JP2016222492A - 微粒子化ペロブスカイト膜及びそれを用いた機能性素子 - Google Patents
微粒子化ペロブスカイト膜及びそれを用いた機能性素子 Download PDFInfo
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- JP2016222492A JP2016222492A JP2015110392A JP2015110392A JP2016222492A JP 2016222492 A JP2016222492 A JP 2016222492A JP 2015110392 A JP2015110392 A JP 2015110392A JP 2015110392 A JP2015110392 A JP 2015110392A JP 2016222492 A JP2016222492 A JP 2016222492A
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- 239000002608 ionic liquid Substances 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical class C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- 229910001507 metal halide Chemical class 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 35
- 150000004693 imidazolium salts Chemical class 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 125000003368 amide group Chemical group 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 238000000089 atomic force micrograph Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- -1 imidazolium cations Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- NKRASMXHSQKLHA-UHFFFAOYSA-M 1-hexyl-3-methylimidazolium chloride Chemical compound [Cl-].CCCCCCN1C=C[N+](C)=C1 NKRASMXHSQKLHA-UHFFFAOYSA-M 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- ILQHIGIKULUQFQ-UHFFFAOYSA-N 1-dodecyl-3-methylimidazolium Chemical compound CCCCCCCCCCCCN1C=C[N+](C)=C1 ILQHIGIKULUQFQ-UHFFFAOYSA-N 0.000 description 1
- IRGDPGYNHSIIJJ-UHFFFAOYSA-N 1-ethyl-2,3-dimethylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1C IRGDPGYNHSIIJJ-UHFFFAOYSA-N 0.000 description 1
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Formation Of Insulating Films (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
この分野において光発電変換効率のさらなる向上や安定した性能、耐久性等の改善が要求されている。
立方晶の各頂点にA:CH3NH3 +,体心にB:Pbを有し、X:I−が立方晶の各面心に有する。
このようなBX6型の八面体は相互の影響を受けやすく、容易に歪みが生じ、大きく物性が変化することが知られている。
例えば、光発電材料においては(110)結晶面が電荷輸送面となる。
例えば、CH3NH3IとPbI2とを溶媒に溶解する例が挙げられる。
イミダゾリウム塩を形成するイミダゾリウムカチオンには、1-Hexyl-3-methylimidazolium,1-Butyl-3-methylimidazolium,1-Ethyl-2,3-dimethylimidazolium,1-Dodecyl-3-methylimidazolium等が例として挙げられる。
塩としてはそれらの、halide,tetrafluoroborate,hexafluorophosphate,acetate,hydrogensulfate,alkylsulfate,tosylate,methanesulfonate等が例として挙げられる。
これにイオン溶液として1-Hexyl-3-methylimidazoliumchloride(HMImCl)を1wt%加えた、この状態では図2に示すように透明な液体(溶液)であった。
これをTiOx/ITO基材の表面にスピンコートし、図1にプロセスを模式的に示すように、常温で30分保持後に所定の温度でアニーリング処理した。
比較のためにイオン液体を加えないものも製作した。
生成された膜のSEM像を図4にAFM像を図5に示す。
図4(a)〜(c)及び図5(b)は、イオン液体を加えない場合であり、リボン状の構造膜になっているのに対して本発明によるイオン溶液を加えたものは、図4(d)〜(f),図5(c)に示すように1μm以下のナノサイズレベルの微粒子が集合した膜構造になっていた。
図7(a)はRT,(b)は70℃,(c)は100℃,(d)は130℃で、それぞれ10分間の処理である。
アニーリング処理にて、微粒子化されたペロブスカイト膜が得られていることが分かる。
図8,図9にイオン液体の有無による吸光度比較したグラフを示す。
イオン液体の添加により光学特性が変化していることがわかる。
図10,図11にはイオン液体の添加量の影響を調査した結果を示す。
図10で(a)はイオン液体の添加量3wt%,(b)は7wt%,(c)は10wt%のSEM像である。
これによりイオン液体の添加量も膜構造に影響を与え、本実施例に用いたイオン液体の場合は7wt%以下が好ましいことが分かる。
また、ペロブスカイト膜構造は従来のイオン液体の加えないものがリボン構造であったのに対して、イオン液体を加えることにより、膜構造がナノ微粒子構造になることで特性が大きく変化することが明らかになり、従来のペロブスカイト結晶を光発電材料に用いた薄膜太陽電池の変換効率向上が期待される。
Claims (5)
- ペロブスカイト型結晶を生成する前駆体物質とイオン液体とを溶媒に溶解した溶液を塗布及び乾燥することで得られる、微粒子化ペロブスカイト膜。
- 前記前駆体物質は、ハロゲン化アルキルアミンとハロゲン化金属との混合物であることを特徴とする請求項1記載の微粒子化ペロブスカイト膜。
- 前記イオン液体は、イミダゾリム塩、ピリジニウム塩、アンモニウム塩、ピロリジニウム塩、ホスホニウム塩、スルホニウム塩のうち、いずれか1つ以上であることを特徴とする請求項1又は2記載の微粒子化ペロブスカイト膜。
- 前記溶媒は、アミド系溶媒、ブチロラクトン、ジメチルスルホキシドのうちいずれかであることを特徴とする請求項1〜3のいずれかに記載の微粒子化ペロブスカイト膜。
- 請求項1〜4のいずれかに記載の微粒子化ペロブスカイト膜を用いたことを特徴とする機能性素子。
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109326709A (zh) * | 2018-10-10 | 2019-02-12 | 业成科技(成都)有限公司 | 感测膜及其制备方法、电子装置 |
CN109817810A (zh) * | 2019-01-22 | 2019-05-28 | 西北工业大学深圳研究院 | 一种掺杂三唑离子液体的钙钛矿太阳能电池及制备方法 |
CN110224069A (zh) * | 2019-06-13 | 2019-09-10 | 天合光能股份有限公司 | 一种具有防水功能的钙钛矿太阳能电池及其制备方法 |
JP2020025059A (ja) * | 2018-08-09 | 2020-02-13 | 国立大学法人九州工業大学 | 熱電変換素子 |
CN111710780A (zh) * | 2020-06-18 | 2020-09-25 | 西北工业大学 | 阴极原位修饰的无电子传输层钙钛矿太阳能电池的制备方法 |
CN112071987A (zh) * | 2020-09-02 | 2020-12-11 | 西北工业大学 | 一种离子液体钙钛矿介质及制备方法 |
JP2022511773A (ja) * | 2018-11-28 | 2022-02-01 | オックスフォード ユニヴァーシティ イノヴェーション リミテッド | 長期安定光電子デバイス |
US20220310929A1 (en) * | 2019-06-11 | 2022-09-29 | Oxford University Innovation Limited | Optoelectronic device |
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Cited By (12)
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JP2020025059A (ja) * | 2018-08-09 | 2020-02-13 | 国立大学法人九州工業大学 | 熱電変換素子 |
JP7244044B2 (ja) | 2018-08-09 | 2023-03-22 | 国立大学法人九州工業大学 | 熱電変換素子 |
CN109326709A (zh) * | 2018-10-10 | 2019-02-12 | 业成科技(成都)有限公司 | 感测膜及其制备方法、电子装置 |
CN109326709B (zh) * | 2018-10-10 | 2022-05-13 | 业成科技(成都)有限公司 | 感测膜及其制备方法、电子装置 |
JP2022511773A (ja) * | 2018-11-28 | 2022-02-01 | オックスフォード ユニヴァーシティ イノヴェーション リミテッド | 長期安定光電子デバイス |
CN109817810A (zh) * | 2019-01-22 | 2019-05-28 | 西北工业大学深圳研究院 | 一种掺杂三唑离子液体的钙钛矿太阳能电池及制备方法 |
CN109817810B (zh) * | 2019-01-22 | 2020-09-22 | 西北工业大学深圳研究院 | 一种掺杂三唑离子液体的钙钛矿太阳能电池及制备方法 |
US20220310929A1 (en) * | 2019-06-11 | 2022-09-29 | Oxford University Innovation Limited | Optoelectronic device |
CN110224069A (zh) * | 2019-06-13 | 2019-09-10 | 天合光能股份有限公司 | 一种具有防水功能的钙钛矿太阳能电池及其制备方法 |
CN110224069B (zh) * | 2019-06-13 | 2023-04-18 | 天合光能股份有限公司 | 一种具有防水功能的钙钛矿太阳能电池及其制备方法 |
CN111710780A (zh) * | 2020-06-18 | 2020-09-25 | 西北工业大学 | 阴极原位修饰的无电子传输层钙钛矿太阳能电池的制备方法 |
CN112071987A (zh) * | 2020-09-02 | 2020-12-11 | 西北工业大学 | 一种离子液体钙钛矿介质及制备方法 |
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