JP5788832B2 - ソルボサーマル法を用いるCu,Zn,Sn及びSを含有する硫化物系化合物半導体ナノ粒子の製造方法 - Google Patents
ソルボサーマル法を用いるCu,Zn,Sn及びSを含有する硫化物系化合物半導体ナノ粒子の製造方法 Download PDFInfo
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- JP5788832B2 JP5788832B2 JP2012114566A JP2012114566A JP5788832B2 JP 5788832 B2 JP5788832 B2 JP 5788832B2 JP 2012114566 A JP2012114566 A JP 2012114566A JP 2012114566 A JP2012114566 A JP 2012114566A JP 5788832 B2 JP5788832 B2 JP 5788832B2
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- 229910052718 tin Inorganic materials 0.000 title claims description 34
- 229910052725 zinc Inorganic materials 0.000 title claims description 34
- 229910052802 copper Inorganic materials 0.000 title claims description 33
- 238000004729 solvothermal method Methods 0.000 title claims description 33
- 229910052717 sulfur Inorganic materials 0.000 title claims description 22
- 239000004065 semiconductor Substances 0.000 title claims description 19
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- 150000003839 salts Chemical group 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
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- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical class OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 239000011028 pyrite Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
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Description
(1) CuとZnとSnとSとを有機溶媒中でソルボサーマル反応させるソルボサーマル工程を含む、Cu, Zn, Sn及びSを含有する硫化物系化合物半導体の製造方法。
(2) ソルボサーマル工程において、Sを硫黄粉末又はチオ尿素の形態でソルボサーマル反応させる、前記(1)の方法。
(3) ソルボサーマル工程において、Cu, Zn及びSnの少なくとも1種を金属の形態でソルボサーマル反応させる、前記(2)の方法。
(4) ソルボサーマル工程において、Cu, Zn及びSnを塩の形態でソルボサーマル反応させる、前記(2)の方法。
(6) ソルボサーマル工程において、200〜450℃の範囲の温度で1〜24時間ソルボサーマル反応させる、前記(1)〜(5)のいずれかの方法。
(7) Cu, Zn, Sn及びSを含有する硫化物系化合物半導体のロッド状結晶体。
本発明の方法は、CuとZnとSnとSとを有機溶媒中でソルボサーマル反応させるソルボサーマル工程を含む。本発明者らは、CuとZnとSnとSとを有機溶媒中でソルボサーマル反応させると、結晶性の高い微細粒径のCZTSナノ粒子が生成することを見出した。それ故、本工程を実施することにより、結晶性の高い微細粒径のCZTSを製造することが可能となる。
本発明者らは、本発明の方法によって得られるCZTSが、原料として金属塩を用いることにより微細な粒径の結晶形態となることを見出した。具体的には、本発明の方法によって得られるCZTSは、通常、5〜200 nmの粒径であり、典型的には30〜200 nmの粒径である。本発明の方法によって得られるCZTSは、上記の粒径を有する一次粒子が凝集して、5 nm〜500 μmの粒径を有する二次粒子を形成する。固相反応を用いる方法によって得られるCZTSは、通常、1μm以上の粒径であることから、本発明の方法を用いることにより、従来技術の方法と比較して微細な粒径のCZTSのナノ粒子を得ることが可能となる。
<1. ソルボサーマル反応による硫化物系化合物半導体(CZTS)の調製(1)>
2 mmolのCu源と1 mmolのZn源と1 mmolのSn源とを、種々のモル数の硫黄(S)粉末と一緒に10 mlの有機溶媒に分散させ、オートクレーブに充填して30分間撹拌した。上記の分散物を、オートクレーブ中でソルボサーマル反応させた(ソルボサーマル工程)。得られた生成物を濾過し、大気中、50℃、22時間の条件で乾燥処理した(乾燥工程)。これにより、CZTSを得た。各実施例の調製条件を表1に示す。
得られた実施例1〜21の粉末を、X線粉末回折(XRD)、示差熱分析(DTA)、透過型電子顕微鏡(TEM)、エネルギー分散型蛍光X線分析(EDX)及び走査型電子顕微鏡(SEM)によって解析した。結果を表1及び図1〜21に示す。
2 mmolのCu源と1 mmolのZn源と1 mmolのSn源と5 mmolのS源とをハステロイ(登録商標)製オートクレーブに充填し、充填率50%になるように30 mlの有機溶媒を加えた。実施例33及び35の場合、さらに添加物としてポリビニルピロリドンを加えた。オートクレーブを密閉してから240℃で24時間加熱し、ソルボサーマル反応させた(ソルボサーマル工程)。得られた生成物を自然冷却した。その後、生成物を遠心分離し、沈殿物を純粋及びエタノールで洗浄した。洗浄後の生成物を、70℃、30分〜10時間の条件で乾燥処理した(乾燥工程)。これにより、CZTSを得た。各実施例の調製条件を表2に示す。
得られた実施例31〜35の粉末を、走査型電子顕微鏡(SEM)、透過型電子顕微鏡(TEM)、透過型電子顕微鏡に備えられたエネルギー分散型蛍光X線分析(TEM/EDX)、X線粉末回折(XRD)、X線光電子分光分析(XPS)、ラマン分光分析及び示差熱重量分析(TG-DTA)によって解析した。
図31に示すように、いずれの実施例の場合も、主ピークは338 cm-1の領域に観察された。Cu2SnS3及び他のCu-Sn-S化合物は、この波数領域にピークは存在しないので、実施例31〜35の粉末中には、CZTS黄錫亜鉛鉱(おうしゃくあえんこう)構造が存在していることが示された。また、主ピークが355 cm-1の領域に存在するβ-ZnSは、いずれの実施例の粉末にもほとんど存在しないことは明らかである。475 cm-1の小さなピークは、2次相としてはCu2-xSの存在を示している。
Claims (4)
- CuとZnとSnとSとを有機溶媒中で200〜450℃の範囲の温度で1〜24時間ソルボサーマル反応させるソルボサーマル工程を含み、Cu, Zn及びSnが以下:(i)Cu, Zn及びSnがいずれも金属の形態である;(ii)Cu, Zn及びSnの少なくとも1種が金属の形態であり、且つその他が有機酸の共役塩基との塩の形態である;又は(iii)Cu, Zn及びSnがいずれも有機酸の共役塩基との塩の形態である;を満足し、且つSが硫黄粉末の形態である、Cu, Zn, Sn及びSを含有する硫化物系化合物半導体の製造方法。
- CuとZnとSnとSとのモル比が、Cu、Zn及びSnに対するSの組成比として、2:1:1:4〜2:1:1:12の範囲である、請求項1の方法。
- 硫化物系化合物半導体が、5〜200 nmの粒径を有する一次粒子を含有するか、又は長軸方向の長さが30〜70 nmの範囲であり、短軸方向の長さが5〜10 nmの範囲であり、短軸方向の長さに対する長軸方向の長さの比が4〜10の範囲であるロッド状結晶体を含有する、請求項1又は2の方法。
- Cu, Zn, Sn及びSを含有する硫化物系化合物半導体のロッド状結晶体であって、ロッド状の結晶の長軸方向の長さが30〜70 nmの範囲であり、短軸方向の長さが5〜10 nmの範囲であり、短軸方向の長さに対する長軸方向の長さの比が4〜10の範囲である、前記ロッド状結晶体。
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PCT/IB2012/001223 WO2012168792A1 (en) | 2011-06-06 | 2012-06-06 | Method of producing sulfide compound semiconductor by use of solvothermal method and rod-like crystal of sulfide compound semiconductor |
US14/124,156 US20140110640A1 (en) | 2011-06-06 | 2012-06-06 | Method of producing sulfide compound semiconductor by use of solvothermal method and rod-like crystal of sulfide compound semiconductor |
CN201280027494.1A CN103596882A (zh) | 2011-06-06 | 2012-06-06 | 通过使用溶剂热方法制备硫化物化合物半导体的方法及硫化物化合物半导体的棒状晶体 |
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