JP2016521232A - 薄膜ソーラーセル用の銅−インジウム−ガリウム−カルコゲナイド・ナノ粒子前駆体 - Google Patents
薄膜ソーラーセル用の銅−インジウム−ガリウム−カルコゲナイド・ナノ粒子前駆体 Download PDFInfo
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- JP2016521232A JP2016521232A JP2015560800A JP2015560800A JP2016521232A JP 2016521232 A JP2016521232 A JP 2016521232A JP 2015560800 A JP2015560800 A JP 2015560800A JP 2015560800 A JP2015560800 A JP 2015560800A JP 2016521232 A JP2016521232 A JP 2016521232A
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
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Abstract
Description
この出願は、2013年3月4日出願の米国仮特許出願61/772,372の非仮出願であり、その内容の全ては、参照により本明細書の一部となる。
[1.技術分野]
本発明は、光起電材料に関しており、より具体的には、CuInxGa1−xS2ナノ粒子(0≦x≦1)の製造に関する。
商品競争力を持つためには、光起電力セルは、化石燃料と競争できるコストで発電する必要がある。低コスト材料を用いて、安価なデバイス作製プロセスで光起電力セルを作る必要がある。光起電力セルは、中から高程度の太陽光電気変換効率を持つ必要がある。更に、材料合成とデバイス作製が、工業規模に拡大可能である必要がある。
5mlの1−オクタデセン中で、Cu(OAc)(122.3mg、0.9976mmol;OAc=アセテート)とIn(OAc)3(292.0mg、1.000mmol)を混合し、120℃で20分間加熱した。この混合物に窒素ガスを充填し、5mlのオクタンチオールを注入して黄/オレンジ色の懸濁液を得た。懸濁液を200℃に加熱して、この温度で1時間維持した。この間に、懸濁液は赤変した。反応液を170℃で17時間熱処理し、室温に冷却し、生成物をアセトンで分離した。得られた凝集固体を遠心分離で捕集し、クロロホルムに再分散させ、濾過し、アセトン中で他のサイクルの沈澱とともに洗浄した。光学的に透明なナノ粒子溶液の吸収スペクトル(図1参照)は、525nmに明確な励起子ピークを、約640nmに吸収端を示した。このピークは、バルクのCuInS2のもの(810nm)よりもかなり青方偏移しており、期待される量子閉じ込め効果と一致した。そのXRDパターン(図2のA)は、既に報告されている正方晶CuInS2相とよく一致した。
30.121gのIn(OAc)3(103mmol)と、12.002gのCu(OAc)(97.9mmol)と、180mlの1−オクタデセンとを、オーブン乾燥した1リットルの三口丸底フラスコに投入した。フラスコにリービッヒ冷却器を取り付け、窒素ガスでパージした。混合物を100℃で1時間脱気し、窒素ガスで充填した。
191.49gのIn(OAc)3(0.66mmol)と122.39gのCu(OAc)(1.00mmol)とをフラスコに加え、真空下室温で保存した。5mlのオクタデセンを注入し、得られた緑色がかった懸濁液を100℃真空下で20分間加熱した。フラスコに窒素を充填し、5mlのオクタンチオール(29mmol)を注入し、温度を200℃まで上げた。温度が上がるにつれて溶液の色が徐々に黄色、オレンジ色、最後に赤へと変化した。反応液を200℃で10分間維持した。
オーブン乾燥した100−mlの三口丸底フラスコに、1.25gのIn(OAc)3(4.28mmol)と、0.51gのCu(OAc)(4.2mmol)と、7.5mlの1−オクタデセンとを投入した。フラスコにリービッヒ冷却器を取り付け、窒素ガスでパージした。混合物を100℃で1時間、次いで140℃で10分間脱気後、窒素ガスを充填した。5mlの1−オクタンチオールを加え、混合物を180℃で加熱した。5mlの1.71MのTOP:S溶液を約7.5ml/hrの速度で添加した。溶液を200℃で2時間加熱し、次いで160℃で18時間熱処理した。熱処理後加熱をやめ、反応液を60℃まで冷却した。40mlのメタノールを添加し、得られた混合物を室温で1時間撹拌し、次いで無撹拌で15分間放置した。このプロセスももう一度繰り返した。赤色固体が分離され、50mlのアセトンで洗浄し、遠心分離で捕集した。この固体を30mlのジクロロメタンに分散し、濾過し、75mlのメタノールで再沈殿させた。固体を10mlのジクロロメタンに再分散させ、再沈殿させて分離した。
XRDパターン(図2のC)のピークは、JCPDS32−0339の値に非常によく一致し、正方晶構造のCuInS2と同定された。
292.10gのIn(OAc)3(1.00mmol)と、122.57gのCu(OAc)と、5mlのオクタデセンとをフラスコに投入し、120℃真空下で30分間加熱した。この緑色懸濁液に窒素を充填し、フラスコに8.8mlのヘキサデカンチオールを加えて黄色/オレンジ色の懸濁液を得た。懸濁液を270℃に加熱したところ、その色が徐々に濃赤色に、最後には褐色に変化した。1時間後に懸濁液を室温まで冷却し、アセトンを加えて粒子を分離させた。オクタンチオール中での合成(図6のB)と比較して、ヘキサデカンチオール(図6のA)はより高温での加熱を可能とするが、吸収スペクトル(図6)に示されるように、より広いサイズ分布のナノ粒子を与えた。
Cu(OAc)(1.48g、12.1mmol)と、In(OAc)3(2.82g、9.66mmol)と、GaCl3(1.28g、7.27mmol)と、ODE(25ml)とを250mlの丸底フラスコに入れ、100℃で2時間脱気した。1−オクタンチオール(18ml、104mmol)を素早く添加し、温度を125℃に上げ、次いで溶液を30分間熱処理した。温度を200℃に上げ、溶液を2時間熱処理した。温度を160℃に下げ、一夜撹拌し、室温まで冷却した。
Cu(OAc)(1.48g、12.1mmol)と、In(OAc)3(2.82g、9.66mmol)と、GaCl3(0.73g、4.1mmol)と、ODE(25ml)とを250ml丸底フラスコに入れ、100℃で1時間脱気した。1−オクタンチオール(18ml、104mmol)を素早く添加し、温度を125℃に上げ、次いでこの溶液を30分間熱処理した。温度を200℃に上げて溶液を2時間熱処理した。温度を160℃に下げて一夜撹拌し、室温まで冷却した。
Cu(OAc)(1.48g、12.1mmol)と、In(OAc)3(2.82g、9.66mmol)と、Ga(acac)3(2.67g、7.27mmol;acac=アセチルアセトネート)と、ODE(25ml)とを250ml丸底フラスコに投入し、100℃で1時間脱気させた。1−オクタンチオール(18ml、104mmol)を素早く加え、温度を125℃に上げ、次いで溶液を30分間熱処理した。温度を200℃まで上げて溶液を2時間熱処理した。温度を160℃まで下げて一夜撹拌し、室温まで冷却した。
Cu(OAc)(0.369g、3.01mmol)と、In(OAc)3(0.7711g、2.64mmol)と、Ga(acac)3(0.4356g、1.19mmol)と、硫黄(0.2885g、9.00mmol)と、ベンジルエーテル(15ml)と、1−オクタンチオール(13.8ml、79.5mmol)とを、リービッヒ冷却器と捕集器を備えた100ml丸底フラスコに投入した。混合物を真空下60℃で1時間脱気させた。窒素充填後、温度を200℃に上げ2時間維持した。溶液を160℃に冷却して18時間熱処理し、室温まで冷却した。生成物をトルエンで洗浄し、エタノールで沈殿させた。
Cu(OAc)(0.369g、3.01mmol)と、In(OAc)3(0.7711g、2.64mmol)と、Ga(acac)3(0.4356g、1.19mmol)と、硫黄(0.2885g、9.00mmol)と、オレイルアミン(9ml)とを、リービッヒ冷却器と捕集器を備えた100ml丸底フラスコに投入した。混合物を真空下60℃で1時間脱気した。窒素で充填後、1−オクタンチオール(4.8ml、27.7mmol)を注入した。温度を200℃まで上げて2時間保持した。溶液を160℃に冷却し18時間熱処理後、室温まで冷却した。生成物をトルエンで洗浄し、エタノールで沈殿させた。
Cu(OAc)(1.48g、12.1mmol)と、GaCl3(6.72g、38.2mmol)と、ODE(20ml)とを100ml丸底フラスコに入れ、100℃で1.5時間脱気した。1−オクタンチオール(18ml、104mmol)を加え、温度を200℃に上げ、次いで溶液を2時間熱処理した。温度を160℃に下げて一夜撹拌し、室温まで冷却した。
5.003g(17.1mmol)のIn(OAc)3と、2.005g(16.3mmol)のCu(OAc)と、30mlのベンジルエーテルとを、オーブン乾燥した100mlの丸底フラスコに投入した。フラスコにリービッヒ冷却器と捕集ヘッドを取り付け、これを真空下100℃で1時間加熱し、その後窒素を充填した。
3.529g(12.1mmol)のIn(OAc)3と、1.901g(5.2mmol)のGa(acac)3と、3.227g(16.2mmol)のCu(OAc)2・H2Oと、22.5mlのオレイルアミンと、30mlのベンジルエーテルとを、オーブン乾燥した250ml丸底フラスコに投入した。フラスコにリービッヒ冷却器と捕集ヘッドを取り付け、混合物を真空下で100℃で1時間加熱し、その後窒素を充填した。
Claims (19)
- 実験式CuInxGa1−xS2(式中、0<x<1)で表される一群のナノ粒子を含む組成物であって、
各ナノ粒子は、そのナノ粒子の表面に結合している有機リガンド層を備えており、前記有機リガンド層は、実質的にチオールからなる、組成物。 - 前記チオールは、10個以下の炭素原子を含む、請求項1に記載の組成物。
- 前記チオールは、8個以下の炭素原子を含む、請求項1に記載の組成物。
- 前記チオールは、6個以下の炭素原子を含む、請求項1に記載の組成物。
- 前記一群のナノ粒子が300℃未満の温度に加熱されると、前記チオールは、前記一群のナノ粒子から追い出される、請求項1に記載の組成物。
- 前記チオールの沸点は200℃未満である、請求項1に記載の組成物。
- 前記チオールの沸点は150℃未満である、請求項1に記載の組成物。
- 前記チオールの沸点は100℃未満である、請求項1に記載の組成物。
- 前記一群のナノ粒子は、FWHMが約200nm未満である発光スペクトルを示す、請求項1に記載の組成物。
- 前記一群のナノ粒子は、FWHMが約100nm未満である発光スペクトルを示す、請求項1に記載の組成物。
- ナノ粒子の製造プロセスであって
有機溶媒中で銅塩、インジウム塩、ガリウム塩、及びチオールを混合する工程と、
前記有機溶媒を220℃以下の温度に加熱する工程と、
を含むプロセス。 - 前記温度は200℃以下である、請求項11に記載のプロセス。
- 前記温度は150℃以下である、請求項11に記載のプロセス。
- 前記有機溶媒にTOP:Sの溶液をさらに添加する工程を含む、請求項11に記載のプロセス。
- 前記チオールの沸点は150℃未満である、請求項11に記載のプロセス。
- 前記チオールの沸点は100℃未満である、請求項11に記載のプロセス。
- 前記チオールは、10個以下の炭素原子を含む、請求項11に記載のプロセス。
- 前記チオールは、8個以下の炭素原子を含む、請求項11に記載のプロセス。
- 前記チオールは、6個以下の炭素原子を含む、請求項11に記載のプロセス。
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PCT/IB2014/000827 WO2014135979A1 (en) | 2013-03-04 | 2014-03-03 | Copper-indium-gallium-chalcogenide nanoparticle precursors for thin-film solar cells |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018053202A (ja) * | 2016-09-30 | 2018-04-05 | 日立化成株式会社 | 量子ドット蛍光体及びそれを用いた発光装置 |
WO2018159699A1 (ja) * | 2017-02-28 | 2018-09-07 | 国立大学法人名古屋大学 | 半導体ナノ粒子およびその製造方法ならびに発光デバイス |
JP2018141141A (ja) * | 2017-02-28 | 2018-09-13 | 国立大学法人名古屋大学 | 半導体ナノ粒子およびその製造方法ならびに発光デバイス |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9960314B2 (en) | 2013-09-13 | 2018-05-01 | Nanoco Technologies Ltd. | Inorganic salt-nanoparticle ink for thin film photovoltaic devices and related methods |
US9893220B2 (en) | 2013-10-15 | 2018-02-13 | Nanoco Technologies Ltd. | CIGS nanoparticle ink formulation having a high crack-free limit |
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US10319589B2 (en) * | 2014-09-12 | 2019-06-11 | The Regents Of The University Of California | High performance thin films from solution processible two-dimensional nanoplates |
CN105964217B (zh) * | 2016-06-17 | 2018-10-12 | 中国科学院城市环境研究所 | 一种磁性KMS-1/Fe3O4复合材料的制备方法及其用于去除环丙沙星 |
US9859450B2 (en) * | 2016-08-01 | 2018-01-02 | Solar-Tectic, Llc | CIGS/silicon thin-film tandem solar cell |
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US11926776B2 (en) | 2020-12-22 | 2024-03-12 | Shoei Chemical Inc. | Films comprising bright silver based quaternary nanostructures |
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EP4183825A1 (en) | 2021-11-23 | 2023-05-24 | SHPP Global Technologies B.V. | Thermoplastic film compositions having improved blue led light stability |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008192542A (ja) * | 2007-02-07 | 2008-08-21 | Nippon Oil Corp | カルコパイライトナノ粒子の製造方法及び光電変換素子 |
JP2010129658A (ja) * | 2008-11-26 | 2010-06-10 | Kyocera Corp | 化合物半導体薄膜の製法および薄膜太陽電池の製法 |
US20110039104A1 (en) * | 2008-03-06 | 2011-02-17 | Bayer Technology Services Gmbh | Copper Indium Sulfide Semiconducting Nanoparticles and Process for Preparing the Same |
US7892519B2 (en) * | 2006-12-14 | 2011-02-22 | Idaho State University | Rapid synthesis and size control of chalcopyrite-based semi-conductor nanoparticles using microwave irradiation |
JP2012515708A (ja) * | 2009-01-21 | 2012-07-12 | パデュー リサーチ ファンデーション | CuInS2ナノ粒子を含む前駆体層のセレン化 |
US20120192930A1 (en) * | 2011-02-02 | 2012-08-02 | Battelle Energy Alliance, Llc | Methods for forming particles, methods of forming semiconductor materials, methods of forming semiconductor devices, and devices formed using such methods |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080038558A1 (en) * | 2006-04-05 | 2008-02-14 | Evident Technologies, Inc. | I-iii-vi semiconductor nanocrystals, i-iii-vi water stable semiconductor nanocrystals, and methods of making same |
WO2011066205A1 (en) | 2009-11-25 | 2011-06-03 | E. I. Du Pont De Nemours And Company | Aqueous process for producing crystalline copper chalcogenide nanoparticles, the nanoparticles so-produced, and inks and coated substrates incorporating the nanoparticles |
-
2014
- 2014-03-03 JP JP2015560800A patent/JP6093044B2/ja active Active
- 2014-03-03 US US14/195,651 patent/US9466743B2/en active Active
- 2014-03-03 KR KR1020187032506A patent/KR101960945B1/ko active IP Right Grant
- 2014-03-03 KR KR1020177004158A patent/KR101935270B1/ko active IP Right Grant
- 2014-03-03 KR KR1020157026978A patent/KR20150127636A/ko not_active Application Discontinuation
- 2014-03-03 CN CN201480025307.5A patent/CN105190836B/zh active Active
- 2014-03-03 WO PCT/IB2014/000827 patent/WO2014135979A1/en active Application Filing
- 2014-03-03 EP EP14728626.4A patent/EP2964566B1/en active Active
-
2016
- 2016-01-14 HK HK16100386.4A patent/HK1212666A1/zh unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7892519B2 (en) * | 2006-12-14 | 2011-02-22 | Idaho State University | Rapid synthesis and size control of chalcopyrite-based semi-conductor nanoparticles using microwave irradiation |
JP2008192542A (ja) * | 2007-02-07 | 2008-08-21 | Nippon Oil Corp | カルコパイライトナノ粒子の製造方法及び光電変換素子 |
US20110039104A1 (en) * | 2008-03-06 | 2011-02-17 | Bayer Technology Services Gmbh | Copper Indium Sulfide Semiconducting Nanoparticles and Process for Preparing the Same |
JP2011513181A (ja) * | 2008-03-06 | 2011-04-28 | バイエル・テクノロジー・サービシーズ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | 銅インジウム硫化物半導体ナノ粒子及びその調製方法 |
JP2010129658A (ja) * | 2008-11-26 | 2010-06-10 | Kyocera Corp | 化合物半導体薄膜の製法および薄膜太陽電池の製法 |
JP2012515708A (ja) * | 2009-01-21 | 2012-07-12 | パデュー リサーチ ファンデーション | CuInS2ナノ粒子を含む前駆体層のセレン化 |
US20120192930A1 (en) * | 2011-02-02 | 2012-08-02 | Battelle Energy Alliance, Llc | Methods for forming particles, methods of forming semiconductor materials, methods of forming semiconductor devices, and devices formed using such methods |
Non-Patent Citations (1)
Title |
---|
JPN5016003013; C. SUN et al.: 'A Large-Scale Synthesis and Characterization of Quaternary CuInxGa1-xS2 Chalcopyrite Nanoparticles v' INTERNATIONAL JOURNAL OF CHEMICAL ENGINEERING Vo.104, No.11, 20110101, p.2467-8 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018053202A (ja) * | 2016-09-30 | 2018-04-05 | 日立化成株式会社 | 量子ドット蛍光体及びそれを用いた発光装置 |
WO2018159699A1 (ja) * | 2017-02-28 | 2018-09-07 | 国立大学法人名古屋大学 | 半導体ナノ粒子およびその製造方法ならびに発光デバイス |
JP2018141141A (ja) * | 2017-02-28 | 2018-09-13 | 国立大学法人名古屋大学 | 半導体ナノ粒子およびその製造方法ならびに発光デバイス |
KR20190124737A (ko) * | 2017-02-28 | 2019-11-05 | 고쿠리츠 다이가쿠 호우징 나고야 다이가쿠 | 반도체 나노 입자 및 그 제조 방법 및 발광 디바이스 |
JP7070826B2 (ja) | 2017-02-28 | 2022-05-18 | 国立大学法人東海国立大学機構 | 半導体ナノ粒子およびその製造方法ならびに発光デバイス |
JP2022115866A (ja) * | 2017-02-28 | 2022-08-09 | 国立大学法人東海国立大学機構 | 半導体ナノ粒子およびその製造方法ならびに発光デバイス |
KR102495692B1 (ko) | 2017-02-28 | 2023-02-06 | 고쿠리츠 다이가쿠 호우징 도우카이 고쿠리츠 다이가쿠 기코우 | 반도체 나노 입자 및 그 제조 방법 및 발광 디바이스 |
KR20230020589A (ko) * | 2017-02-28 | 2023-02-10 | 고쿠리츠 다이가쿠 호우징 도우카이 고쿠리츠 다이가쿠 기코우 | 반도체 나노 입자 및 그 제조 방법 및 발광 디바이스 |
JP7308433B2 (ja) | 2017-02-28 | 2023-07-14 | 国立大学法人東海国立大学機構 | 半導体ナノ粒子およびその製造方法ならびに発光デバイス |
KR102604186B1 (ko) | 2017-02-28 | 2023-11-20 | 고쿠리츠 다이가쿠 호우징 도우카이 고쿠리츠 다이가쿠 기코우 | 반도체 나노 입자 및 그 제조 방법 및 발광 디바이스 |
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US20140249324A1 (en) | 2014-09-04 |
KR20150127636A (ko) | 2015-11-17 |
WO2014135979A1 (en) | 2014-09-12 |
HK1212666A1 (zh) | 2016-06-17 |
KR101960945B1 (ko) | 2019-03-20 |
CN105190836B (zh) | 2021-01-22 |
KR20170021360A (ko) | 2017-02-27 |
EP2964566A1 (en) | 2016-01-13 |
CN105190836A (zh) | 2015-12-23 |
KR20180123197A (ko) | 2018-11-14 |
US9466743B2 (en) | 2016-10-11 |
JP6093044B2 (ja) | 2017-03-08 |
KR101935270B1 (ko) | 2019-01-04 |
EP2964566B1 (en) | 2021-02-17 |
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