で攪拌しながら4時間保持した後、溶液を多量のイオン交換水に投入し、静置した。容器の底部に堆積した沈殿物を濾過により分離し、更にイオン交換水による洗浄を3回行い、乾燥して白色粉末状の酸化亜鉛前駆物質を得た。得られた酸化亜鉛前駆物質をジルコニア製のセッターに載置し、電気炉にて大気中で仮焼することにより、酸化亜鉛板状多孔質粉末を得た。仮焼時の温度スケジュールは、室温から900℃まで昇温速度100℃/hにて昇温した後、900℃で30分間保持し、自然放冷とした。
得られた酸化亜鉛板状粒子100重量部に対し、バインダー(ポリビニルブチラール:品番BM−2、積水化学工業株式会社製)15重量部と、可塑剤(DOP:ジ(2−エチルヘキシル)フタレート、黒金化成株式会社製)10重量部と、分散剤(製品名レオドールSP−O30、花王株式会社製)3重量部と、分散媒(2−エチルヘキサノール)とを混合した。分散媒の量はスラリー粘度が10000cPとなるように調整した。こうして調製されたスラリーを、ドクターブレード法により、PETフィルムの上に、乾燥後の厚さが20μmとなるようにシート状に成形した。得られたテープを20×20cmのシートに切断し、500枚の切断テープ片を積層し、厚さ10mmのアルミニウム板の上に載置した後、真空パックを行った。この真空パックを85℃の温水中で、100kgf/cm2の圧力にて静水圧プレスを行い、板状の成形体を作製した。得られた成形体を脱脂炉中に配置し、600℃で20時間の条件で脱脂を行った。得られた脱脂体を窒素中、1400℃で5時間の条件で常圧焼成して、板状のZnO配向焼結体基板を作製した。
得られたZnO焼結体基板について以下の評価を行った。
得られた焼結体の(002)配向度F(002)をXRDにより測定した。この測定は、XRD装置(株式会社リガク製、製品名「RINT−TTR III」)を用い、板状酸化亜鉛の表面に対してX線を照射したときのXRDプロファイルを測定し、以下の式によって評価した。
焼結体粒子の平均粒径を以下の方法により測定した。得られた板状焼結体より、5×5×3mmの試料を切り出し、板面と垂直な面を研磨し、濃度0.3Mの硝酸にて10秒間エッチングを行った後、走査電子顕微鏡にて画像を撮影した。視野範囲は、板面に平行及び垂直な直線を引いた場合に、いずれの直線も10個から30個の粒子と交わるような直線が引けるような視野範囲とした。板面に平行に引いた3本の直線において、直線が交わる全ての粒子に対し、個々の粒子の内側の線分の長さを平均したものに1.5を乗じた値をa1とし、同様に、板面に垂直に引いた3本の直線において、直線が交わる全ての粒子に対し、個々の粒子の内側の線分の長さを平均したものに1.5を乗じた値をa2とし、(a1+a2)/2を平均粒径とした。
抵抗率計(三菱化学株式会社製、ロレスタAX MCP−T370型)を用い、板状焼結体板面の中心部近傍にて四探針法により、焼結体の体積抵抗率を測定した。
得られたノンドープZnO配向焼結体基板上に、多結晶Siを、n層、i層、及びp層をこの順に堆積した。多結晶Si層の形成は、励起周波数13.36MHzのプラズマCVDを用い、基板温度180℃にて行った。シリコン原料には水素希釈のSiH4原料ガスを使用し、p層及びn層の積層時のドーピングガスとしてB2H6及びPH3をそれぞれ使用した。各層の形成は約3Å/秒程度の積層レートで行った。その後、リソグラフィープロセスを経てp型層上及びn型層上に各々電極を形成した。
光起電力素子のp型層上に設けた電極と、n型層上に設けた電極とをリード線を介してテスターに接続し、擬似太陽光(AM1.5、100mW・cm−2)を光起電力素子上面より照射したところ、開放電圧0.50V、短絡電流20mA・cm−2の出力を確認した。太陽光照射による光起電力及び光電流の発生が確認できたことから、本例で作製した光起電力素子は太陽電池として機能することが分かった。
Alドープされたn型ZnO配向焼結体基板を用いて、p−i−n積層構造による光起電力機能層を備えた光起電力素子を以下のようにして作製した。
(1a)原料粉末の作製
Alドープされた(002)面配向ZnO粉末を次のようにして作製した。塩化アルミニウム六水和物(高純度化学研究所製)8.8重量部をエタノール200重量部に投入して溶解させた。その後、例1で作製した酸化亜鉛板状粒子に上記の溶液を亜鉛:アルミニウム=100:0.2(原子比)となるように投入し、ロータリーエバポレーターを用いて乾燥することにより、アルミニウム成分が均一に分散した酸化亜鉛板状粒子を作製した。
例1の(1b)と同様にして、板状のZnO配向焼結体基板を作製した。
例1の(1c)と同様にして、得られたZnO焼結体基板の評価を行った。その結果、焼結体基板の(002)配向度は80%であり、焼結粒子の平均粒径は35μmであり、体積抵抗率は8×10−4Ω・cmであった。
得られたAlドープされたn型ZnO配向焼結体基板上にi−ZnO層及びp−Zn層をこの順に積層した。すなわち、本例では基板自身がAlドーピングによってn型半導体となり、十分に低抵抗なことから、n型ZnO層の成膜を省略した。各層の形成方法は以下のとおりとした。
市販のノンドープのZnO粉末を成膜原料として、ZnO配向焼結体基板上にp型ZnO膜をエアロゾルデポジション法(以下、ADという)により堆積させた。AD成膜は図2に示す成膜装置120を使用した。この成膜装置120は、原料成分を含む原料粉末のエアロゾルを生成するエアロゾル生成部122と、成膜粉を種基板121に噴射して原料成分を含む膜を形成する成膜部130とを備えている。
ノンドープのZnO粉末の代わりに、市販のNドープしたp型ZnO粉末(古河電子製)を成膜原料として用いたこと以外はi型ZnO層と同様にして、i型ZnO層上にp型ZnO膜をエアロゾルデポジション法(以下、ADという)により堆積させ、その後固相エピタキシャル成長させた。この固相エピタキシャル成長を生じ、c軸に配向したNドープZnO層が得られた。例1で述べたXRDによる配向性評価を行ったところ、配向度は78%であることがわかった。
p型層上及び基板裏面の各々に電極を形成した。具体的には、p型ZnO層上に、Auを電子ビーム蒸着法にて30nm成膜して電極とした。基板裏面に対しても上記同様にして電極を形成した。なお、p型ZnO層上の電極は、光の透過効率を高めるため格子状とした。
得られた光起電力素子のp型層上に設けた電極と、基板裏面に設けた電極とをリード線を介してテスターに接続し、紫外線(ブラックライト、波長300−400nm、ピーク波長350nm)を光起電力素子上面より照射したところ、開放電圧1.0V、短絡電流100μAの出力を確認した。紫外線照射による光起電力及び光電流の発生が確認できたことから、本例で作製した光起電力素子は紫外線センサーとして機能することが分かった。
Claims (14)
- 板状の配向多結晶酸化亜鉛焼結体から構成される基板と、
前記基板上に設けられる光起電力層と、
前記光起電力層上に設けられる電極と、
を備え、
前記光起電力層が、前記配向多結晶酸化亜鉛焼結体の配向性に倣ってエピタキシャル成長した構造を有し、それにより法線方向に揃った結晶方位を有し、
前記基板が25cm 2 以上の面積を有する、光起電力素子。 - 前記配向多結晶酸化亜鉛焼結体を構成する酸化亜鉛単結晶粒子の平均粒径が、1〜100μmである、請求項1に記載の光起電力素子。
- 前記配向多結晶酸化亜鉛焼結体が、(100)面、(002)面、又は(101)面に配向している、請求項1又は2に記載の光起電力素子。
- 前記配向多結晶酸化亜鉛焼結体が50%以上の配向度を有する、請求項1〜3のいずれか一項に記載の光起電力素子。
- 前記光起電力層が、n型層、i型層及びp型層の組合せ、n型層、バッファ層及びp型層の組合せ、n型層及びp型層の組合せ、並びにn型層及び金属薄膜の組合せからなる群から選択されるいずれか一つを備えてなる、請求項1〜4のいずれか一項に記載の光起電力素子。
- 前記光起電力層が、i型層及びp型層の組合せ、バッファ層及びp型層の組合せ、p型層単独、並びに金属薄膜単独からなる群から選択されるいずれか一つを備えてなり、且つ、前記配向多結晶酸化亜鉛焼結体がn型ドーパントでドープされ、それにより前記基板がn型層として機能する、請求項1〜4のいずれか一項に記載の光起電力素子。
- 前記n型ドーパントが、アルミニウム(Al)、ガリウム(Ga)、インジウム(In)、硼素(B)、フッ素(F)、塩素(Cl)、臭素(Br)、ヨウ素(I)及びシリコン(Si)からなる群から選択される1種以上を含む、請求項6に記載の光起電力素子。
- 前記配向多結晶酸化亜鉛焼結体が、MgO、CdO、ZnS、ZnSe及びZnTeからなる群から選択される一種以上の結晶と混晶化されたZnOからなる、請求項1〜7のいずれか一項に記載の光起電力素子。
- 前記基板が対向電極として機能する、請求項1〜8のいずれか一項に記載の光起電力素子。
- 前記基板上の前記光起電力層と反対側に、対向電極を更に備えてなる、請求項1〜8のいずれか一項に記載の光起電力素子。
- 前記電極が、透明導電膜、又は格子構造若しくはモスアイ構造を有する金属電極である、請求項1〜10のいずれか一項に記載の光起電力素子。
- PIN型フォトダイオード、PN型フォトダイオード、及びショットキーフォトダイオードのいずれか一種である、請求項1〜11のいずれか一項に記載の光起電力素子。
- シリコン系太陽電池又はCIGS系太陽電池として用いられる、請求項1〜12のいずれか一項に記載の光起電力素子。
- 紫外線センサーとして用いられる、請求項1〜12のいずれか一項に記載の光起電力素子。
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