JP2021174840A - Photoelectric conversion material and photoelectric conversion element - Google Patents
Photoelectric conversion material and photoelectric conversion element Download PDFInfo
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- JP2021174840A JP2021174840A JP2020076483A JP2020076483A JP2021174840A JP 2021174840 A JP2021174840 A JP 2021174840A JP 2020076483 A JP2020076483 A JP 2020076483A JP 2020076483 A JP2020076483 A JP 2020076483A JP 2021174840 A JP2021174840 A JP 2021174840A
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- SJFZRVWNUGYHML-UHFFFAOYSA-N diethylsilyloxy-diethyl-triethylsilyloxysilane Chemical compound CC[SiH](CC)O[Si](CC)(CC)O[Si](CC)(CC)CC SJFZRVWNUGYHML-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XUKFPAQLGOOCNJ-UHFFFAOYSA-N dimethyl(trimethylsilyloxy)silicon Chemical compound C[Si](C)O[Si](C)(C)C XUKFPAQLGOOCNJ-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910001849 group 12 element Inorganic materials 0.000 description 1
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- 150000007857 hydrazones Chemical class 0.000 description 1
- PFEAZKFNWPIFCV-UHFFFAOYSA-N hydroxy-[hydroxy(dimethyl)silyl]oxy-dimethylsilane Chemical compound C[Si](C)(O)O[Si](C)(C)O PFEAZKFNWPIFCV-UHFFFAOYSA-N 0.000 description 1
- FGOLZCPMTWJPOU-UHFFFAOYSA-N hydroxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O FGOLZCPMTWJPOU-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000004297 night vision Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical class C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052696 pnictogen Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
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- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical group C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
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- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
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- 239000004332 silver Substances 0.000 description 1
- YRSQDSCQMOUOKO-KVVVOXFISA-M silver;(z)-octadec-9-enoate Chemical compound [Ag+].CCCCCCCC\C=C/CCCCCCCC([O-])=O YRSQDSCQMOUOKO-KVVVOXFISA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
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- 238000003980 solgel method Methods 0.000 description 1
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- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 150000003513 tertiary aromatic amines Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Light Receiving Elements (AREA)
Abstract
Description
本発明は、光電変換材料及び光電変換素子に関する。 The present invention relates to photoelectric conversion materials and photoelectric conversion elements.
光エネルギーを電気エネルギーに変える光電変換素子は、太陽電池、光センサー、複写
機などに利用されている。これらの内、光エネルギーとして近赤外光を使用した光センサ
ーは、暗視、測距、セキュリティ、半導体ウエハ検査等への用途展開が注目されている。
Photoelectric conversion elements that convert light energy into electrical energy are used in solar cells, optical sensors, copiers, and the like. Of these, optical sensors that use near-infrared light as light energy are attracting attention for their use in night vision, ranging, security, semiconductor wafer inspection, and the like.
ところで近年、ＰｂＳ等の半導体粒子（量子ドット）を光電変換素子や太陽電池等の光
電変換の材料に用いることが報告されている。例えば、非特許文献１には、ＰｂＳｅの半
導体粒子の周囲のオレイン酸をエタンジチオールに置換する事によって、半導体粒子同士
が近接化し、電気伝導性が向上することが報告されている。また、特許文献１には、Ｃｄ
Ｓ等の複数の超微粒子がベンゼンジチオール等の分子鎖で結合された超微粒子が記載され
ており、光学材料、電子材料等の各種用途に使用可能であることが開示されている。特許
文献２には、ＰｂＳｅの半導体粒子の周囲のオレイン酸を２−アミノエタン−１−チオー
ル等に置換する事によって、半導体粒子同士がより近接化し、高い光電流値が得られるこ
とが開示されている。特許文献３には、オレイン酸の替わりに、ベンゼンチオール、ベン
ゼンジチオール、３−メルカプトプロピオン酸、エチレンジアミン、テトラブチルアンモ
ニウムのハライド塩等をリガンドとして用いることで、ＰｂＳ量子ドットのエネルギーレ
ベルを制御し、光電変換素子特性を改善可能であることが示唆されている。
By the way, in recent years, it has been reported that semiconductor particles (quantum dots) such as PbS are used as materials for photoelectric conversion such as photoelectric conversion elements and solar cells. For example, Non-Patent Document 1 reports that by substituting ethanedithiol for oleic acid around the semiconductor particles of PbSe, the semiconductor particles are brought closer to each other and the electrical conductivity is improved. Further, in Patent Document 1, Cd
Ultrafine particles in which a plurality of ultrafine particles such as S are bonded by a molecular chain such as benzenedithiol are described, and it is disclosed that they can be used for various purposes such as optical materials and electronic materials. Patent Document 2 discloses that by substituting oleic acid around the semiconductor particles of PbSe with 2-aminoethane-1-thiol or the like, the semiconductor particles are closer to each other and a high photocurrent value can be obtained. There is. In Patent Document 3, the energy level of PbS quantum dots is controlled by using a halide salt of benzenethiol, benzenedithiol, 3-mercaptopropionic acid, ethylenediamine, tetrabutylammonium, etc. as a ligand instead of oleic acid. It is suggested that the characteristics of the photoelectric conversion element can be improved.
しかしながら、上記発明では、光電変換能の一層の改善が必要となっていた。また、光
検出用途ではノイズの原因となる暗電流を十分に抑制できておらず、課題となっていた。
したがって、本発明が解決しようとする課題は、優れた光電変換効率と暗電流を抑制でき
る光電変換素子とそれを得るための光電変換材料を提供することにある。
However, in the above invention, it is necessary to further improve the photoelectric conversion ability. Further, in light detection applications, dark currents that cause noise cannot be sufficiently suppressed, which has been a problem.
Therefore, an object to be solved by the present invention is to provide a photoelectric conversion element capable of suppressing dark current and excellent photoelectric conversion efficiency, and a photoelectric conversion material for obtaining the photoelectric conversion element.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、本発明に至った。
すなわち、本発明は、半導体粒子が正孔輸送性リガンドで表面処理されている半導体粒
子（Ａ１）及び半導体粒子が電子輸送性リガンドで表面処理されている半導体粒子（Ａ２
）を含んでなる光電変換材料に関する。
The present inventors have reached the present invention as a result of repeated diligent studies to solve the above problems.
That is, in the present invention, the semiconductor particles (A1) in which the semiconductor particles are surface-treated with the hole-transporting ligand and the semiconductor particles (A2) in which the semiconductor particles are surface-treated with the electron-transporting ligand.
) Containing a photoelectric conversion material.
また、本発明は、上記半導体粒子（Ａ１）又は上記半導体粒子（Ａ２）が、化合物半導
体を含んでなる上記光電変換材料に関する。
The present invention also relates to the photoelectric conversion material in which the semiconductor particles (A1) or the semiconductor particles (A2) contain a compound semiconductor.
また、本発明は、上記正孔輸送性リガンドの最高被占軌道（ＨＯＭＯ）のエネルギー準
位が、−６．５ｅＶ以上−４．６ｅＶ以下である、上記光電変換材料に関する。
The present invention also relates to the photoelectric conversion material in which the energy level of the highest occupied molecular orbital (HOMO) of the hole transporting ligand is −6.5 eV or more and −4.6 eV or less.
また、本発明は、上記電子輸送性リガンドの最低空軌道（ＬＵＭＯ）のエネルギー準位
が、−４．５ｅＶ以上−２．５ｅＶ以下である、上記光電変換材料に関する。
The present invention also relates to the photoelectric conversion material in which the energy level of the lowest unoccupied molecular orbital (LUMO) of the electron transporting ligand is −4.5 eV or more and −2.5 eV or less.
また、本発明は、上記正孔輸送性リガンドのＨＯＭＯのエネルギー準位が、上記電子輸
送性リガンドのＨＯＭＯのエネルギー準位よりも０．２ｅＶ以上大きい、上記光電変換材
料に関する。
The present invention also relates to the photoelectric conversion material in which the energy level of HOMO of the hole transporting ligand is 0.2 eV or more higher than the energy level of HOMO of the electron transporting ligand.
また、本発明は、上記正孔輸送性リガンドのＬＵＭＯのエネルギー準位が、上記電子輸
送性リガンドのＬＵＭＯのエネルギー準位よりも０．２ｅＶ以上大きい、上記光電変換材
料に関する。
The present invention also relates to the photoelectric conversion material in which the LUMO energy level of the hole transporting ligand is 0.2 eV or more higher than the LUMO energy level of the electron transporting ligand.
また、本発明は、半導体粒子（Ａ１）又は半導体粒子（Ａ２）の少なくともいずれかが
、波長７００〜２５００ｎｍの電磁波を吸収し得る上記光電変換材料に関する。
The present invention also relates to the photoelectric conversion material in which at least one of the semiconductor particles (A1) and the semiconductor particles (A2) can absorb electromagnetic waves having a wavelength of 700 to 2500 nm.
また、本発明は、上記半導体粒子（Ａ１）又は上記半導体粒子（Ａ２）の少なくともい
ずれかが、ＰｂＳ、ＰｂＳｅ及びＡｇ2Ｓからなる群より選ばれる一種以上を含んでなる
上記光電変換材料に関する。
Further, the present invention is at least one of said semiconductor particles (A1) or the semiconductor particles (A2) are, PbS, relates the photoelectric conversion material comprising one or more kinds selected from the group consisting of PbSe and Ag 2 S.
また、本発明は、陽極と、少なくとも１層の光電変換層と、陰極と、を有する光電変換
素子であって、光電変換層が、上記光電変換材料を含む光電変換素子に関する。
The present invention also relates to a photoelectric conversion element having an anode, at least one photoelectric conversion layer, and a cathode, wherein the photoelectric conversion layer contains the above-mentioned photoelectric conversion material.
本発明によれば、優れた光電変換効率と暗電流を抑制できる光電変換素子を得ることが
できる。
According to the present invention, it is possible to obtain a photoelectric conversion element capable of suppressing dark current and excellent photoelectric conversion efficiency.
以下、本発明の実施形態について説明する。
＜光電変換材料＞
本発明の光電変換材料は、半導体粒子が正孔輸送性リガンドで表面処理されている半導
体粒子（Ａ１）及び半導体粒子が電子輸送性リガンドで表面処理されている半導体粒子（
Ａ２）を含んでなることが特徴である。半導体粒子（Ａ１）及び半導体粒子（Ａ２）中の
半導体粒子は、以下で説明する半導体粒子が挙げられ、これらは同一であっても異なって
いても良い。
Hereinafter, embodiments of the present invention will be described.
<Photoelectric conversion material>
The photoelectric conversion material of the present invention includes semiconductor particles (A1) in which semiconductor particles are surface-treated with a hole-transporting ligand and semiconductor particles in which semiconductor particles are surface-treated with an electron-transporting ligand (A1).
It is characterized by containing A2). Examples of the semiconductor particles in the semiconductor particles (A1) and the semiconductor particles (A2) include the semiconductor particles described below, which may be the same or different.
＜半導体粒子＞
半導体粒子とは、半導体からなる平均粒径０．５ｎｍ〜１００ｎｍの粒子を指す。半導
体粒子の平均粒径は、安定性及び光電変換効率を向上させる観点から、好ましくは１ｎｍ
以上、より好ましくは１．５ｎｍ以上、更に好ましくは２ｎｍ以上であり、成膜性及び光
電変換効率を向上させる観点から、好ましくは２０ｎｍ以下、より好ましくは１０ｎｍ以
下である。尚、本明細書における半導体粒子の粒径は、透過型電子顕微鏡観察によって測
定した数値である。半導体粒子は、化合物半導体を含有することが好ましい。化合物半導
体とは、周期表１族元素、２族元素、１０族元素、１１族元素、１２族元素、１３族元素
、１４族元素、１５族元素、１６族元素及び１７族元素からなる群から選ばれる少なくと
も２種以上の元素を含む化合物からなる半導体であることが好ましい。半導体粒子は、波
長７００〜２５００ｎｍの電磁波を吸収し得ることが好ましい。波長７００〜２５００ｎ
ｍの電磁波は、一般に近赤外光（近赤外線ともいう）と呼称され、半導体粒子が波長７０
０〜２５００ｎｍの電磁波を吸収し得るためには、半導体粒子が波長７００〜２５００ｎ
ｍの電磁波を吸収し得る化合物半導体を含有することが好ましい。波長７００〜２５００
ｎｍの電磁波を吸収し得る化合物半導体としては、例えば、ペロブスカイト結晶構造を有
する化合物半導体や金属カルコゲナイド（例えば、酸化物、硫化物、セレン化物、及びテ
ルル化物など）が挙げられる。ペロブスカイト結晶構造を有する化合物半導体としては、
具体的には、ＣＨ3ＮＨ3ＰｂＦ3、ＣＨ3ＮＨ3ＰｂＣｌ3、ＣＨ3ＮＨ3ＰｂＢｒ3、ＣＨ3Ｎ
Ｈ3ＰｂＩ3、ＣｓＰｂＦ3、ＣｓＰｂＣｌ3、ＣｓＰｂＢｒ3、ＣｓＰｂＩ3、ＲｂＰｂＦ3
、ＲｂＰｂＣｌ3、ＲｂＰｂＢｒ3、ＲｂＰｂＩ3、ＫＰｂＦ3、ＫＰｂＣｌ3、ＫＰｂＢｒ3
、ＫＰｂＩ3などが挙げられる。また、金属カルコゲナイドとしては、具体的には、Ｐｂ
Ｓ、ＰｂＳｅ、ＰｂＴｅ、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、Ｓｂ2Ｓ3、Ｂｉ2Ｓ3、Ａｇ2Ｓ
、Ａｇ2Ｓｅ、Ａｇ2Ｔｅ、Ａｕ2Ｓ、Ａｕ2Ｓｅ、Ａｕ2Ｔｅ、Ｃｕ2Ｓ、Ｃｕ2Ｓｅ、Ｃｕ2
Ｔｅ、Ｆｅ2Ｓ、Ｆｅ2Ｓｅ、Ｆｅ2Ｔｅ、Ｉｎ2Ｓ3、ＳｎＳ、ＳｎＳｅ、ＳｎＴｅ、Ｃｕ
ＩｎＳ2、ＣｕＩｎＳｅ2、ＣｕＩｎＴｅ2、ＥｕＳ、ＥｕＳｅ、ＥｕＴｅなどが挙げられ
る。これらの中でも、ＰｂＳ、ＰｂＳｅ、Ａｇ2Ｓが好ましい。
<Semiconductor particles>
The semiconductor particles refer to particles made of semiconductors having an average particle size of 0.5 nm to 100 nm. The average particle size of the semiconductor particles is preferably 1 nm from the viewpoint of improving stability and photoelectric conversion efficiency.
Above, it is more preferably 1.5 nm or more, further preferably 2 nm or more, and from the viewpoint of improving film forming property and photoelectric conversion efficiency, it is preferably 20 nm or less, more preferably 10 nm or less. The particle size of the semiconductor particles in the present specification is a numerical value measured by observation with a transmission electron microscope. The semiconductor particles preferably contain a compound semiconductor. The compound semiconductor is composed of a group consisting of Group 1 element, Group 2 element, Group 10 element, Group 11 element, Group 12 element, Group 13 element, Group 14 element, Group 15 element, Group 16 element and Group 17 element in the periodic table. It is preferably a semiconductor composed of a compound containing at least two selected elements. It is preferable that the semiconductor particles can absorb electromagnetic waves having a wavelength of 700 to 2500 nm. Wavelength 700-2500n
The electromagnetic wave of m is generally called near-infrared light (also called near-infrared light), and the semiconductor particles have a wavelength of 70.
In order to be able to absorb electromagnetic waves of 0 to 2500 nm, semiconductor particles have a wavelength of 700 to 2500 n.
It is preferable to contain a compound semiconductor capable of absorbing m electromagnetic waves. Wavelength 700-2500
Examples of the compound semiconductor capable of absorbing an electromagnetic wave of nm include a compound semiconductor having a perovskite crystal structure and a metal chalcogenide (for example, an oxide, a sulfide, a selenium compound, and a telluride compound). As a compound semiconductor having a perovskite crystal structure,
Specifically, CH 3 NH 3 PbF 3 , CH 3 NH 3 PbCl 3 , CH 3 NH 3 PbBr 3 , CH 3 N
H 3 PbI 3 , CsPbF 3 , CsPbCl 3 , CsPbBr 3 , CsPbI 3 , RbPbF 3
, RbPbCl 3 , RbPbBr 3 , RbPbI 3 , KPbF 3 , KPbCl 3 , KPbBr 3
, KPbI 3 and the like. Further, as the metal chalcogenide, specifically, Pb
S, PbSe, PbTe, CdS, CdSe, CdTe, Sb 2 S 3 , Bi 2 S 3 , Ag 2 S
, Ag 2 Se, Ag 2 Te, Au 2 S, Au 2 Se, Au 2 Te, Cu 2 S, Cu 2 Se, Cu 2
Te, Fe 2 S, Fe 2 Se, Fe 2 Te, In 2 S 3 , SnS, SnSe, SnTe, Cu
Examples thereof include InS 2 , CuInSe 2 , CuInTe 2 , EuS, EuSe, and EuTe. Among these, PbS, PbSe, Ag 2 S is preferred.
＜リガンド＞
リガンドは、半導体粒子の表面処理に用いられ、前記半導体粒子表面の少なくとも一部
を覆うものである。
<Ligand>
The ligand is used for surface treatment of semiconductor particles and covers at least a part of the surface of the semiconductor particles.
［正孔輸送性リガンド］
正孔輸送性リガンドは、半導体粒子表面への吸着部位と、正孔輸送する機能を持つ正孔
輸送性部位からなる。吸着部位と正孔輸送性部位は完全に分離している必要は無く、例え
ば、正孔輸送性部位の一部が吸着部位となっていてもよい。
[Hole-transporting ligand]
The hole-transporting ligand consists of an adsorption site on the surface of semiconductor particles and a hole-transporting site having a hole-transporting function. The adsorption site and the hole transporting site do not have to be completely separated. For example, a part of the hole transporting site may be an adsorption site.
吸着部位としては、一価の基としては、カルボキシル基（−ＣＯＯＨ）、アミノ基（−
ＮＨ2）、ホスフィノ基（−ＰＨ2）、及び、スルファニル基（−ＳＨ）等が挙げられ、ま
た、２価の基としては、カルボニル基（＞（Ｃ＝Ｏ））等があげられ、また、３価の基と
しては、ホスホロソ基（＞（Ｐ＝Ｏ）−）等が挙げられる。
As the adsorption site, the monovalent group includes a carboxyl group (-COOH) and an amino group (-).
NH2), phosphino group (-PH 2 ), sulfanyl group (-SH) and the like can be mentioned, and examples of the divalent group include a carbonyl group (> (C = O)) and the like. Examples of the trivalent group include a phosphoroso group (> (P = O)-) and the like.
正孔輸送性部位は、有機電界発光素子材料として用いられる公知の正孔輸送性化合物及
びその誘導体からなる構造を有する部位が挙げられ、特に限定されないが、例えば、第三
級芳香族アミン、チオフェンオリゴマー、チオフェンポリマー、ピロールオリゴマー、ピ
ロールポリマー、フェニレンビニレンオリゴマー、フェニレンビニレンポリマー、ビニル
カルバゾールオリゴマー、ビニルカルバゾールポリマー、フルオレンオリゴマー、フルオ
レンポリマー、フェニレンエチンオリゴマー、フェニレンエチンポリマー、フェニレンオ
リゴマー、フェニレンポリマー、アセチレンオリゴマー、アセチレンポリマー、フタロシ
アニン、フタロシアニン誘導体、ポルフィリン、及びポルフィリン誘導体等が挙げられる
。また、以下に示す化合物及びその誘導体から水素原子を一つ以上除いた有機残基も、正
孔輸送性部位として機能し得る。
Examples of the hole-transporting moiety include a moiety having a structure composed of a known hole-transporting compound used as an organic electroluminescent element material and a derivative thereof, and are not particularly limited, but for example, a tertiary aromatic amine and thiophene. Oligomers, thiophene polymers, pyrrole oligomers, pyrrol polymers, phenylene vinylene oligomers, phenylene vinylene polymers, vinyl carbazole oligomers, vinyl carbazole polymers, fluorene oligomers, fluorene polymers, phenylene ethine oligomers, phenylene ethine polymers, phenylene oligomers, phenylene polymers, acetylene oligomers, Examples thereof include acetylene polymers, phthalocyanines, phthalocyanine derivatives, porphyrins, and porphyrin derivatives. In addition, an organic residue obtained by removing one or more hydrogen atoms from the following compounds and derivatives thereof can also function as a hole transporting site.
さらに、正孔輸送リガンドの好ましい構造として下記一般式（１）、一般式（２）又は
一般式（３）で表されるものが挙げられる。
Further, as a preferable structure of the hole transporting ligand, those represented by the following general formula (1), general formula (2) or general formula (3) can be mentioned.
［一般式（１）中、Ｘ1は、水素原子、置換基を有してもよい脂肪族炭化水素基、置換基
を有してもよい芳香環基、又は置換基を有してもよいアシル基であり、Ｒ1〜Ｒ8は、それ
ぞれ独立して、水素原子、置換基を有してもよい脂肪族炭化水素基、置換基を有してもよ
い芳香環基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ
基、置換基を有してもよいアシル基、置換基を有してもよいアミノ基、置換基を有しても
よい（ポリ）オルガノシロキサン基、カルボキシル基又はスルファニル基であり、Ｘ1及
びＲ1〜Ｒ8の内、少なくとも１つが、カルボキシル基を有する基又はスルファニル基を有
する基である。］
[In the general formula (1), X 1 may have a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or a substituent. It is an acyl group, and R 1 to R 8 each independently have a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, and a substituent. It may have an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an acyl group which may have a substituent, an amino group which may have a substituent, and a substituent (which may have a substituent (). Poly) It is an organosiloxane group, a carboxyl group or a sulfanyl group, and at least one of X 1 and R 1 to R 8 is a group having a carboxyl group or a group having a sulfanyl group. ]
［一般式（２）中、Ｒ11〜Ｒ25は、それぞれ独立して、水素原子、置換基を有してもよい
脂肪族炭化水素基、置換基を有してもよい芳香環基、置換基を有してもよいアルコキシ基
、置換基を有してもよいアリールオキシ基、置換基を有してもよいアシル基、置換基を有
してもよい（ポリ）オルガノシロキサン基、ニトロ基、置換基を有してもよいアミノ基、
カルボキシル基又はスルファニル基であり、Ｒ11〜Ｒ25の内、少なくとも１つが、カルボ
キシル基を有する基又はスルファニル基を有する基である。］
[In the general formula (2), R 11 to R 25 are independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, and a substituent. An alkoxy group which may have a group, an aryloxy group which may have a substituent, an acyl group which may have a substituent, a (poly) organosiloxane group which may have a substituent, and a nitro group. , Amino group which may have a substituent,
It is a carboxyl group or a sulfanil group, and at least one of R 11 to R 25 is a group having a carboxyl group or a group having a sulfanil group. ]
［一般式（３）中、Ｘ2は、水素原子、置換基を有してもよい脂肪族炭化水素基、置換基
を有してもよい芳香環基（ただしフェニル基を除く）、又は置換基を有してもよいアシル
基であり、Ｒ26〜Ｒ35は、それぞれ独立して、水素原子、置換基を有してもよい脂肪族炭
化水素、置換基を有してもよい芳香環基、置換基を有してもよいアルコキシ基、置換基を
有してもよいアリールオキシ基、置換基を有してもよい（ポリ）オルガノシロキサン基、
置換基を有してもよいアミノ基、置換基を有してもよいアシル基、カルボキシル基又はス
ルファニル基であり、Ｘ2及びＲ26〜Ｒ35の内、少なくとも１つが、カルボキシル基を有
する基又はスルファニル基を有する基である。］
[In the general formula (3), X 2 is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent (excluding a phenyl group), or a substituent. It is an acyl group which may have a group, and R 26 to R 35 are independently hydrogen atoms, an aliphatic hydrocarbon which may have a substituent, and an aromatic ring which may have a substituent. A group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a (poly) organosiloxane group which may have a substituent,
An amino group which may have a substituent, an acyl group which may have a substituent, a carboxyl group or a sulfanyl group, and at least one of X 2 and R 26 to R 35 is a group having a carboxyl group. Alternatively, it is a group having a sulfanyl group. ]
以下に、上記一般式（１）〜（３）における基について説明する。
脂肪族炭化水素基は、脂肪族炭化水素から形式的に水素原子を１つ取り除いた一価の残
基であり、飽和脂肪族炭化水素基及び不飽和脂肪族炭化水素基が挙げられる。飽和脂肪族
炭化水素基としては、アルキル基、シクロアルキル基等が挙げられる。不飽和脂肪族炭化
水素基としては、アルケニル基、アルキニル基、シクロアリケニル基等が挙げられる。
脂肪族炭化水素基は、直鎖、分岐又は環状であっても良い。脂肪族炭化水素基の具体例と
しては、メチル基、エチル基、ヘキシル基、ドデシル基、エイコシル基等の直鎖アルキル
基；２−エチルヘキシル基等の分岐アルキル基；シクロヘキシル基、３−シクロヘキシル
プロピル基等のシクロアルキル基；エテニル基、ドデセン基等のアルケニル基；プロパ−
２−イン−１−基、プロパルギル基等のアルキニル基が挙げられる。脂肪族炭化水素基の
炭素数は１〜３０が好ましい。
The groups in the general formulas (1) to (3) will be described below.
The aliphatic hydrocarbon group is a monovalent residue obtained by formally removing one hydrogen atom from the aliphatic hydrocarbon, and examples thereof include saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups. Examples of the saturated aliphatic hydrocarbon group include an alkyl group and a cycloalkyl group. Examples of the unsaturated aliphatic hydrocarbon group include an alkenyl group, an alkynyl group, a cycloarikenyl group and the like.
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear alkyl group such as a methyl group, an ethyl group, a hexyl group, a dodecyl group and an eicosyl group; a branched alkyl group such as a 2-ethylhexyl group; a cyclohexyl group and a 3-cyclohexylpropyl group. Cycloalkyl groups such as; alkenyl groups such as ethenyl groups and dodecene groups; propars
Examples thereof include alkynyl groups such as 2-in-1-group and propargyl group. The aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms.
芳香環基は、芳香環から形式的に水素原子を１つ取り除いた一価の残基であり、芳香族
炭化水素基と芳香族複素環基が挙げられる。芳香族炭化水素基としては、単環、縮合環及
び環集合からなる群より選ばれる芳香族炭化水素基であるアリール基が挙げられる。アリ
ール基の具体例としては、ベンゼン、ナフタレン、ピレン、ビフェニル、ターフェニル等
の芳香族炭化水素から形式的に水素原子を１つ取り除いた一価の残基が挙げられる。アリ
ール基の炭素数は６〜３０が好ましい。芳香族複素環基は、芳香族複素環から形式的に水
素原子を１つ取り除いた一価の残基である。芳香族複素環基の具体例としては、ピリジン
、ピリミジン、ピリダジン、ピラジン、キノリン、フラン、ピロール、チオフェン、イミ
ダゾール、ピラゾール、オキサゾール、チアゾール、インドール、ベンズイミダゾール、
ベンゾフラン、プリン、アクリジン、フェノチアジン等の芳香族複素環から形式的に水素
原子を１つ取り除いた一価の残基が挙げられる。芳香族複素環基の炭素数は２〜３０が好
ましい。
The aromatic ring group is a monovalent residue obtained by formally removing one hydrogen atom from the aromatic ring, and examples thereof include an aromatic hydrocarbon group and an aromatic heterocyclic group. Examples of the aromatic hydrocarbon group include an aryl group which is an aromatic hydrocarbon group selected from the group consisting of a monocyclic ring, a fused ring and a ring assembly. Specific examples of the aryl group include a monovalent residue obtained by formally removing one hydrogen atom from aromatic hydrocarbons such as benzene, naphthalene, pyrene, biphenyl, and terphenyl. The aryl group preferably has 6 to 30 carbon atoms. An aromatic heterocyclic group is a monovalent residue obtained by formally removing one hydrogen atom from an aromatic heterocycle. Specific examples of aromatic heterocyclic groups include pyridine, pyrimidine, pyridazine, pyrazine, quinoline, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, thiazole, indol, benzimidazole,
Examples thereof include monovalent residues in which one hydrogen atom is formally removed from an aromatic heterocycle such as benzofuran, purine, acridine, and phenothiazine. The aromatic heterocyclic group preferably has 2 to 30 carbon atoms.
アルコキシ基は、エーテル結合を介してアルキル基が結合した官能基であり、当該アル
キル基としては、上記アルキル基が挙げられる。
The alkoxy group is a functional group in which an alkyl group is bonded via an ether bond, and examples of the alkyl group include the above-mentioned alkyl group.
アリールオキシ基は、エーテル結合を介してアリール基が結合した官能基であり、当該
アリール基としては、上記アリール基が挙げられる。
The aryloxy group is a functional group to which an aryl group is bonded via an ether bond, and examples of the aryl group include the above-mentioned aryl group.
アシル基は、カルボニル基を介してアルキル基又はアリール基が結合した官能基であり
、当該アルキル基及びアリール基としては、上記アルキル基及びアリール基が挙げられる
。
The acyl group is a functional group in which an alkyl group or an aryl group is bonded via a carbonyl group, and examples of the alkyl group and the aryl group include the above-mentioned alkyl group and the aryl group.
（ポリ）オルガノシロキサン基は、オルガノシロキサンから形式的に水素原子を１つ取
り除いた残基である。オルガノシロキサンとしては、例えば、ペンタメチルジシロキサン
、ヘプタエチルトリシロキサン、ウンデカメチルテトラシロキサン、トリメチルシロキシ
ジメチルシラノール、１，１，３，３，テトラメチル−１，３−ジヒドロキシジシロキサ
ン又は１，１，３，３，５，５−ヘキサメチル−１，５−ジヒドロキシ−トリシロキサン
等が挙げられる。（ポリ）オルガノシロキサン基中のシロキサン結合の繰返し単位数は、
１〜４であることが好ましい。
A (poly) organosiloxane group is a residue obtained by formally removing one hydrogen atom from an organosiloxane. Examples of the organosiloxane include pentamethyldisiloxane, heptaethyltrisiloxane, undecamethyltetrasiloxane, trimethylsiloxydimethylsilanol, 1,1,3,3, tetramethyl-1,3-dihydroxydisiloxane or 1,1. , 3,3,5,5-hexamethyl-1,5-dihydroxy-trisiloxane and the like. The number of repeating units of the siloxane bond in the (poly) organosiloxane group is
It is preferably 1 to 4.
また、一般式（１）〜（３）における脂肪族炭化水素基、芳香環基、アルコキシ基、ア
リールオキシ基、アシル基、アミノ基、（ポリ）オルガノシロキサン基は、さらに、置換
基を有していてもよい。
Further, the aliphatic hydrocarbon group, aromatic ring group, alkoxy group, aryloxy group, acyl group, amino group and (poly) organosiloxane group in the general formulas (1) to (3) further have a substituent. May be.
また、カルボキシル基又はスルファニル基を有する基とは、カルボキシル基及びスルフ
ァニル基の他、置換基としてカルボキシル基又はスルファニル基を有する、アルキル基、
アリール基、アルコキシ基、アリールオキシ基、アミノ基、（ポリ）オルガノシロキサン
基又はアシル基等の一価の有機残基が挙げられる。
The group having a carboxyl group or a sulfanyl group is an alkyl group having a carboxyl group or a sulfanyl group as a substituent in addition to the carboxyl group and the sulfanyl group.
Examples thereof include monovalent organic residues such as an aryl group, an alkoxy group, an aryloxy group, an amino group, a (poly) organosiloxane group or an acyl group.
カルボキシル基を有するアルキル基、又はカルボキシル基を有するアリール基の例とし
ては、例えば、２−カルボシキシルエチル基、２，２−ジカルボキシルエチル基、２−カ
ルボシキシルエテニル基、２−シアノ−２−カルボシキシルエテニル基、２−トリフルオ
ロメチル−２−カルボシキシルエテニル基、２−フルオロ−２−カルボシキシルエテニル
基等が挙げられる。
Examples of an alkyl group having a carboxyl group or an aryl group having a carboxyl group include, for example, a 2-carbosixyl ethyl group, a 2,2-dicarboxyethyl group, a 2-carbosixyl ethenyl group, and a 2-cyano-. Examples thereof include 2-carbosixyl ethenyl group, 2-trifluoromethyl-2-carbosixyl ethenyl group, 2-fluoro-2-carbosixyl ethenyl group and the like.
スルファニル基を有するアルキル基、スルファニル基を有するアリール基、又はスルフ
ァニル基を有するアシル基としては、例えば、［（３−スルファニルプロパノイル）オキ
シ］エチル基、［（２−スルファニルアセチル）オキシ］エチル基、４−（スルファニル
メチル）フェニル基、［（３−スルファニルプロパノイル）オキシ］プロピル基、３−ス
ルファニル［（３−スルファニルプロパノイル）オキシ］エチル基、又は｛［（２−スル
ファニルエトキシ）プロパノイル］オキシ｝エチル基等が挙げられる。
Examples of the alkyl group having a sulfanyl group, the aryl group having a sulfanyl group, or the acyl group having a sulfanyl group include [(3-sulfanylpropanoyl) oxy] ethyl group and [(2-sulfanylacetyl) oxy] ethyl group. , 4- (Sulfanylmethyl) phenyl group, [(3-sulfanylpropanoyl) oxy] propyl group, 3-sulfanyl [(3-sulfanylpropanoyl) oxy] ethyl group, or {[(2-sulfanylethoxy) propanoyl] Oxy} ethyl group and the like can be mentioned.
一般式（１）〜（３）で表されるリガンドの具体例を以下に示すが、これらに限定され
るものではない。なお、下記構造式において、シス型及びトランス型の幾何異性体が存在
する場合は、シス型であってもよく、トランス型であってもよく、シス型及びトランス型
の異性体混合物であってもよい。シン−アンチの幾何異性についても同様である。
Specific examples of the ligands represented by the general formulas (1) to (3) are shown below, but the present invention is not limited thereto. In the following structural formula, when cis-type and trans-type geometric isomers are present, they may be cis-type, trans-type, or a mixture of cis-type and trans-type isomers. May be good. The same applies to the thin-anti geometric isomerism.
［電子輸送性リガンド］
電子輸送性リガンドは、半導体粒子表面への吸着部位と、電子輸送する機能を持つ電子
輸送性部位からなる。吸着部位と電子輸送性部位は完全に分離している必要は無く、例え
ば、電子輸送性部位の一部が吸着部位となっていても良い。吸着部位としては、正孔輸送
性リガンドの項で説明したものと同じものが挙げられる。加えて、２，２’−ビピリジン
骨格や８−キノリノール骨格等も吸着部位として使用できる。
[Electron-transporting ligand]
The electron-transporting ligand consists of an adsorption site on the surface of semiconductor particles and an electron-transporting site having an electron-transporting function. The adsorption site and the electron transporting site do not have to be completely separated. For example, a part of the electron transporting site may be an adsorption site. Examples of the adsorption site include those described in the section on hole-transporting ligands. In addition, a 2,2'-bipyridine skeleton, an 8-quinolinol skeleton, or the like can also be used as an adsorption site.
なお、上述の正孔輸送性部位及び電子輸送性部位に、同一の構造が含まれているが、こ
れは、電子輸送性部位と正孔輸送性部位のどちらにもなりえるためである。リガンドが正
孔輸送性又は電子輸送性のどちらとして振る舞うかは、正孔輸送性リガンドと電子輸送性
リガンドの相対的な最高被占軌道（ＨＯＭＯ）のエネルギー準位と最低空軌道（ＬＵＭＯ
）のエネルギー準位の関係、及び電界発光素子で用いられる他の化合物との相対的なＨＯ
ＭＯのエネルギー準位及びＬＵＭＯのエネルギー準位の関係によって決まり、さらに、特
定の構造であっても、電子吸引性や電子供与性の置換基の存在によりＨＯＭＯのエネルギ
ー準位やＬＵＭＯのエネルギー準位は変化する。以下に示す化合物及びその誘導体から水
素原子を一つ以上除いた有機残基は、電子輸送性部位として機能し得るが、電子輸送性部
位はこれらに限定されるものではない。
The hole-transporting site and the electron-transporting site described above contain the same structure, because they can be both an electron-transporting site and a hole-transporting site. Whether the ligand behaves as hole-transporting or electron-transporting depends on the energy level and the lowest empty orbital (LUMO) of the relative highest occupied molecular orbital (HOMO) between the hole-transporting ligand and the electron-transporting ligand.
) Energy level relationship and relative HO with other compounds used in electroluminescent devices
It is determined by the relationship between the energy level of MO and the energy level of LUMO, and even if it has a specific structure, the energy level of HOMO and the energy level of LUMO are determined by the presence of electron-withdrawing and electron-donating substituents. Changes. The organic residues obtained by removing one or more hydrogen atoms from the compounds and derivatives thereof shown below can function as electron-transporting sites, but the electron-transporting sites are not limited thereto.
本発明の光電変換材料において、正孔輸送性リガンドのＨＯＭＯのエネルギー準位は、
−６．５ｅＶ以上−４．６ｅＶ以下であることが好ましい。また、電子輸送性リガンドの
ＬＵＭＯエネルギー準位は、−４．５ｅＶ以上−２．５ｅＶ以下であることが好ましい。
また、正孔輸送性リガンドのＨＯＭＯのエネルギー準位は、電子輸送性リガンドのＨＯ
ＭＯのエネルギー準位よりも０．２ｅＶ以上大きいことが好ましい。また、正孔輸送性リ
ガンドのＬＵＭＯのエネルギー準位は、電子輸送性リガンドのＬＵＭＯのエネルギー準位
よりも０．２ｅＶ以上大きいことが好ましい。
In the photoelectric conversion material of the present invention, the energy level of HOMO of the hole transporting ligand is
It is preferably −6.5 eV or more and −4.6 eV or less. The LUMO energy level of the electron transporting ligand is preferably −4.5 eV or more and −2.5 eV or less.
The energy level of HOMO of the hole-transporting ligand is the HO of the electron-transporting ligand.
It is preferably 0.2 eV or more higher than the energy level of MO. Further, the energy level of LUMO of the hole-transporting ligand is preferably 0.2 eV or more higher than the energy level of LUMO of the electron-transporting ligand.
正孔輸送性リガンド及び電子輸送性リガンドの、ＨＯＭＯのエネルギー及び／又はＬＵ
ＭＯのエネルギーが上述の条件を満たす場合、光電変換素子中での電子や正孔の輸送や半
導体粒子からの電子や正孔の取出しを優れたものとすることができ、高性能な光電変換素
子が得られるため好ましい
HOMO energy and / or LU of hole-transporting and electron-transporting ligands
When the energy of MO satisfies the above conditions, the transport of electrons and holes in the photoelectric conversion element and the extraction of electrons and holes from the semiconductor particles can be excellent, and the photoelectric conversion element has high performance. Is preferable because
＜光電変換素子＞
本発明の光電変換素子は、一対の電極間に光電変換層を有するものである。光電変換層
は、電荷分離に寄与し、電磁波（主として光）の吸収によって生じた電子及び正孔をそれ
ぞれ反対方向の電極に向かって輸送する機能を有しているが、本発明に用いられる光電変
換層は、本発明の光電変換材料を含んでなる。また、本発明の光電変換素子において、公
知の光電変換素子の構成を適用することができる。
<Photoelectric conversion element>
The photoelectric conversion element of the present invention has a photoelectric conversion layer between a pair of electrodes. The photoelectric conversion layer has a function of contributing to charge separation and transporting electrons and holes generated by absorption of electromagnetic waves (mainly light) toward electrodes in opposite directions. The photoelectric conversion layer used in the present invention has a function of transporting electrons and holes in opposite directions. The conversion layer comprises the photoelectric conversion material of the present invention. Further, in the photoelectric conversion element of the present invention, a known configuration of the photoelectric conversion element can be applied.
光電変換素子は、光電変換効率の向上などを目的に、電極と半導体粒子のエネルギー的
なマッチングや半導体粒子から成る光電変換層の作製方法などによってさまざまな形の素
子構造が提案されている。例えば、以下に示す公知の構成からなる光電変換素子を作製す
ることができる。
For the purpose of improving the photoelectric conversion efficiency, various types of element structures have been proposed for the photoelectric conversion element, depending on the energy matching between the electrode and the semiconductor particles and the method for producing the photoelectric conversion layer composed of the semiconductor particles. For example, a photoelectric conversion element having the known configuration shown below can be manufactured.
１．ショットキー型光電変換素子
電子供与性（ｐ型）又は電子受容性（ｎ型）の半導体粒子と電極との界面において形
成されるショットキー障壁を利用し、光起電力を得る光電変換素子である。例えば、ｐ型
の光電変換層を用いた場合には、一対の電極の内仕事関数が小さいほうの電極との界面
にショットキー障壁が形成され、その界面に電荷分離が生じ光電変換が行われる。
1. 1. Schottky type photoelectric conversion element A photoelectric conversion element that obtains photovoltaic power by using a Schottky barrier formed at the interface between an electron-donating (p-type) or electron-accepting (n-type) semiconductor particle and an electrode. .. For example, when a p-type photoelectric conversion layer is used, a Schottky barrier is formed at the interface between the pair of electrodes and the electrode having the smaller internal work function, and charge separation occurs at the interface to perform photoelectric conversion. ..
２．バイレイヤーヘテロ接合型光電変換素子
一対の電極の間に、電子供与性（ｐ型）及び電子受容性（ｎ型）の半導体粒子やその他
の半導体材料を個々に形成し、ｐｎ接合界面に光電荷分離を生じさせ光電流を得る光電変
換素子である。
2. Bilayer heterojunction photoelectric conversion element Electron-donating (p-type) and electron-accepting (n-type) semiconductor particles and other semiconductor materials are individually formed between a pair of electrodes, and light charges are applied to the pn junction interface. It is a photoelectric conversion element that causes separation and obtains a photocurrent.
３．バルクヘテロ接合型光電変換素子
一対の電極の間に、電子供与性（ｐ型）及び電子受容性（ｎ型）の半導体粒子やその他
の半導体材料を任意の比率で混合させ有機半導体層を形成する。この際、ｐ型及びｎ型の
材料は均一に分散していても、不均一であっても構わない。個々のｐ型材料、ｎ型材料が
形成する界面で光電荷分離が起こるため、バイレイヤーヘテロ接合型よりもｐｎ接合を広
く形成させることが出来る。
3. 3. Bulk heterojunction type photoelectric conversion element An organic semiconductor layer is formed by mixing electron-donating (p-type) and electron-accepting (n-type) semiconductor particles and other semiconductor materials at an arbitrary ratio between a pair of electrodes. At this time, the p-type and n-type materials may be uniformly dispersed or non-uniform. Since photocharge separation occurs at the interface formed by each p-type material and n-type material, the pn junction can be formed wider than the bilayer heterojunction type.
＜電極＞
光電変換素子を構成する一対の電極の内、少なくとも一つは光を透過することが好まし
い。具体的な例としては、酸化スズ、酸化亜鉛、酸化インジウム、酸化インジウムスズ（
ＩＴＯ）等の導電性金属酸化物、あるいは金、銀、白金、クロム、ニッケル、リチウム、
インジウム、アルミニウム、カルシウム、マグネシウム等の金属、さらにこれらの金属と
導電性金属酸化物との混合物又は積層物などが挙げられる。
<Electrode>
It is preferable that at least one of the pair of electrodes constituting the photoelectric conversion element transmits light. Specific examples include tin oxide, zinc oxide, indium oxide, and indium tin oxide (
Conductive metal oxides such as ITO), or gold, silver, platinum, chromium, nickel, lithium,
Examples thereof include metals such as indium, aluminum, calcium and magnesium, and mixtures or laminates of these metals and conductive metal oxides.
電極の形状としては、フラットな形状が一般的であるが、エネルギー変換効率を向上さ
せるために、波型、ピラミッド型、くし型等の形状であっても良い。これら電極の形成方
法としては、一般的な電極の形成方法を用いることができ、真空蒸着法、スパッタリング
法、イオンプレーティング法等のＰＶＤ法、ＣＶＤ法、化学反応法（ゾルゲル法など）、
キャスト法、スプレーコーティング法、インクジェット法、スピンコート法などを挙げる
ことができる。
The shape of the electrode is generally flat, but may be corrugated, pyramid, comb, or the like in order to improve energy conversion efficiency. As a method for forming these electrodes, a general electrode forming method can be used, and PVD methods such as vacuum deposition method, sputtering method, ion plating method, CVD method, chemical reaction method (sol-gel method, etc.),
Examples thereof include a casting method, a spray coating method, an inkjet method, and a spin coating method.
光電変換素子は、一対の電極の間に光電変換層以外の層を備えていてもよく、正孔注入
層、正孔輸送層、電子輸送層、及び／又は、電子注入層を有していてもよい。
The photoelectric conversion element may include a layer other than the photoelectric conversion layer between the pair of electrodes, and has a hole injection layer, a hole transport layer, an electron transport layer, and / or an electron injection layer. May be good.
＜正孔注入層＞
正孔注入層には、光電変換層に対して優れた正孔注入効果を示し、かつ陽極界面との密
着性と薄膜形成性に優れた正孔注入層を形成できる正孔注入材料が用いられる。また、こ
のような材料を多層積層させ、正孔注入効果の高い材料と正孔輸送効果の高い材料とを多
層積層させた場合、それぞれに用いる材料を正孔注入材料、正孔輸送材料と呼ぶことがあ
る。これら正孔注入材料や正孔輸送材料は、正孔移動度が大きく、イオン化エネルギーが
通常５．５ｅＶ以下と小さい必要がある。このような正孔注入層としては、より低い電界
強度で正孔を発光層に輸送する材料が好ましく、更に正孔の移動度が、例えば１０4〜１
０6Ｖ／ｃｍの電界印加時に、少なくとも１０-6ｃｍ2／Ｖ・秒であるものが好ましい。正
孔注入材料及び正孔輸送材料としては、上記の好ましい性質を有するものであれば特に制
限はなく、従来、光導伝材料において正孔の電荷輸送材料として慣用されているものや、
有機ＥＬ素子の正孔注入層に使用されている公知のものの中から任意のものを選択して用
いることができる。
<Hole injection layer>
For the hole injection layer, a hole injection material that exhibits an excellent hole injection effect on the photoelectric conversion layer and can form a hole injection layer having excellent adhesion to the anode interface and thin film formation is used. .. Further, when such a material is laminated in multiple layers and a material having a high hole injection effect and a material having a high hole transport effect are laminated in multiple layers, the materials used for each are referred to as a hole injection material and a hole transport material. Sometimes. These hole injection materials and hole transport materials need to have a large hole mobility and a small ionization energy of usually 5.5 eV or less. For the hole injecting layer is preferably made of a material which can transport holes to the emitting layer at a lower electric field intensity, further hole mobility is, for example, 10 4 to 1
0 at 6 V / cm electric field is applied, those that are least 10 -6 cm 2 / V · sec is preferred. The hole injecting material and the hole transporting material are not particularly limited as long as they have the above-mentioned preferable properties.
Any known material used for the hole injection layer of the organic EL element can be selected and used.
このような正孔注入材料や正孔輸送材料としては、例えば、カルバゾール誘導体、ポリ
アリールアルカン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置
換カルコン誘導体、スチリルアントラセン誘導体、フルオレン誘導体、ヒドラゾン誘導体
、スチルベン誘導体、シラザン誘導体、芳香族第三級アミン化合物、スチリルアミン化合
物、芳香族ジメチリディン系化合物、ポルフィリン系化合物、フタロシアニン系化合物、
オリゴチオフェン誘導体、ポリチオフェン誘導体、ポリピロール誘導体、及びポリパラフ
ェニレンビニレン誘導体などが挙げられる。
Examples of such hole injection materials and hole transport materials include carbazole derivatives, polyarylalkane derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted calcon derivatives, styrylanthracene derivatives, fluorene derivatives, hydrazone derivatives, and stillben derivatives. , Cilazan derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethidyldin-based compounds, porphyrin-based compounds, phthalocyanine-based compounds,
Examples thereof include oligothiophene derivatives, polythiophene derivatives, polypyrrole derivatives, and polyparaphenylene vinylene derivatives.
更に、正孔注入層に使用できる材料としては、酸化モリブデン（ＭоＯx）、酸化バナ
ジウム（ＶＯX）、酸化ルテニウム（ＲｕＯX）、酸化銅（ＣｕＯX）、酸化タングステン
（ＷＯX）、酸化イリジウム（ＩｒＯX）等の無機酸化物及びそれらのドープ体も挙げられ
る。
Further, as materials that can be used for the hole injection layer, molybdenum oxide (MоOx), vanadium oxide (VO X ), ruthenium oxide (RuO X ), copper oxide (CuO X ), tungsten oxide (WO X ), and iridium oxide (Iridium oxide) IrO X) inorganic oxides and their doped body such may be mentioned.
正孔注入層を形成するには、上述の化合物を、例えば真空蒸着法、スピンコート法、キ
ャスト法、ラングミュア−ブロジェット法（ＬＢ法）等の公知の方法により薄膜化する。
正孔注入層の膜厚は、特に制限はないが、通常は５ｎｍ〜５μｍである。
To form the hole injection layer, the above-mentioned compound is thinned by a known method such as a vacuum deposition method, a spin coating method, a casting method, or a Langmuir-Bloget method (LB method).
The film thickness of the hole injection layer is not particularly limited, but is usually 5 nm to 5 μm.
＜電子注入層＞
電子注入層には、光電変換層に対して優れた電子注入効果を示し、かつ陰極界面との密
着性と薄膜形成性に優れた電子注入層を形成できる電子注入材料が用いられる。また、こ
のような材料を多層積層させ、電子注入効果の高い材料と電子輸送効果の高い材料とを多
層積層させた場合、それぞれに用いる材料を電子注入材料、電子輸送材料と呼ぶことがあ
る。そのような電子注入材料の例としては、金属錯体化合物、含窒素五員環誘導体、フル
オレノン誘導体、アントラキノジメタン誘導体、ジフェノキノン誘導体、チオピランジオ
キシド誘導体、ペリレンテトラカルボン酸誘導体、フレオレニリデンメタン誘導体、アン
トロン誘導体、シロール誘導体、トリアリールホスフィンオキシド誘導体、ポリキノリン
及びその誘導体、ポリキノキサリン及びその誘導体、ポリフルオレン及びその誘導体、カ
ルシウムアセチルアセトナート、酢酸ナトリウム等が挙げられる。また、セシウム等の金
属をバソフェナントロリンにドープした無機／有機複合材料（高分子学会予稿集，第５０
巻，４号，６６０頁，２００１年発行）や、第５０回応用物理学関連連合講演会講演予稿
集、Ｎｏ．３、１４０２頁、２００３年発行記載のＢＣＰ、ＴＰＰ、Ｔ５ＭＰｙＴＺ等も
電子注入材料の例として挙げられるが、素子作成に必要な薄膜を形成し、陰極からの電子
を注入できて、電子を輸送できる材料であれば、特にこれらに限定されるものではない。
<Electron injection layer>
As the electron injection layer, an electron injection material that exhibits an excellent electron injection effect on the photoelectric conversion layer and can form an electron injection layer having excellent adhesion to the cathode interface and thin film formation is used. Further, when such a material is laminated in multiple layers and a material having a high electron injection effect and a material having a high electron transport effect are laminated in multiple layers, the materials used for each may be referred to as an electron injection material and an electron transport material. Examples of such electron-injected materials include metal complex compounds, nitrogen-containing five-membered ring derivatives, fluorenone derivatives, anthracinodimethane derivatives, diphenoquinone derivatives, thiopyrandioxide derivatives, perylenetetracarboxylic acid derivatives, fleolenilidenemethane. Examples thereof include derivatives, anthron derivatives, silol derivatives, triarylphosphine oxide derivatives, polyquinolin and its derivatives, polyquinoxalin and its derivatives, polyfluorene and its derivatives, calcium acetylacetonate, sodium acetate and the like. Inorganic / organic composite materials obtained by doping vasofenanthroline with a metal such as cesium (Proceedings of the Society of Polymer Science, No. 50).
Vol. 4, No. 4, p. 660, published in 2001) and Proceedings of the 50th Joint Lecture on Applied Physics, No. BCP, TPP, T5MPyTZ, etc. described on page 3, 1402, published in 2003 are also mentioned as examples of electron injection materials, but can form a thin film necessary for device fabrication, inject electrons from a cathode, and transport electrons. As long as it is a material, it is not particularly limited to these.
更に、電子注入層に使用できる材料としては、酸化亜鉛（ＺｎＯx）、酸化チタン（Ｔ
ｉＯx）、等の無機酸化物及びそれらのドープ体、さらに、フッ化リチウム（ＬｉＦ）、
フッ化セシウム（ＣｓＦ）などのアルカリ金属のフッ化物も挙げられる。
Further, as materials that can be used for the electron injection layer, zinc oxide (ZnOx) and titanium oxide (T)
Inorganic oxides such as iOx) and their dope, as well as lithium fluoride (LiF),
Alkali metal fluorides such as cesium fluoride (CsF) can also be mentioned.
光電変換素子は、光電変換素子を構成する各層以外に、その他の構成部材を備えていて
も良い。例えば、紫外線を透過させない光学膜（フィルタ）を備えていても良い。紫外線
は、エネルギーが高いため光電変換素子を構成する材料を劣化させる一因となる。この紫
外線を遮断することにより、素子を長寿命化させることができる。
The photoelectric conversion element may include other constituent members in addition to the layers constituting the photoelectric conversion element. For example, an optical film (filter) that does not transmit ultraviolet rays may be provided. Ultraviolet rays have high energy and therefore contribute to deterioration of materials constituting the photoelectric conversion element. By blocking this ultraviolet ray, the life of the device can be extended.
外部からの衝撃に対して光電変換層を保護する目的で、保護膜を備えていても良い。保
護膜は、例えば、スチレン樹脂、エポキシ樹脂、アクリル樹脂、ポリウレタン、ポリイミ
ド、ポリビニルアルコール、ポリフッ化ビニリデン、ポリエチレンポリビニルアルコール
共重合体等のポリマー膜、酸化珪素、窒化珪素、酸化アルミニウム等の無機酸化膜や窒化
膜、アルミニウム等の金属板もしくは金属箔、あるいはこれらの積層膜などにより構成す
ることができる。なお、これらの保護膜の材料は、１種のみを用いてもよく、２種以上を
も良い。
A protective film may be provided for the purpose of protecting the photoelectric conversion layer from an external impact. The protective film is, for example, a polymer film such as styrene resin, epoxy resin, acrylic resin, polyurethane, polyimide, polyvinyl alcohol, polyvinylidene fluoride, polyethylene polyvinyl alcohol copolymer, or an inorganic oxide film such as silicon oxide, silicon nitride, or aluminum oxide. It can be composed of a nitride film, a metal plate such as aluminum or a metal foil, or a laminated film thereof. As the material of these protective films, only one kind may be used, or two or more kinds may be used.
一般に半導体粒子は、空気中の水分や酸素により劣化を招くといわれている。それを防
ぐため、バリア膜を備えていても良い。例えば、金属又は無機酸化物が好ましく、Ｔｉ、
Ａｌ、Ｍｇ、Ｚｒ、酸化珪素、酸化アルミニウム、酸化窒化珪素、酸化窒化アルミニウム
、酸化マグネシウム、酸化亜鉛、酸化インジウム、酸化スズ、酸化イットリウム、酸化ホ
ウ素、酸化カルシウム等を挙げることができる。これら各種機能性膜を積層させる順番は
特になく、これらの機能を併せ持つ機能性膜を用いても良い。
Generally, it is said that semiconductor particles are deteriorated by moisture and oxygen in the air. A barrier membrane may be provided to prevent this. For example, metals or inorganic oxides are preferred, Ti,
Examples thereof include Al, Mg, Zr, silicon oxide, aluminum oxide, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, yttrium oxide, boron oxide and calcium oxide. There is no particular order in which these various functional films are laminated, and a functional film having these functions may be used.
以下、本発明について、実施例に基づき具体的に説明する。特に断りのない限り、「部
」は「質量部」、「％」は「質量％」を表す。また、特に断りのない限り、全ての測定は
２５℃で行った。
Hereinafter, the present invention will be specifically described based on examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". Unless otherwise specified, all measurements were performed at 25 ° C.
＜半導体粒子ＰｂＳ−０の調製＞
まず、硫黄源溶液として、単体硫黄０．４０部とオレイルアミン６．０部を反応容器中
、窒素雰囲気下、１２０℃に加熱して均一な溶液をした後、２５℃に冷却した。次に、鉛
源溶液として、塩化鉛０．３２部、オレイルアミン６．０部を別の反応容器中、窒素雰囲
気下、１２０℃に加熱した。その後、鉛源溶液を４０℃に調製した後、上記の硫黄源溶液
１．８部を一気に加えた。３０秒間反応させた後、容器を氷浴に漬けて急冷した後、ヘキ
サン１３部で希釈した。遠心分離（４０００ｒｐｍ、５分間）を行って未反応の原料を除
去した後、ブタノール：メタノール＝２：１（体積比）からなる混合液を１２部加えて半
導体粒子を沈降させ、遠心分離（４０００ｒｐｍ、５分間）を行い半導体粒子を回収した
。その後、ヘキサン：オレイン酸＝１：２（体積比）からなる混合液を２４部加えて３０
分間攪拌し、遠心分離を行い、上澄みを回収した。半導体粒子沈降、再分散、不純物沈降
を更に２回繰り返し、最後に半導体粒子を沈降させ、真空乾燥した後、ｎ−オクタンを用
いて固形分濃度５％に調製し、半導体粒子ＰｂＳ−０を得た（平均粒径３．５ｎｍ）。
<Preparation of semiconductor particles PbS-0>
First, as a sulfur source solution, 0.40 parts of elemental sulfur and 6.0 parts of oleylamine were heated to 120 ° C. in a nitrogen atmosphere in a reaction vessel to form a uniform solution, and then cooled to 25 ° C. Next, as a lead source solution, 0.32 parts of lead chloride and 6.0 parts of oleylamine were heated to 120 ° C. in another reaction vessel under a nitrogen atmosphere. Then, after preparing the lead source solution at 40 ° C., 1.8 parts of the above sulfur source solution was added at once. After reacting for 30 seconds, the container was immersed in an ice bath to quench it, and then diluted with 13 parts of hexane. After removing the unreacted raw material by centrifugation (4000 rpm, 5 minutes), 12 parts of a mixed solution of butanol: methanol = 2: 1 (volume ratio) was added to precipitate the semiconductor particles, and the semiconductor particles were centrifuged (4000 rpm). 5 minutes) to recover the semiconductor particles. Then, 24 parts of a mixed solution consisting of hexane: oleic acid = 1: 2 (volume ratio) was added to 30 parts.
The mixture was stirred for 1 minute, centrifuged, and the supernatant was collected. Semiconductor particle precipitation, redispersion, and impurity precipitation were repeated twice, and finally the semiconductor particles were precipitated and vacuum dried, and then adjusted to a solid content concentration of 5% using n-octane to obtain semiconductor particles PbS-0. (Average particle size 3.5 nm).
＜半導体粒子ＰｂＳｅ−０の合成＞
鉛源溶液として、酸化鉛０．２２部、オレイン酸０．７３部、１−オクタデセン１０部
を反応容器中、窒素雰囲気下、１５０℃に加熱した。その後、１Mトリオクチルホスフィ
ン-セレン溶液を２．５部とジフェニルホスフィン０．０２８部からなる混合物を素早く
加え、反応溶液を１８０℃に加熱した後、１６０℃に保温し、２分間反応させたあと、反
応溶液を急冷した。１０部のヘキサンで希釈した後、アセトンで沈殿させた。沈殿物をア
セトンで5回洗浄し、真空乾燥させて半導体粒子ＰｂＳｅ−０を得た（平均粒径２．７ｎ
ｍ）。
<Semiconductor particle PbSe-0 synthesis>
As a lead source solution, 0.22 parts of lead oxide, 0.73 parts of oleic acid, and 10 parts of 1-octadecene were heated to 150 ° C. in a reaction vessel under a nitrogen atmosphere. Then, a mixture of 2.5 parts of 1M trioctylphosphine-selenium solution and 0.028 parts of diphenylphosphine was quickly added, the reaction solution was heated to 180 ° C., kept at 160 ° C., and reacted for 2 minutes. , The reaction solution was quenched. After diluting with 10 parts of hexane, it was precipitated with acetone. The precipitate was washed with acetone 5 times and vacuum dried to obtain semiconductor particles PbSe-0 (average particle size 2.7 n).
m).
＜半導体粒子Ａｇ2Ｓ−０の合成＞
０．０４部のオレイン酸銀と、８部のオクタンチオールと、４部のドデシルアミンとを
反応容器中、Ａｒ雰囲気下、２００℃で０．５時間加熱した。この溶液を室温に放冷した
後、４０部の無水エタノールを添加した。得られた混合物を遠心分離し、真空乾燥させて
半導体粒子Ａｇ2Ｓ−０を得た（平均粒径２．５ｎｍ）。
<Semiconductor particle Ag 2 S-0 synthesis>
0.04 parts of silver oleate, 8 parts of octanethiol, and 4 parts of dodecylamine were heated in a reaction vessel at 200 ° C. for 0.5 hours in an Ar atmosphere. After allowing this solution to cool to room temperature, 40 parts of absolute ethanol was added. The obtained mixture was centrifuged and vacuum dried to obtain semiconductor particles Ag 2 S-0 (average particle size 2.5 nm).
＜半導体粒子ＰｂＳ−１＞
半導体粒子ＰｂＳ−０を固形分濃度１％のトルエン溶液に調製した。調製した溶液１部
と表１記載の正孔輸送性リガンド（１）の５％のトルエン溶液１部とを混合した後、１２
時間撹拌した。トルエンとエタノールを用いて再沈殿法で精製を行った。沈殿を真空乾燥
し、トルエンの１０質量％溶液として、半導体粒子ＰｂＳ−１を調製した。
<Semiconductor particles PbS-1>
Semiconductor particles PbS-0 were prepared in a toluene solution having a solid content concentration of 1%. After mixing 1 part of the prepared solution and 1 part of a 5% toluene solution of the hole transporting ligand (1) shown in Table 1, 12
Stir for hours. Purification was carried out by the reprecipitation method using toluene and ethanol. The precipitate was vacuum dried to prepare semiconductor particles PbS-1 as a 10% by mass solution of toluene.
＜半導体粒子ＰｂＳ−２〜８＞
正孔輸送性リガンド（１）を表１記載の正孔輸送性リガンド（２）〜（６）及び電子輸
送性リガンド（７）、（８）にそれぞれ変えた以外は半導体粒子ＰｂＳ−１と同様にして
ＰｂＳ−２〜８をそれぞれ調製した。
<Semiconductor particles PbS-2 to 8>
Similar to semiconductor particles PbS-1 except that the hole-transporting ligand (1) was changed to the hole-transporting ligands (2) to (6) and the electron-transporting ligands (7) and (8) shown in Table 1, respectively. PbS-2 to 8 were prepared respectively.
＜半導体粒子ＰｂＳ−９＞
表面処理剤をベンゼンチオールに変えた以外は半導体粒子ＰｂＳ−１と同様にしてＰｂ
Ｓ−９を調製した。
<Semiconductor particles PbS-9>
Pb in the same manner as the semiconductor particles PbS-1 except that the surface treatment agent was changed to benzenethiol.
S-9 was prepared.
＜半導体粒子ＰｂＳｅ−１＞
半導体粒子ＰｂＳｅ−０を固形分濃度１％のトルエン溶液に調製した。調製した溶液１
部と表１記載の正孔輸送性リガンド（１）の５％のトルエン溶液１部とを混合した後、１
２時間撹拌した。トルエンとエタノールを用いて再沈殿法で精製を行った。沈殿を真空乾
燥し、トルエンの１０質量％溶液として、半導体粒子ＰｂＳｅ−１を調製した。
<Semiconductor particles PbSe-1>
Semiconductor particles PbSe-0 were prepared in a toluene solution having a solid content concentration of 1%. Prepared solution 1
1 part after mixing 1 part with 1 part of a 5% toluene solution of the hole transporting ligand (1) shown in Table 1.
The mixture was stirred for 2 hours. Purification was carried out by the reprecipitation method using toluene and ethanol. The precipitate was vacuum dried to prepare semiconductor particles PbSe-1 as a 10% by mass solution of toluene.
＜半導体粒子ＰｂＳｅ−２〜８＞
正孔輸送性リガンド（１）を表１記載の正孔輸送性リガンド（２）〜（６）及び電子輸
送性リガンド（７）、（８）にそれぞれ変えた以外は半導体粒子ＰｂＳｅ−１と同様にし
てＰｂＳｅ−２〜８をそれぞれ調製した。
<Semiconductor particles PbSe-2 to 8>
Similar to the semiconductor particle PbSe-1 except that the hole transporting ligand (1) was changed to the hole transporting ligands (2) to (6) and the electron transporting ligands (7) and (8) shown in Table 1, respectively. PbSe-2 to 8 were prepared respectively.
＜半導体粒子Ａｇ2Ｓ−１の調整＞
半導体粒子Ａｇ2Ｓ−０を固形分濃度１％のトルエン溶液に調製した。調製した溶液１
部と表１記載の正孔輸送性リガンド（１）の５％のトルエン溶液１部とを混合した後、１
２時間撹拌した。トルエンとエタノールを用いて再沈殿法で精製を行った。沈殿を真空乾
燥し、トルエンの１０質量％溶液として、半導体粒子Ａｇ2Ｓ−１を調製した。
<Adjustment of semiconductor particles Ag 2 S-1>
Was prepared semiconductor particles Ag 2 S-0 to a solid concentration of 1% toluene solution. Prepared solution 1
1 part after mixing 1 part with 1 part of a 5% toluene solution of the hole transporting ligand (1) shown in Table 1.
The mixture was stirred for 2 hours. Purification was carried out by the reprecipitation method using toluene and ethanol. The precipitate was vacuum dried to prepare semiconductor particles Ag 2 S-1 as a 10 mass% solution of toluene.
＜半導体粒子Ａｇ2Ｓ−２〜８＞
正孔輸送性リガンド（１）を表１記載の正孔輸送性リガンド（２）〜（６）及び電子輸
送性リガンド（７）、（８）にそれぞれ変えた以外は半導体粒子Ａｇ2Ｓ−１と同様にし
てＡｇ2Ｓ−２〜８をそれぞれ調製した。
<Semiconductor particles Ag 2 S-2 to 8>
Semiconductor particles Ag 2 S-1 except that the hole-transporting ligand (1) was changed to the hole-transporting ligands (2) to (6) and the electron-transporting ligands (7) and (8) shown in Table 1, respectively. Ag 2 S-2 to 8 were prepared in the same manner as in the above.
＜リガンドのＨＯＭＯのエネルギー準位及びＬＵＭＯのエネルギー準位の測定＞
以下の評価方法で、正孔輸送性リガンド及び電子輸送性リガンドの、ＨＯＭＯのエネル
ギー準位及びＬＵＭＯのエネルギー準位を測定した。
<Measurement of HOMO energy level and LUMO energy level of ligand>
The energy level of HOMO and the energy level of LUMO of the hole-transporting ligand and the electron-transporting ligand were measured by the following evaluation methods.
（ＨＯＭＯのエネルギー準位）
ＨＯＭＯのエネルギー準位の測定は、光電子収量分光装置ＰＹＳ−２０２（住友重機械
メカトロニクス社製）を用いて行った。ＩＴＯ（酸化インジウム錫）付のガラス基板上に
、導電性カーボン両面テープ（不織布基材、日進ＥＭ社製）を貼り付け、その上に評価対
象のリガンド粉末を付着させてサンプルを形成した。ＩＴＯ表面でアースを取り、カーボ
ン両面テープ上の評価対象の化合物粉末に対してプローブ光を照射して測定を行った。測
定範囲は：４．０〜７．０（ｅＶ）、測定間隔：０．１（ｅＶ）、測定雰囲気：真空中（
１０-2（Ｐａ）台）とした。
(HOMO energy level)
The energy level of HOMO was measured using a photoelectron yield spectroscope PYS-202 (manufactured by Sumitomo Heavy Industries Mechatronics). A conductive carbon double-sided tape (nonwoven fabric base material, manufactured by Nissin EM Co., Ltd.) was attached onto a glass substrate with ITO (indium tin oxide), and a ligand powder to be evaluated was attached thereto to form a sample. The surface of the ITO was grounded, and the compound powder to be evaluated on the carbon double-sided tape was irradiated with probe light for measurement. Measurement range: 4.0 to 7.0 (eV), measurement interval: 0.1 (eV), measurement atmosphere: in vacuum (
10-2 (Pa) level).
（ＬＵＭＯのエネルギー準位）
ＬＵＭＯエネルギー準位は、吸収スペクトルの吸収端からバンドギャップを見積り、前
述の方法で測定したＨＯＭＯの値とバンドギャップの値より算出を行った。吸収スペクト
ルは、トルエンを用いて１０-5（ｍｏｌ／Ｌ）の濃度に調整し、光路長１ｃｍの石英セル
を用いて測定した。用いた正孔輸送性リガンド及び電子輸送性リガンドのＨＯＭＯのエネ
ルギー準位及びＬＵＭＯのエネルギー準位の測定値を表１に示す。
(LUMO energy level)
The LUMO energy level was calculated from the HOMO value and the bandgap value measured by the above method by estimating the bandgap from the absorption edge of the absorption spectrum. The absorption spectrum was adjusted to a concentration of 10-5 (mol / L) using toluene, and measured using a quartz cell having an optical path length of 1 cm. Table 1 shows the measured values of the HOMO energy level and the LUMO energy level of the hole-transporting ligand and the electron-transporting ligand used.
＜光電変換材料の調整＞
＜実施例１＞
半導体粒子（Ａ１）としてＰｂＳ−１を、半導体粒子（Ａ２）としてＰｂＳ−７を選定
し、１：１の質量比で混合することで、本発明の光電変換材料ＰｂＳ−Ｘ１を調製した。
<Adjustment of photoelectric conversion material>
<Example 1>
The photoelectric conversion material PbS-X1 of the present invention was prepared by selecting PbS-1 as the semiconductor particles (A1) and PbS-7 as the semiconductor particles (A2) and mixing them at a mass ratio of 1: 1.
＜実施例２〜２４＞
半導体粒子（Ａ１）及び半導体粒子（Ａ２）として表２に示したものを利用し、また、
（Ａ１）と（Ａ２）の混合比（質量比）を表２に示した値とした以外は、実施例１と同様
にして、本発明の光電変換材料ＰｂＳ−Ｘ２〜Ｘ８、ＰｂＳｅ−Ｘ１〜Ｘ８、Ａｇ2Ｓ−
Ｘ１〜Ｘ８を調製した。
<Examples 2 to 24>
The semiconductor particles (A1) and the semiconductor particles (A2) shown in Table 2 are used, and also.
The photoelectric conversion materials PbS-X2 to X8 and PbSe-X1 to the present invention are the same as in Example 1 except that the mixing ratio (mass ratio) of (A1) and (A2) is set to the value shown in Table 2. X8, Ag 2 S-
X1 to X8 were prepared.
＜比較例１＞
ＰｂＳ−９をそのまま用いた。
<Comparative example 1>
PbS-9 was used as it was.
上記光電変換材料を用い、以下の様にして光電変換素子を作製・評価した。
（光電変換素子の作製）
以下に光電変換素子の作製と評価について説明する。蒸着は、１０-6Ｔｏｒｒの真空中
にて基板の加熱や冷却等の温度制御は行わない条件下で行った。素子の評価は、素子面積
２ｍｍ×２ｍｍの光電変換素子を用いて測定した。まず、洗浄したＩＴＯ電極付きガラス
板上に、ＰＥＤＯＴ／ＰＳＳ（ポリ(３，４−エチレンジオキシ)−２，５−チオフェン／
ポリスチレンスルホン酸、Ｈｅｒａｅｕｓ社製ＣＬＥＶＩＯＵＳ（登録商標） ＰＶＰ
ＣＨ８０００）をスピンコート法にて塗工し、１１０℃にて２０分間乾燥させて、厚み３
５ｎｍの正孔注入層を得た。正孔注入層上に、光電変換層形成用組成物ＰｂＳ−１をスピ
ンコート法で塗工し、厚み１５０ｎｍの光電変換層を形成した。 次いで、光電変換層上
に、Ａｖａｎｔａｍａ社製ＺｎＯ分散液Ｎ−１０をスピンコートで製膜して厚み５０ｎｍ
の電子輸送層を形成した。次いで、電子輸送層上に、厚み２００ｎｍでアルミニウム（以
下、Ａｌ）を蒸着して電極を形成し、光電変換素子を得た。
Using the above photoelectric conversion material, a photoelectric conversion element was prepared and evaluated as follows.
(Manufacturing of photoelectric conversion element)
The production and evaluation of the photoelectric conversion element will be described below. The vapor deposition was carried out in a vacuum of 10-6 Torr under the condition that the temperature was not controlled such as heating and cooling of the substrate. The evaluation of the element was measured using a photoelectric conversion element having an element area of 2 mm × 2 mm. First, PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene /
Polystyrene sulfonic acid, CLEVIOUS® PVP manufactured by Heraeus
CH8000) is applied by a spin coating method, dried at 110 ° C. for 20 minutes, and has a thickness of 3
A 5 nm hole injection layer was obtained. The composition for forming a photoelectric conversion layer PbS-1 was applied onto the hole injection layer by a spin coating method to form a photoelectric conversion layer having a thickness of 150 nm. Next, a ZnO dispersion N-10 manufactured by Avantama was formed on the photoelectric conversion layer by spin coating to have a thickness of 50 nm.
Formed an electron transport layer. Next, aluminum (hereinafter referred to as Al) was vapor-deposited on the electron transport layer to a thickness of 200 nm to form an electrode to obtain a photoelectric conversion element.
（光電変換素子の評価）
得られた素子について、以下に示す方法によってＩ−Ｖ曲線を測定した。
Ｉ−Ｖ曲線は、Ｉ−Ｖ特性計測装置（ペクセル・テクノロジーズ株式会社製、ＰＥＣＫ２
４００−Ｎ）を用いて走査速度０．１Ｖ／ｓｅｃ（０．０１Ｖｓｔｅｐ）、電圧設定後待
ち時間５０ ｍｓｅｃ、測定積算時間５０ｍｓｅｃ、開始電圧−０．５Ｖ、終了電圧１．
１Ｖの条件で測定した。また、Ｉ−Ｖ曲線は、遮光状態と光照射状態で測定をおこなった
。キセノンランプ白色光を光源（ペクセル・テクノロジーズ株式会社製、ＰＥＣ―Ｌ０１
）とし、太陽光（ＡＭ１．５）相当の光強度（１００ ｍＷ／ｃｍ2）にて、光照射面積０
．０３６３ ｃｍ2（２ｍｍ角）のマスク下実施した。光照射状態のＩ−Ｖ曲線の印可電圧
０Ｖの電流密度である短絡電流密度ＩL（ｍＡ／ｃｍ2）、及び、遮光状態のＩ−Ｖ曲線よ
りの印可電圧−０．５Ｖでの電流である暗電流密度ＩD（μＡ／ｃｍ2）を表２に記す。Ｉ
Lは高いほど、ＩDは低いほど良好であるといえる。尚、表２中、「ＨＯＭＯ差」とは、｜
正孔輸送性リガンドのＨＯＭＯのエネルギー準位−電子輸送性リガンドのＨＯＭＯのエネ
ルギー準位｜を表し、「ＬＵＭＯ差」とは、｜正孔輸送性リガンドのＬＵＭＯのエネルギ
ー準位−電子輸送性リガンドのＬＵＭＯのエネルギー準位｜を表す。
(Evaluation of photoelectric conversion element)
The IV curve of the obtained device was measured by the method shown below.
The IV curve is an IV characteristic measuring device (manufactured by Pexel Technologies Co., Ltd., PECK2).
Using 400-N), the scanning speed is 0.1 V / sec (0.01 Vstep), the waiting time after voltage setting is 50 msec, the measurement integration time is 50 msec, the start voltage is -0.5 V, and the end voltage is 1.
It was measured under the condition of 1V. The IV curve was measured in a light-shielded state and a light irradiation state. Xenon lamp White light as a light source (manufactured by Pexel Technologies Co., Ltd., PEC-L01
), With a light intensity (100 mW / cm 2 ) equivalent to sunlight (AM1.5), the light irradiation area is 0.
.. It was carried out under a mask of 0363 cm 2 (2 mm square). Short-circuit current density is the current density of the applied voltage of 0V I-V curve of the light irradiation state I L (mA / cm 2) , and, in current at applied voltage -0.5V than I-V curve of the light-shielding state A dark current density ID (μA / cm 2 ) is shown in Table 2. I
It can be said that the higher the L and the lower the ID, the better. In Table 2, "HOMO difference" means |
HOMO energy level of hole transporting ligand-HOMO energy level of electron transporting ligand | "LUMO difference" means | LUMO energy level of hole transporting ligand-electron transporting ligand LUMO energy level |
本発明の光電変換素子（実施例１〜２４）は、いずれも比較例の素子よりも、高い短絡
電流密度ＩLと低い暗電流密度ＩDを示した。すなわち、比較例より感度や光電変換能が高
く、比較例より低いノイズであることが明らかとなった。本発明の光電変換材料は、正孔
輸送性リガンド（Ａ１）半導体粒子（Ａ１）及び半導体粒子（Ａ２）を含んでなることで
、光吸収で発生した励起子が効率よく乖離して輸送されることで光電変換能が高いと考え
られる。また、正孔輸送性リガンド（Ａ１）半導体粒子（Ａ１）及び半導体粒子（Ａ２）
を含んでなることで、光電変換層内でバルクヘテロのような状態が形成されることで整流
特性が強まり暗電流密度が抑制されたと考えられる。
The photoelectric conversion elements of the present invention (Examples 1 to 24) all showed a higher short-circuit current density IL and a lower dark current density ID than the elements of the comparative examples. That is, it was clarified that the sensitivity and photoelectric conversion ability were higher than those of the comparative example, and the noise was lower than that of the comparative example. The photoelectric conversion material of the present invention contains the hole transporting ligand (A1) semiconductor particles (A1) and the semiconductor particles (A2), so that excitons generated by light absorption are efficiently separated and transported. Therefore, it is considered that the photoelectric conversion ability is high. In addition, hole transporting ligand (A1) semiconductor particles (A1) and semiconductor particles (A2)
It is considered that the inclusion of the above causes the formation of a bulk hetero-like state in the photoelectric conversion layer, thereby strengthening the rectification characteristics and suppressing the dark current density.
Claims (9)
粒子が電子輸送性リガンドで表面処理されている半導体粒子（Ａ２）を含んでなる光電変
換材料。 A photoelectric conversion material containing semiconductor particles (A1) in which semiconductor particles are surface-treated with a hole-transporting ligand and semiconductor particles (A2) in which semiconductor particles are surface-treated with an electron-transporting ligand.
載の光電変換材料。 The photoelectric conversion material according to claim 1, wherein the semiconductor particles (A1) or the semiconductor particles (A2) include a compound semiconductor.
上−４．６ｅＶ以下である、請求項１又は２に記載の光電変換材料。 The photoelectric conversion material according to claim 1 or 2, wherein the energy level of the highest occupied molecular orbital (HOMO) of the hole transporting ligand is -6.5 eV or more and -4.6 eV or less.
−２．５ｅＶ以下である、請求項１〜３いずれか１項に記載の光電変換材料。 The photoelectric conversion material according to any one of claims 1 to 3, wherein the energy level of the lowest unoccupied molecular orbital (LUMO) of the electron transporting ligand is −4.5 eV or more and −2.5 eV or less.
エネルギー準位よりも０．２ｅＶ以上大きい、請求項１〜４いずれか１項に記載の光電変
換材料。 The photoelectric conversion material according to any one of claims 1 to 4, wherein the energy level of HOMO of the hole-transporting ligand is 0.2 eV or more higher than the energy level of HOMO of the electron-transporting ligand.
エネルギー準位よりも０．２ｅＶ以上大きい、請求項１〜５いずれか１項に記載の光電変
換材料。 The photoelectric conversion material according to any one of claims 1 to 5, wherein the energy level of LUMO of the hole-transporting ligand is 0.2 eV or more higher than the energy level of LUMO of the electron-transporting ligand.
５００ｎｍの電磁波を吸収し得る請求項１〜６いずれか１項に記載の光電変換材料。 At least one of the semiconductor particles (A1) and the semiconductor particles (A2) has a wavelength of 700 to 2.
The photoelectric conversion material according to any one of claims 1 to 6, which can absorb an electromagnetic wave of 500 nm.
ｅ及びＡｇ2Ｓからなる群より選ばれる一種以上を含んでなる請求項１〜７いずれか１項
に記載の光電変換材料。 At least one of the semiconductor particles (A1) and the semiconductor particles (A2) is PbS, PbS.
The photoelectric conversion material according to claims 1-7 1 wherein one comprising one or more members selected from the group consisting of e and Ag 2 S.
電変換層が、請求項１〜８いずれか１項に記載の光電変換材料を含む光電変換素子。 A photoelectric conversion element having an anode, at least one photoelectric conversion layer, and a cathode, wherein the photoelectric conversion layer contains the photoelectric conversion material according to any one of claims 1 to 8.
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|---|---|---|---|---|
| JP2005538573A (en) * | 2002-09-05 | 2005-12-15 | ナノシス・インク． | Compositions based on nanostructures and nanocomposites |
| JP2017516320A (en) * | 2014-05-09 | 2017-06-15 | マサチューセッツ インスティテュート オブ テクノロジー | Energy level modification of nanocrystals via ligand exchange |
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|---|---|---|---|---|
| JP2005538573A (en) * | 2002-09-05 | 2005-12-15 | ナノシス・インク． | Compositions based on nanostructures and nanocomposites |
| JP2017516320A (en) * | 2014-05-09 | 2017-06-15 | マサチューセッツ インスティテュート オブ テクノロジー | Energy level modification of nanocrystals via ligand exchange |
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