JP2023143104A - Compound, hole transport material, and photoelectric conversion element using the same - Google Patents
Compound, hole transport material, and photoelectric conversion element using the same Download PDFInfo
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- JP2023143104A JP2023143104A JP2022050309A JP2022050309A JP2023143104A JP 2023143104 A JP2023143104 A JP 2023143104A JP 2022050309 A JP2022050309 A JP 2022050309A JP 2022050309 A JP2022050309 A JP 2022050309A JP 2023143104 A JP2023143104 A JP 2023143104A
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- 125000003277 amino group Chemical group 0.000 claims description 18
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- 125000000753 cycloalkyl group Chemical group 0.000 claims description 13
- 125000006413 ring segment Chemical group 0.000 claims description 13
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- 125000003545 alkoxy group Chemical group 0.000 claims description 11
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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- 238000005486 sulfidation Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 125000006836 terphenylene group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000000464 thioxo group Chemical group S=* 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、化合物、正孔輸送材料、およびそれを用いた光電変換素子に関する。 The present invention relates to a compound, a hole transport material, and a photoelectric conversion element using the same.
近年、クリーンエネルギーとして、太陽光発電が注目を浴びており、太陽電池の開発が盛んに行われている。その中でも、低コストかつ溶液プロセスで製造可能な次世代型の太陽電池として、ペロブスカイト材料を光電変換層に用いた太陽電池(以下、ペロブスカイト型太陽電池と表記)の開発が注目を集めている(例えば、特許文献1、非特許文献1~2)。 In recent years, solar power generation has been attracting attention as a clean energy source, and the development of solar cells has been actively conducted. Among these, the development of solar cells that use perovskite materials in the photoelectric conversion layer (hereinafter referred to as perovskite solar cells) is attracting attention as a next-generation solar cell that can be manufactured at low cost using a solution process. For example, Patent Document 1, Non-Patent Documents 1 to 2).
ペロブスカイト型太陽電池では、素子中に正孔輸送材料を使用することが多い。使用する目的として、(1)正孔を選択的に輸送する機能を高めて光電変換効率を向上させる、(2)ペロブスカイト光電変換層と接合して水分や酸素からの影響を受けやすいペロブスカイト材料を保護する、ことが挙げられる(例えば、非特許文献3)。標準的な正孔輸送材料としてスピロビフルオレン系有機化合物のSpiro-OMeTADが使用されることが多いが、当該材料より光電変換特性に高く寄与する正孔輸送材料の報告は少ない。 Perovskite solar cells often use hole-transporting materials in the device. The purpose of its use is (1) to improve the photoelectric conversion efficiency by enhancing the function of selectively transporting holes, and (2) to bond the perovskite photoelectric conversion layer to a perovskite material that is easily affected by moisture and oxygen. protection (for example, Non-Patent Document 3). Spiro-OMeTAD, a spirobifluorene-based organic compound, is often used as a standard hole transport material, but there are few reports of hole transport materials that contribute more to photoelectric conversion characteristics than this material.
本発明が解決しようとする課題は、効率よく電流を取り出すことが可能な光電変換素子用の正孔輸送材料として有用な化合物、および該化合物を正孔輸送層に用いた、光電変換特性が良好な光電変換素子ならびに太陽電池を提供することである。 The problem to be solved by the present invention is to provide a compound useful as a hole transport material for a photoelectric conversion element that can efficiently extract current, and a compound that has good photoelectric conversion characteristics using the compound in a hole transport layer. An object of the present invention is to provide a photoelectric conversion element and a solar cell.
上記課題を解決するため、発明者らは、光電変換特性向上について鋭意検討した結果、特定の構造を有する化合物を設計開発し、正孔輸送層として光電変換素子に用いることにより、充分な光電変換効率および高い耐久性を示す光電変換素子ならびにペロブスカイト型太陽電池が得られることを見出した。すなわち、本発明は以下を要旨とするものである。 In order to solve the above problems, the inventors conducted intensive studies on improving photoelectric conversion characteristics, and as a result, designed and developed a compound with a specific structure, and used it as a hole transport layer in a photoelectric conversion element to achieve sufficient photoelectric conversion. It has been discovered that a photoelectric conversion element and a perovskite solar cell that exhibit high efficiency and high durability can be obtained. That is, the gist of the present invention is as follows.
1.下記一般式(1)で表される化合物。 1. A compound represented by the following general formula (1).
[式中、R1~R20は、それぞれ独立して、
水素原子、ハロゲン原子、カルボキシル基、トリメチルシリル基、
置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルキル基、
置換基を有していてもよい炭素原子数2~20の直鎖状もしくは分岐状のアルケニル基、
置換基を有していてもよい炭素原子数3~12のシクロアルキル基、
置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルコキシ基、
置換基を有していてもよい炭素原子数3~10のシクロアルコキシ基、
置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアシル基、
置換基を有していてもよい炭素原子数1~18のチオ基、
置換基を有していてもよい炭素原子数1~20のアミノ基、
置換基を有する炭素原子数6~36の芳香族炭化水素基、
または置換基を有していてもよい環形成原子数5~36の複素環基を表し、
R1~R5、R6~R10、R11~R15、R16~R20は隣り合う基同士で互いに結合して環を形成していてもよく、R5とR6およびR15とR16は互いに結合して環を形成していてもよい。
X1およびX2は、2価基を表し、同一でも異なっていてもよい。
Y1は、酸素原子、硫黄原子またはCR21R22を表し、
R21およびR22は、それぞれ独立して、ニトリル基、置換基を有していてもよい炭素原子数1~10の直鎖状もしくは分岐状のアシル基、または、置換基を有していてもよい炭素原子数1~10の直鎖状もしくは分岐状のアルコキシカルボニル基を表し、R21とR22は、互いに結合して環を形成していてもよい。]
[In the formula, R 1 to R 20 are each independently,
Hydrogen atom, halogen atom, carboxyl group, trimethylsilyl group,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent,
A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,
a cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent,
A linear or branched acyl group having 1 to 20 carbon atoms that may have a substituent,
a thio group having 1 to 18 carbon atoms which may have a substituent,
an amino group having 1 to 20 carbon atoms which may have a substituent,
an aromatic hydrocarbon group having 6 to 36 carbon atoms having a substituent;
or a heterocyclic group having 5 to 36 ring atoms which may have a substituent,
R 1 to R 5 , R 6 to R 10 , R 11 to R 15 , and R 16 to R 20 may be adjacent groups that are bonded to each other to form a ring, and R 5 and R 6 and R 15 and R 16 may be bonded to each other to form a ring.
X 1 and X 2 represent divalent groups and may be the same or different.
Y 1 represents an oxygen atom, a sulfur atom or CR 21 R 22 ,
R 21 and R 22 each independently have a nitrile group, a linear or branched acyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent; R 21 and R 22 may be bonded to each other to form a ring. ]
2.前記一般式(1)において、X1およびX2が下記一般式(2)で表される化合物。 2. A compound in which in the general formula (1), X 1 and X 2 are represented by the following general formula (2).
[式中、R23~R28は、それぞれ独立して、
水素原子、
置換基を有していてもよい炭素原子数1~10の直鎖状もしくは分岐状のアルキル基、
置換基を有していてもよい炭素原子数2~10の直鎖状もしくは分岐状のアルケニル基、
置換基を有していてもよい炭素原子数3~12のシクロアルキル基、
置換基を有していてもよい炭素原子数6~18の芳香族炭化水素基、
または置換基を有していてもよい環形成原子数5~18の複素環基を表し、
R24とR25、R26とR27およびR28とR29は互いに結合して環を形成していてもよい。
Zは酸素原子、硫黄原子またはセレン原子を表し、mおよびnはそれぞれ0~2の整数を表す。
ただし、mまたはnのいずれか一方が1または2である。]
[In the formula, R 23 to R 28 are each independently,
hydrogen atom,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent,
a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent,
Aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent,
or a heterocyclic group having 5 to 18 ring atoms which may have a substituent,
R 24 and R 25 , R 26 and R 27 , and R 28 and R 29 may be bonded to each other to form a ring.
Z represents an oxygen atom, a sulfur atom or a selenium atom, and m and n each represent an integer of 0 to 2.
However, either m or n is 1 or 2. ]
3.前記一般式(2)のmが1である化合物。 3. A compound in which m in the general formula (2) is 1.
4.前記一般式(1)において、R1~R20が、水素原子、置換基を有していてもよい炭素原子数1~20のアルコキシ基、置換基を有していてもよい炭素原子数1~20のアミノ基である化合物。 4. In the general formula (1), R 1 to R 20 are a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and 1 carbon atom which may have a substituent. Compounds with ~20 amino groups.
5.前記一般式(1)において、Y1が酸素原子である化合物。 5. A compound in which Y 1 is an oxygen atom in the general formula (1).
6.前記記載の化合物で表される正孔輸送材料。 6. A hole transport material represented by the compound described above.
7.前記記載の正孔輸送材料を用いた光電変換素子。 7. A photoelectric conversion element using the hole transport material described above.
本発明に係る化合物、該化合物を用いた正孔輸送層によれば、充分な光電変換効率および高い耐久性を有する光電変換素子およびペロブスカイト型太陽電池を得ることができる。 According to the compound according to the present invention and the hole transport layer using the compound, a photoelectric conversion element and a perovskite solar cell having sufficient photoelectric conversion efficiency and high durability can be obtained.
以下、本発明の実施の形態について、詳細に説明する。本発明の正孔輸送材料は、光電変換素子ならびにペロブスカイト型の光電変換素子に用いられる。 Embodiments of the present invention will be described in detail below. The hole transport material of the present invention is used for photoelectric conversion devices and perovskite photoelectric conversion devices.
以下に、本発明の前記一般式(1)で表される化合物について具体的に説明するが、本発明はこれらに限定されるものではない。 The compound represented by the general formula (1) of the present invention will be specifically explained below, but the present invention is not limited thereto.
一般式(1)において、R1~R20はそれぞれ独立して、
水素原子、ハロゲン原子、カルボキシル基、トリメチルシリル基、
置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルキル基、
置換基を有していてもよい炭素原子数2~20の直鎖状もしくは分岐状のアルケニル基、
置換基を有していてもよい炭素原子数3~12のシクロアルキル基、
置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルコキシ基、
置換基を有していてもよい炭素原子数3~10のシクロアルコキシ基、
置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアシル基、
置換基を有していてもよい炭素原子数1~18のチオ基、
置換基を有していてもよい炭素原子数1~20のアミノ基、
置換基を有する炭素原子数6~36の芳香族炭化水素基、または
置換基を有していてもよい環形成原子数5~36の複素環基を表す。
In general formula (1), R 1 to R 20 are each independently,
Hydrogen atom, halogen atom, carboxyl group, trimethylsilyl group,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent,
A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,
a cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent,
A linear or branched acyl group having 1 to 20 carbon atoms that may have a substituent,
a thio group having 1 to 18 carbon atoms which may have a substituent,
an amino group having 1 to 20 carbon atoms which may have a substituent,
Represents an aromatic hydrocarbon group having 6 to 36 carbon atoms having a substituent, or a heterocyclic group having 5 to 36 ring atoms which may have a substituent.
一般式(1)において、R1~R20で表される「ハロゲン原子」としては、フッ素、塩素、臭素およびヨウ素があげられる。 In the general formula (1), examples of the "halogen atom" represented by R 1 to R 20 include fluorine, chlorine, bromine and iodine.
一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルキル基」における「炭素原子数1~20の直鎖状もしくは分岐状のアルキル基」としては具体的に、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基、n-ペンチル基、イソペンチル基、n-ヘキシル基、2-エチルヘキシル基、ヘプチル基、オクチル基、イソオクチル基、ノニル基、デシル基などをあげることができる。 In the general formula (1), in the "linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by R 1 to R 20 , 20 straight-chain or branched alkyl groups" specifically include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, Examples include n-pentyl group, isopentyl group, n-hexyl group, 2-ethylhexyl group, heptyl group, octyl group, isooctyl group, nonyl group, and decyl group.
一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数2~20の直鎖状もしくは分岐状のアルケニル基」における「炭素原子数2~20の直鎖状もしくは分岐状のアルケニル基」としては具体的に、エテニル基(ビニル基)、1-プロペニル基、2-プロペニル基(アリル基)、1-メチルエテニル基、1-ブテニル基、2-ブテニル基、1-ペンテニル基、1-ヘキセニル基、2-メチル-1-プロペニル基、2-メチル-2-プロペニル基、1-エチルエテニル基、またはこれらのアルケニル基が複数結合した炭素原子数2~20の直鎖状もしくは分岐状のアルケニル基などをあげることができる。 In the general formula (1), in the "linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent" represented by R 1 to R 20 , 20 linear or branched alkenyl groups" specifically include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), 1-methylethenyl group, 1-butenyl group, 2 -Butenyl group, 1-pentenyl group, 1-hexenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, or a group with two or more carbon atoms bonded to these alkenyl groups ~20 linear or branched alkenyl groups, etc. can be mentioned.
一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数3~12のシクロアルキル基」における「炭素原子数3~12のシクロアルキル基」としては、具体的に、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、シクロドデシル基、4-メチルシクロヘキシル基、4-エチルシクロヘキシル基などをあげることができる。 In general formula (1), the "cycloalkyl group having 3 to 12 carbon atoms" in the "cycloalkyl group having 3 to 12 carbon atoms which may have a substituent" represented by R 1 to R 20 Specific examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, etc. I can do it.
一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルコキシ基」における「炭素原子数1~20の直鎖状もしくは分岐状のアルコキシ基」としては、具体的に、メトキシ基、エトキシ基、プロポキシ基、n-ブトキシ基、n-ペンチルオキシ基、n-ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、ノニルオキシ基、デシルオキシ基、イソプロポキシ基、イソブトキシ基、s-ブトキシ基、t-ブトキシ基、イソオクチルオキシ基、t-オクチルオキシ基、フェノキシ基、トリルオキシ基、ビフェニリルオキシ基、ターフェニリルオキシ基、ナフチルオキシ基、アントリルオキシ基、フェナントリルオキシ基、フルオレニルオキシ基、インデニルオキシ基などをあげることができる。 In the general formula (1), in the "linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent" represented by R 1 to R 20 , 20 linear or branched alkoxy groups" specifically include methoxy group, ethoxy group, propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, heptyloxy group, octyl group. Oxy group, nonyloxy group, decyloxy group, isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group, isooctyloxy group, t-octyloxy group, phenoxy group, tolyloxy group, biphenylyloxy group, terphenylene group Examples include a lyloxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, a fluorenyloxy group, and an indenyloxy group.
一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数3~10のシクロアルコキシ基」における「炭素原子数3~10の直鎖状もしくは分岐状のシクロアルコキシ基」としては、具体的に、シクロプロポキシ基、シクロブトキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基、4-メチルシクロヘキシルオキシ基などをあげることができる。 In general formula (1), in the "cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent" represented by R 1 to R 20 , "linear or Specific examples of the branched cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, and a 4-methylcyclohexyloxy group.
一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアシル基」における「炭素原子数1~20の直鎖状もしくは分岐状のアシル基」としては、具体的に、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基、イソバレリル基、ベンゾイルアセチル基、ベンゾイル基などをあげることができ、アルキル鎖を含む場合、水素原子が完全にフッ素原子に置換(パーフルオロ化)されているものを含む。また、アミノ基と結合したもの(-CO-N<)であってもよい。 In the general formula (1), in the "linear or branched acyl group having 1 to 20 carbon atoms which may have a substituent" represented by R 1 to R 20 , Specific examples of the "20 linear or branched acyl groups" include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoylacetyl group, benzoyl group, etc. When it contains an alkyl chain, it includes those in which hydrogen atoms are completely substituted with fluorine atoms (perfluorination). It may also be one bonded to an amino group (-CO-N<).
一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数1~18のチオ基」における「炭素原子数1~18のチオ基」としては、具体的に、メチルチオ基、エチルチオ基、プロピルチオ基、フェニルチオ基、ビフェニルチオ基などをあげることができる。 In general formula (1), the "thio group having 1 to 18 carbon atoms" in the "thio group having 1 to 18 carbon atoms which may have a substituent" represented by R 1 to R 20 is Specific examples thereof include methylthio group, ethylthio group, propylthio group, phenylthio group, and biphenylthio group.
一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数1~20のアミノ基」における「炭素原子数1~20のアミノ基」としては、具体的に、一置換アミノ基としてエチルアミノ基、アセチルアミノ基、フェニルアミノ基など、また、二置換アミノ基としてジエチルアミノ基、ジフェニルアミノ基、アセチルフェニルアミノ基などをあげることができる。 In general formula (1), the "amino group having 1 to 20 carbon atoms" in the "amino group having 1 to 20 carbon atoms which may have a substituent" represented by R 1 to R 20 is Specifically, monosubstituted amino groups include ethylamino, acetylamino, and phenylamino groups, and disubstituted amino groups include diethylamino, diphenylamino, and acetylphenylamino groups.
一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数6~36の芳香族炭化水素基」における「炭素原子数6~36の芳香族炭化水素基」としては具体的に、フェニル基、ビフェニル基、テルフェニル基、ナフチル基、ビフェニル基、アントラセニル基(アントリル基)、フェナントリル基、フルオレニル基、インデニル基、ピレニル基、ペリレニル基、フルオランテニル基、トリフェニレニル基などをあげることができる。なお、本発明において芳香族炭化水素基には、「縮合多環芳香族基」が含まれるものとする。 In the general formula (1), in the "aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent" represented by R 1 to R 20 , Specific examples of "hydrocarbon groups" include phenyl group, biphenyl group, terphenyl group, naphthyl group, biphenyl group, anthracenyl group (anthryl group), phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, and fluoran. Examples include tenyl group and triphenylenyl group. In addition, in the present invention, the aromatic hydrocarbon group includes a "fused polycyclic aromatic group".
一般式(1)において、R1~R20で表される「置換基を有していてもよい環形成原子数5~36の複素環基」における「環形成原子数5~36の複素環基」としては具体的に、ピリジル基、ピリミジニル基、トリアジニル基、チエニル基、フリル基(フラニル基)、ピロリル基、イミダゾリル基、ピラゾリル基、トリアゾリル基、キノリル基、イソキノリル基、ナフチリジニル基、アクリジニル基、フェナントロリニル基、ベンゾフラニル基、ベンゾチエニル基、オキサゾリル基、インドリル基、カルバゾリル基、ベンゾオキサゾリル基、チアゾリル基、ベンゾチアゾリル基、キノキサリニル基、ベンゾイミダゾリル基、ピラゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、カルボニリル基などをあげることができる。 In the general formula (1), in the "heterocyclic group having 5 to 36 ring atoms which may have a substituent" represented by R 1 to R 20 , "heterocyclic group having 5 to 36 ring atoms" Examples of "groups" include pyridyl groups, pyrimidinyl groups, triazinyl groups, thienyl groups, furyl groups (furanyl groups), pyrrolyl groups, imidazolyl groups, pyrazolyl groups, triazolyl groups, quinolyl groups, isoquinolyl groups, naphthyridinyl groups, and acridinyl groups. , phenanthrolinyl group, benzofuranyl group, benzothienyl group, oxazolyl group, indolyl group, carbazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, quinoxalinyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzo Examples include thienyl group and carbonyl group.
一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数1~18の直鎖状もしくは分岐状のアルキル基」、「置換基を有していてもよい炭素原子数2~20の直鎖状もしくは分岐状のアルケニル基」、「置換基を有していてもよい炭素原子数3~12のシクロアルキル基」、「置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルコキシ基」、「置換基を有していてもよい炭素原子数3~10のシクロアルコキシ基」、「置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアシル基」、「置換基を有していてもよい炭素原子数1~18のチオ基」、「置換基を有していてもよい炭素原子数1~20のアミノ基」、「置換基を有する炭素原子数6~36の芳香族炭化水素基」、または「置換基を有していてもよい環形成原子数5~36の複素環基」における「置換基」としては、具体的に、フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子;シアノ基;水酸基;ニトロ基;ニトロソ基;カルボキシル基;リン酸基;チオキソ基(>C=S);トリメチルシリル基;
メチルエステル基、エチルエステル基などのカルボン酸エステル基;
メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基、n-ペンチル基、イソペンチル基、n-ヘキシル基、2-エチルヘキシル基、ヘプチル基、オクチル基、イソオクチル基、ノニル基、デシル基などの炭素原子数1~18の直鎖状もしくは分岐状のアルキル基;
エテニル基(ビニル基)、1-プロペニル基、2-プロペニル基(アリル基)、1-ブテニル基、2-ブテニル基、1-ペンテニル基、1-ヘキセニル基、2-メチル-1-プロペニル基、2-メチル-2-プロペニル基、1-エチルエテニル基、など炭素原子数2~18の直鎖状もしくは分岐状のアルケニル基;
メトキシ基、エトキシ基、プロポキシ基、t-ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基などの炭素原子数1~18のアルコキシ基;
フェニル基、ナフチル基、アントリル基、フェナントリル基、ピレニル基などの炭素原子数6~30の芳香族炭化水素基;
ピリジル基、ピリミジニル基、トリアジニル基、チエニル基、フリル基(フラニル基)、ピロリル基、イミダゾリル基、ピラゾリル基、トリアゾリル基、キノリル基、イソキノリル基、ナフチリジニル基、アクリジニル基、フェナントロリニル基、ベンゾフラニル基、ベンゾチエニル基、オキサゾリル基、インドリル基、カルバゾリル基、ベンゾオキサゾリル基、チアゾリル基、ベンゾチアゾリル基、キノキサリニル基、ベンゾイミダゾリル基、ピラゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、カルボニリル基などの環形成原子数5~30の複素環基;
無置換アミノ基(―NH2)、エチルアミノ基、アセチルアミノ基、フェニルアミノ基などの一置換アミノ基、またはジエチルアミノ基、ジフェニルアミノ基、アセチルフェニルアミノ基などの二置換アミノ基である、炭素原子数0~18のアミノ基;
無置換チオ基(チオール基:―SH)、メチルチオ基、エチルチオ基、プロピルチオ基、フェニルチオ基、ビフェニルチオ基などの炭素原子数0~18のチオ基;
などをあげることができる。これらの「置換基」は、1つのみ含まれてもよく、複数含まれてもよく、複数含まれる場合は互いに同一でも異なっていてもよい。また、これら「置換基」はさらに前記例示した置換基を有していてもよい。
In the general formula (1), "a linear or branched alkyl group having 1 to 18 carbon atoms which may have a substituent" and " a linear or branched alkyl group having a substituent and "A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent", "a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent""A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent", "a cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent", "A cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent""A linear or branched acyl group having 1 to 20 carbon atoms which may optionally have a substituent", "Thio group having 1 to 18 carbon atoms which may have a substituent" an amino group having 1 to 20 carbon atoms which may optionally have a substituent, an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, or an amino group having 5 to 20 ring atoms which may have a substituent. Examples of the "substituent" in "36 heterocyclic groups" include halogen atoms such as fluorine, chlorine, bromine, and iodine; cyano; hydroxyl; nitro; nitroso; carboxyl; phosphoric acid; Group; Thioxo group (>C=S); Trimethylsilyl group;
Carboxylic acid ester groups such as methyl ester groups and ethyl ester groups;
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, 2-ethylhexyl group, Straight-chain or branched alkyl groups having 1 to 18 carbon atoms such as heptyl group, octyl group, isooctyl group, nonyl group, decyl group;
Ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, 2-methyl-1-propenyl group, Straight-chain or branched alkenyl groups having 2 to 18 carbon atoms, such as 2-methyl-2-propenyl group and 1-ethylethenyl group;
Alkoxy groups having 1 to 18 carbon atoms such as methoxy group, ethoxy group, propoxy group, t-butoxy group, pentyloxy group, hexyloxy group;
Aromatic hydrocarbon groups having 6 to 30 carbon atoms such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group;
Pyridyl group, pyrimidinyl group, triazinyl group, thienyl group, furyl group (furanyl group), pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, acridinyl group, phenanthrolinyl group, benzofuranyl group groups, benzothienyl groups, oxazolyl groups, indolyl groups, carbazolyl groups, benzoxazolyl groups, thiazolyl groups, benzothiazolyl groups, quinoxalinyl groups, benzimidazolyl groups, pyrazolyl groups, dibenzofuranyl groups, dibenzothienyl groups, carbonylyl groups, etc. A heterocyclic group having 5 to 30 atoms;
A carbon that is an unsubstituted amino group (-NH 2 ), a monosubstituted amino group such as an ethylamino group, an acetylamino group, or a phenylamino group, or a disubstituted amino group such as a diethylamino group, diphenylamino group, or acetylphenylamino group. Amino group having 0 to 18 atoms;
A thio group having 0 to 18 carbon atoms, such as an unsubstituted thio group (thiol group: -SH), methylthio group, ethylthio group, propylthio group, phenylthio group, biphenylthio group;
etc. can be given. These "substituents" may be included only one, or may be included in plurality, and when included in plurality, they may be the same or different from each other. Moreover, these "substituents" may further have the above-mentioned substituents.
一般式(1)において、R1~R20は、水素原子、置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルコキシ基、置換基を有していてもよい炭素原子数1~18のチオ基、置換基を有していてもよい炭素原子数1~20のアミノ基、または置換基を有する炭素原子数6~36の芳香族炭化水素基であることが好ましく、置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルコキシ基、置換基を有していてもよい炭素原子数1~18のチオ基、置換基を有していてもよい炭素原子数1~20のアミノ基であることがより好ましい。 In the general formula (1), R 1 to R 20 each have a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. a linear or branched alkoxy group having 1 to 20 carbon atoms, a thio group having 1 to 18 carbon atoms which may have a substituent, and a thio group having 1 to 18 carbon atoms which may have a substituent; It is preferably an amino group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms having a substituent, and a linear or More preferred are a branched alkoxy group, a thio group having 1 to 18 carbon atoms which may have a substituent, and an amino group having 1 to 20 carbon atoms which may have a substituent.
一般式(1)において、R1~R5、R6~R10、R11~R15、R16~R20は隣り合う基同士で、単結合、酸素原子、硫黄原子、セレン原子を介した結合もしくは窒素原子を介した結合によって互いに結合して環を形成していてもよく、R5とR6およびR15とR16も、単結合、酸素原子、硫黄原子、セレン原子を介した結合もしくは窒素原子を介した結合によって互いに結合して環を形成していてもよい。また、R5とR6およびR15とR16は、環を形成する場合、単結合、酸素原子、硫黄原子を介した結合によって互いに結合して環を形成することが好ましい。 In the general formula (1), R 1 to R 5 , R 6 to R 10 , R 11 to R 15 , and R 16 to R 20 are adjacent groups separated by a single bond, an oxygen atom, a sulfur atom, or a selenium atom. R 5 and R 6 and R 15 and R 16 may also be bonded to each other through a single bond, an oxygen atom, a sulfur atom, or a selenium atom to form a ring. They may be bonded to each other by a bond or a bond via a nitrogen atom to form a ring. Further, when forming a ring, R 5 and R 6 and R 15 and R 16 are preferably bonded to each other through a single bond, an oxygen atom, or a sulfur atom to form a ring.
一般式(1)において、Y1は、酸素原子、硫黄原子またはCR21R22を表し、
R21およびR22は、それぞれ独立して、
ニトリル基、
置換基を有していてもよい炭素原子数1~10のアシル基、
または、置換基を有していてもよい炭素原子数1~10のアルコキシカルボニル基を表し、電子求引性であることが好ましい。
In general formula (1), Y 1 represents an oxygen atom, a sulfur atom or CR 21 R 22 ,
R 21 and R 22 are each independently,
nitrile group,
an acyl group having 1 to 10 carbon atoms which may have a substituent;
Alternatively, it represents an alkoxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, and is preferably electron-withdrawing.
一般式(1)において、R21およびR22で表される「置換基を有していてもよい炭素原子数1~10の直鎖状もしくは分岐状のアシル基」における「炭素原子数1~10の直鎖状もしくは分岐状のアシル基」としては、一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数1~20のアシル基」のうち、「置換基を有していてもよい炭素原子数1~10の直鎖状もしくは分岐状のアシル基」と同じものをあげることができる。 In the general formula (1), in the "linear or branched acyl group having 1 to 10 carbon atoms which may have a substituent" represented by R 21 and R 22 , 10 linear or branched acyl group" in general formula (1), "an acyl group having 1 to 20 carbon atoms which may have a substituent," represented by R 1 to R 20 . '', the same ones as ``a linear or branched acyl group having 1 to 10 carbon atoms which may have a substituent group'' can be mentioned.
一般式(1)において、R21およびR22で表される「炭素原子数1~10の直鎖状もしくは分岐状のアルコキシカルボニル基」における「炭素原子数1~10の直鎖状もしくは分岐状のアルコキシカルボニル基」としては、具体的に、メトキシカルボニル基、エトキシカルボニル基などをあげることができ、アルキル鎖を含む場合、水素原子が完全にフッ素原子に置換(パーフルオロ化)されているものを含む。 In general formula (1), in the "straight chain or branched alkoxycarbonyl group having 1 to 10 carbon atoms" represented by R 21 and R 22 , "straight chain or branched alkoxycarbonyl group having 1 to 10 carbon atoms" Specific examples of the "alkoxycarbonyl group" include methoxycarbonyl group, ethoxycarbonyl group, etc., and when it contains an alkyl chain, hydrogen atoms are completely substituted with fluorine atoms (perfluorination). including.
一般式(1)において、R21およびR22は、単結合、酸素原子、硫黄原子、セレン原子を介した結合もしくは窒素原子を介して互いに結合し、環を形成していてもよい。また、環を形成する場合、バルビツール酸系、チオバルビツール酸系、インダンジオン系などの酸性の複素環であることが好ましい。 In general formula (1), R 21 and R 22 may be bonded to each other via a single bond, an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom to form a ring. Further, when a ring is formed, it is preferably an acidic heterocycle such as a barbituric acid type, a thiobarbituric acid type, or an indanedione type.
一般式(1)において、Y1は酸素原子であることが好ましい。 In general formula (1), Y 1 is preferably an oxygen atom.
一般式(2)において、R23~R28は、それぞれ独立して、水素原子、
置換基を有していてもよい炭素原子数1~10の直鎖状もしくは分岐状のアルキル基、
置換基を有していてもよい炭素原子数2~10の直鎖状もしくは分岐状のアルケニル基、
置換基を有していてもよい炭素原子数3~12のシクロアルキル基、
置換基を有していてもよい炭素原子数6~18の芳香族炭化水素基、または
置換基を有していてもよい環形成原子数5~18の複素環基を表す。
In general formula (2), R 23 to R 28 are each independently a hydrogen atom,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent,
a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent,
Represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 18 ring atoms which may have a substituent.
一般式(2)において、R23~R28で表される「置換基を有していてもよい炭素原子数1~10の直鎖状もしくは分岐状のアルキル基」における「炭素原子数1~10の直鎖状もしくは分岐状のアルキル基」としては、一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルキル基」のうち「炭素原子数1~10の直鎖状もしくは分岐状のアルキル基」と同じものをあげることができる。 In the general formula (2), in the "linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent" represented by R 23 to R 28 , 10 straight-chain or branched alkyl group" in general formula (1), "straight-chain alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by R 1 to R 20 Among the "linear or branched alkyl groups", the same ones as "straight-chain or branched alkyl groups having 1 to 10 carbon atoms" can be mentioned.
一般式(2)において、R23~R28で表される「置換基を有していてもよい炭素原子数2~10の直鎖状もしくは分岐状のアルケニル基」における「炭素原子数2~10の直鎖状もしくは分岐状のアルケニル基」としては、一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数2~20の直鎖状もしくは分岐状のアルケニル基」のうち「炭素原子数2~10の直鎖状もしくは分岐状のアルケニル基」と同じものをあげることができる。 In the general formula (2), in the "linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent" represented by R 23 to R 28 , 10 straight-chain or branched alkenyl groups" in the general formula (1), "straight-chain alkenyl groups having 2 to 20 carbon atoms which may have a substituent" represented by R 1 to R 20 Among the "linear or branched alkenyl groups", the same ones as "straight-chain or branched alkenyl groups having 2 to 10 carbon atoms" can be mentioned.
一般式(2)において、R23~R28で表される「置換基を有していてもよい炭素原子数3~12のシクロアルキル基」における「炭素原子数3~10のシクロアルキル基」としては、一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数3~12のシクロアルキル基」と同じものをあげることができる。 In general formula (2), the "cycloalkyl group having 3 to 10 carbon atoms" in the "cycloalkyl group having 3 to 12 carbon atoms which may have a substituent" represented by R 23 to R 28 Examples include the same "cycloalkyl group having 3 to 12 carbon atoms which may have a substituent" represented by R 1 to R 20 in general formula (1).
一般式(2)において、R23~R28で表される「置換基を有していてもよい炭素原子数6~18の芳香族炭化水素基」における「炭素原子数6~18の芳香族炭化水素基」としては、一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数6~36の芳香族炭化水素基」のうち「炭素原子数6~18の芳香族炭化水素基」と同じものをあげることができる。 In the general formula (2), in the "aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent" represented by R 23 to R 28 , In the general formula ( 1 ), the term "hydrocarbon group" refers to a "carbon The same thing as "aromatic hydrocarbon group having 6 to 18 atoms" can be mentioned.
一般式(2)において、R23~R28で表される「置換基を有していてもよい環形成原子数5~18の複素環基」における「環形成原子数5~18の複素環基」としては、一般式(1)において、R1~R20で表される「置換基を有していてもよい環形成原子数5~36の複素環基」のうち「環形成原子数5~18の複素環基」と同じものをあげることができる。 In the general formula (2), in the "heterocyclic group having 5 to 18 ring atoms which may have a substituent" represented by R 23 to R 28 , "heterocyclic group having 5 to 18 ring atoms" In general formula (1), the term "group" refers to the "heterocyclic group having 5 to 36 ring atoms which may have a substituent" represented by R 1 to R 20 . 5-18 heterocyclic groups".
一般式(2)において、R23~R28で表される「置換基を有していてもよい炭素原子数1~10の直鎖状もしくは分岐状のアルキル基」、「置換基を有していてもよい炭素原子数2~10の直鎖状もしくは分岐状のアルケニル基」、「置換基を有していてもよい炭素原子数3~12のシクロアルキル基」、「置換基を有していてもよい炭素原子数6~18の芳香族炭化水素基」または「置換基を有していてもよい環形成原子数5~18の複素環基」における「置換基」としては、一般式(1)において、R1~R20で表される「置換基を有していてもよい炭素原子数1~18の直鎖状もしくは分岐状のアルキル基」等における「置換基」のうち炭素原子数および環形成原子数に想到する範囲で同じものをあげることができる。 In the general formula (2), "a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent" and "a linear or branched alkyl group having a substituent and ``A linear or branched alkenyl group having 2 to 10 carbon atoms which may optionally have a substituent'', ``a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent'', ``A linear or branched alkenyl group having 3 to 12 carbon atoms which may have a substituent The "substituent" in the "optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms" or the "optionally substituted heterocyclic group having 5 to 18 ring atoms" includes the general formula In (1), among the "substituents" in the "linear or branched alkyl group having 1 to 18 carbon atoms which may have a substituent" represented by R 1 to R 20 , The same number of atoms and the number of ring-forming atoms can be mentioned within the range that can be considered.
一般式(2)において、R23とR24、R25とR26およびR27とR28は、単結合、酸素原子、硫黄原子、セレン原子を介した結合、もしくは窒素原子を介して互いに結合し、環を形成していてもよい。 In general formula (2), R 23 and R 24 , R 25 and R 26 , and R 27 and R 28 are bonded to each other via a single bond, an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom. However, it may also form a ring.
一般式(2)において、Z1は酸素原子、硫黄原子またはセレン原子を表し、Z1は硫黄原子であることが好ましい。 In general formula (2), Z 1 represents an oxygen atom, a sulfur atom, or a selenium atom, and preferably Z 1 is a sulfur atom.
一般式(2)において、mおよびnはそれぞれ0~2の整数を表し、mが0である場合、nは1または2であるものとし、nが0である場合、mは1または2であり、m及びnのいずれか一方が1以上であり、共に0となる場合は含まないものとする。mは1であることが好ましい。また、一般式(1)の中心骨格であるチオキサントン誘導体部(Y1がCR21R22である場合を含む)とは、一般式(2)で表されるフェニル基および5員環の複素環基のどちらから結合してもよいものとする。 In general formula (2), m and n each represent an integer from 0 to 2; when m is 0, n is 1 or 2; when n is 0, m is 1 or 2; Yes, and cases where either m or n is 1 or more and both are 0 are not included. Preferably, m is 1. In addition, the thioxanthone derivative moiety (including the case where Y 1 is CR 21 R 22 ), which is the central skeleton of the general formula (1), refers to the phenyl group and the 5-membered heterocyclic ring represented by the general formula (2). The bond may be bonded from either side of the group.
一般式(2)において、mが1であり、nが0または1であると好ましい。一般式(2)において、mが1であり、nが1である場合に、一般式(1)の中心骨格であるチオキサントン誘導体部とは、5員環の複素環基が結合していると好ましい。 In general formula (2), m is preferably 1 and n is preferably 0 or 1. In general formula (2), when m is 1 and n is 1, the thioxanthone derivative moiety, which is the central skeleton of general formula (1), has a 5-membered heterocyclic group bonded to it. preferable.
本発明の前記一般式(1)で表される化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。また、以下の例示化合物は水素原子、炭素原子等を一部省略して記載しており、存在し得る異性体のうちの一例を示したものであり、その他すべての異性体を包含するものとする。また、それぞれ2種以上の異性体の混合物であってもよい。 Specific examples of the compound represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto. In addition, the exemplified compounds below are written with some hydrogen atoms, carbon atoms, etc. omitted, and are only examples of possible isomers, and are intended to include all other isomers. do. Further, each of the isomers may be a mixture of two or more types of isomers.
前記一般式(1)で表される本発明の正孔輸送材料は、公知の方法によって合成することができる。 The hole transport material of the present invention represented by the general formula (1) can be synthesized by a known method.
下記式(3)で表される2,7-ジブロモチオキサントンと下記一般式(4)、(5)で表されるボロン酸体化合物または下記一般式(6)、(7)で表されるボロン酸エステル体化合物との鈴木・宮浦クロスカップリング反応を行い、さらに下記一般式(8)で表される化合物とのクネーフェナーゲル縮合反応により、前記一般式(1)において、YにCR21R22を導入したタイプの合成をすることができる。 2,7-dibromothioxanthone represented by the following formula (3) and a boronic acid compound represented by the following general formulas (4) and (5) or boron represented by the following general formulas (6) and (7) By performing a Suzuki-Miyaura cross-coupling reaction with an acid ester compound and further by a Knoevenagel condensation reaction with a compound represented by the following general formula (8), CR 21 is added to Y in the general formula (1). A type of synthesis incorporating R 22 can be performed.
本発明の前記一般式(1)で表される正孔輸送材料の精製方法としては、カラムクロマトグラフィーによる精製、シリカゲル、活性炭、活性白土等による吸着精製、溶媒による再結晶や晶析等により行うことができる。あるいはこれらの方法を併用して、純度を高めた化合物を使用することが有効である。また、これらの化合物の同定は、核磁気共鳴分析(NMR)により行うことができる。 The method for purifying the hole transport material represented by the general formula (1) of the present invention includes purification by column chromatography, purification by adsorption with silica gel, activated carbon, activated clay, etc., recrystallization with a solvent, crystallization, etc. be able to. Alternatively, it is effective to use a compound with increased purity by using these methods in combination. Moreover, these compounds can be identified by nuclear magnetic resonance analysis (NMR).
以下、本発明の光電変換素子の好ましい態様について説明する。 Hereinafter, preferred embodiments of the photoelectric conversion element of the present invention will be described.
〈光電変換素子〉
本発明の光電変換素子は、典型的には、図1の概略断面図に示すように、導電性支持体1、電子輸送層2、光電変換層3、正孔輸送層4、および対極5を有する。
<Photoelectric conversion element>
The photoelectric conversion element of the present invention typically includes a conductive support 1, an electron transport layer 2, a photoelectric conversion layer 3, a hole transport layer 4, and a counter electrode 5, as shown in the schematic cross-sectional view of FIG. have
本発明の光電変換素子は、図1に示す通り、導電性支持体1、電子輸送層2、光電変換層3、正孔輸送層4、および対極5を備えることが好ましいが、これに限定されるものではない。また、本発明の光電変換素子としては、太陽電池として用いることが好ましく、ペロブスカイト型の光電変換素子であることがより好ましいが、これに限定されない。本発明において、ペロブスカイト型の光電変換素子は、導電性支持体(電極)1、電子輸送層2、光電変換層(ペロブスカイト層)3、正孔輸送層4、および対極5をこの順に備えることが好ましい。また、導電性支持体、正孔輸送層、光電変換層(ペロブスカイト層)、電子輸送層、対極の順で構成されていてもよい。 As shown in FIG. 1, the photoelectric conversion element of the present invention preferably includes a conductive support 1, an electron transport layer 2, a photoelectric conversion layer 3, a hole transport layer 4, and a counter electrode 5, but is not limited thereto. It's not something you can do. Further, the photoelectric conversion element of the present invention is preferably used as a solar cell, and more preferably a perovskite type photoelectric conversion element, but is not limited thereto. In the present invention, the perovskite photoelectric conversion element may include a conductive support (electrode) 1, an electron transport layer 2, a photoelectric conversion layer (perovskite layer) 3, a hole transport layer 4, and a counter electrode 5 in this order. preferable. Further, the conductive support, the hole transport layer, the photoelectric conversion layer (perovskite layer), the electron transport layer, and the counter electrode may be configured in this order.
〈導電性支持体〉
本発明の光電変換素子において、図1に示す導電性支持体1は、光電変換に寄与する光を透過可能な透光性を有する必要がある。また、導電性支持体は、光電変換層より電流を取り出す機能を有する部材であることから、導電性基板であることが好ましい。導電性材料の具体例としては、スズドープ酸化インジウム(ITO)、亜鉛をドープしたインジウム酸化物(IZO)、タングステンをドープしたインジウム酸化物(IWO)、亜鉛とアルミニウムとの酸化物(AZO)、フッ素ドープの酸化スズ(FTO)、酸化インジウム(In2O3)、インジウム-スズ複合酸化物などの導電性透明酸化物半導体などをあげることができるが、スズドープ酸化インジウム(ITO)、フッ素ドープの酸化スズ(FTO)などを用いることが好ましい。
<Conductive support>
In the photoelectric conversion element of the present invention, the conductive support 1 shown in FIG. 1 needs to have translucency that allows light that contributes to photoelectric conversion to pass therethrough. Further, since the conductive support is a member having a function of extracting current from the photoelectric conversion layer, it is preferably a conductive substrate. Specific examples of conductive materials include tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), tungsten-doped indium oxide (IWO), zinc and aluminum oxide (AZO), and fluorine. Examples include conductive transparent oxide semiconductors such as doped tin oxide (FTO), indium oxide (In 2 O 3 ), and indium-tin composite oxide, but tin-doped indium oxide (ITO) and fluorine-doped oxide It is preferable to use tin (FTO) or the like.
〈電子輸送層〉
本発明の光電変換素子において、図1に示す電子輸送層2は、前記導電性支持体1と光電変換層(ペロブスカイト層)3との間に位置する層であり、導電性支持体1の上に電子輸送層2が形成されることが好ましいが、特に限定されない。電子輸送層は、光電変換層から電極への電子の移動効率を向上させ、また、正孔の移動をブロックさせるために用いる。
<Electron transport layer>
In the photoelectric conversion element of the present invention, the electron transport layer 2 shown in FIG. 1 is a layer located between the conductive support 1 and the photoelectric conversion layer (perovskite layer) 3, and Although it is preferable that the electron transport layer 2 is formed on the substrate, there is no particular limitation. The electron transport layer is used to improve the efficiency of electron transfer from the photoelectric conversion layer to the electrode and to block the transfer of holes.
本発明において、電子輸送層を形成する半導体の具体例としては、酸化スズ(SnO、SnO2、SnO3等)、酸化チタン(TiO2等)、酸化タングステン(WO2、WO3、W2O3等)、酸化亜鉛(ZnO)、酸化ニオブ(Nb2O5等)、酸化タンタル(Ta2O5等)、酸化イットリウム(Y2O3等)、チタン酸ストロンチウム(SrTiO3等)などの金属酸化物;硫化チタン、硫化亜鉛、硫化ジルコニウム、硫化銅、硫化スズ、硫化インジウム、硫化タングステン、硫化カドミウム、硫化銀などの金属硫化物;セレン化チタン、セレン化ジルコニウム、セレン化インジウム、セレン化タングステンなどの金属セレン化物;シリコン、ゲルマニウムなどの単体半導体などをあげることができ、これらの半導体は1種または2種以上を用いるのが好ましい。本発明においては、半導体として酸化スズ、酸化チタン、酸化亜鉛から選択される1種または2種以上を用いるのが好ましい。 In the present invention, specific examples of semiconductors forming the electron transport layer include tin oxide (SnO, SnO2 , SnO3, etc.), titanium oxide (TiO2 , etc.), and tungsten oxide ( WO2 , WO3 , W2O ). 3, etc.), zinc oxide (ZnO), niobium oxide (Nb 2 O 5 , etc.), tantalum oxide (Ta 2 O 5 , etc.), yttrium oxide (Y 2 O 3, etc.), strontium titanate (SrTiO 3, etc.), etc. Metal oxides; metal sulfides such as titanium sulfide, zinc sulfide, zirconium sulfide, copper sulfide, tin sulfide, indium sulfide, tungsten sulfide, cadmium sulfide, silver sulfide; titanium selenide, zirconium selenide, indium selenide, selenide Examples include metal selenides such as tungsten; and single semiconductors such as silicon and germanium. It is preferable to use one type or two or more types of these semiconductors. In the present invention, it is preferable to use one or more selected from tin oxide, titanium oxide, and zinc oxide as the semiconductor.
本発明において、前記半導体微粒子を含むペーストは市販品を用いてもよく、市販の半導体微粉末を溶媒中に分散させることによって調製したペースト(電子輸送層用塗布液)などを用いてもよい。ペーストを調製する際に使用する溶媒の具体例としては、水;メタノール、エタノール、イソプロピルアルコールなどのアルコール系溶媒;アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶媒;n-ヘキサン、シクロヘキサン、ベンゼン、トルエンなどの炭化水素系溶媒をあげることができるが、これらに限定されない。また、これらの溶媒は1種または2種以上の混合溶媒として使用することができる。 In the present invention, the paste containing semiconductor fine particles may be a commercially available product, or a paste prepared by dispersing commercially available semiconductor fine powder in a solvent (electron transport layer coating liquid) or the like may be used. Specific examples of solvents used when preparing the paste include water; alcohol solvents such as methanol, ethanol, and isopropyl alcohol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; n-hexane, cyclohexane, benzene, Examples include, but are not limited to, hydrocarbon solvents such as toluene. Further, these solvents can be used alone or as a mixed solvent of two or more.
本発明において半導体微粉末を溶媒中に分散させる方法としては、粉末を乳鉢などですりつぶしてから行ってもよく、ボールミル、ペイントコンディショナー、縦型ビーズミル、水平型ビーズミル、アトライターなどの分散機を用いてもよい。ペーストを調製する際には、半導体微粒子の凝集を防ぐために界面活性剤などを添加するのが好ましく、増粘させるためにポリエチレングリコールなどの増粘剤を添加するのが好ましい。 In the present invention, the semiconductor fine powder may be dispersed in a solvent by grinding the powder in a mortar or the like, or by using a dispersing machine such as a ball mill, paint conditioner, vertical bead mill, horizontal bead mill, or attritor. It's okay. When preparing the paste, it is preferable to add a surfactant or the like to prevent agglomeration of the semiconductor fine particles, and it is preferable to add a thickener such as polyethylene glycol to increase the viscosity.
本発明において、電子輸送層は、形成する材料に応じて、公知の製膜方法を用いて得ることができる。電子輸送層の製膜方法としては、塗布液を用いて被覆する任意の塗布方法を用いることができる。スピンコート法、インクジェット法、ドクターブレード法、ドロップキャスティング法、スキージ法、スクリーン印刷法、リバースロールコート法、グラビアコート法、キスコート法、ロールブラッシュ法、スプレーコート法、エアナイフコート法、ワイヤーバーバーコート法、パイプドクター法、含浸・コート法又はカーテンコート法などの湿式塗布法で導電性基板上に塗布した後、焼成により溶媒や添加物を除去して製膜する方法や、スパッタリング法、蒸着法、電着法、電析法、マイクロ波照射法などがあげられるが、これらに限定されない。本発明においては、前記方法により調製した電子輸送層用塗布液を用いてスピンコート法により製膜することが好ましいが、これに限定されない。なお、スピンコートの条件は、適宜設定することができる。製膜する雰囲気は特に制限されなく、大気中でもよい。 In the present invention, the electron transport layer can be obtained using a known film forming method depending on the material to be formed. As a method for forming the electron transport layer, any coating method using a coating liquid can be used. Spin coating method, inkjet method, doctor blade method, drop casting method, squeegee method, screen printing method, reverse roll coating method, gravure coating method, kiss coating method, roll brushing method, spray coating method, air knife coating method, wire barber coating method , a method in which a film is formed by coating on a conductive substrate by a wet coating method such as a pipe doctor method, an impregnation/coating method, or a curtain coating method, and then removing the solvent and additives by baking, a sputtering method, a vapor deposition method, Examples include, but are not limited to, an electrodeposition method, an electrodeposition method, a microwave irradiation method, and the like. In the present invention, it is preferable to form a film by a spin coating method using the coating liquid for an electron transport layer prepared by the method described above, but the method is not limited thereto. Note that the conditions for spin coating can be set as appropriate. The atmosphere in which the film is formed is not particularly limited, and may be in the air.
電子輸送層の膜厚は、光電変換効率をより向上させる観点から、緻密な電子輸送層が用いられる場合は、電子輸送層の厚みは通常5nm~100nmであることが好ましく、また10nm~50nmであることがより好ましい。本発明において、緻密な層に加えて、多孔質(メソポーラス)な金属酸化物が用いられる場合は、その膜厚は通常20~200nm以下であることが好ましく、また50~150nmであることがより好ましい。 From the viewpoint of further improving photoelectric conversion efficiency, when a dense electron transport layer is used, the thickness of the electron transport layer is usually preferably 5 nm to 100 nm, and preferably 10 nm to 50 nm. It is more preferable that there be. In the present invention, when a porous (mesoporous) metal oxide is used in addition to the dense layer, the film thickness is usually preferably 20 to 200 nm or less, and more preferably 50 to 150 nm. preferable.
〈光電変換層〉
本発明の光電変換素子において、図1に示す前記電子輸送層2の上に、光電変換層(ペロブスカイト層)3が形成されることが好ましい。
<Photoelectric conversion layer>
In the photoelectric conversion element of the present invention, it is preferable that a photoelectric conversion layer (perovskite layer) 3 is formed on the electron transport layer 2 shown in FIG.
本発明において、ペロブスカイト型光電変換素子として用いる場合、光電変換層であるペロブスカイト材料は、一般式ABX3で表される構造を持つ一連の材料を表す。ここで、A、B、およびXとしては、それぞれ、有機カチオンあるいは1価の金属カチオン、金属カチオン、およびハロゲン化物アニオンを表し、例として、A=K+、Rb+、Cs+、CH3NH3 +(以下、MA:メチルアンモニウム)、NH=CHNH2 +(以下、FA:ホルムアミジニウム)、CH3CH2NH3 +(以下、EA:エチルアンモニウム);B=Pb、Sn;X=I-、Br-があげられる。さらに、具体的には、MAPbI3、FAPbI3、EAPbI3、CsPbI3、MASnI3、FASnI3、EASnI3、MAPbBr3、FAPbBr3、EAPbBr3、MASnBr3、FASnBr3、EASnBr3の任意の組成で表されるペロブスカイト材料、及びFAMA)Pb(IBr)3、K(FAMA)Pb(IBr)3、Rb(FAMA)Pb(IBr)3、Cs(FAMA)Pb(IBr)3の任意の組成で表される混合カチオン、混合アニオンのペロブスカイト材料を含有する層を用いることができるが、これらに限定されない。これらのペロブスカイト材料は、1種または2種以上を用いることが好ましい。また、ペロブスカイト材料以外の光吸収剤を含んでいてもよい。 In the present invention, when used as a perovskite photoelectric conversion element, the perovskite material that is the photoelectric conversion layer represents a series of materials having a structure represented by the general formula ABX3 . Here, A, B, and X each represent an organic cation, a monovalent metal cation, a metal cation, and a halide anion; for example, A=K + , Rb + , Cs + , CH 3 NH 3 + (hereinafter, MA: methyl ammonium), NH=CHNH 2 + (hereinafter, FA: formamidinium), CH 3 CH 2 NH 3 + (hereinafter, EA: ethyl ammonium); B = Pb, Sn; Examples include I- and Br- . Further, specifically, MAPbI 3 , FAPbI 3 , EAPbI 3 , CsPbI 3 , MASnI 3 , FASnI 3 , EASnI 3 , MAPbBr 3 , FAPbBr 3 , EAPbBr 3 , MASnBr 3 , FASnBr 3 , EAS At any composition of nBr 3 The perovskite material represented by Layers containing mixed cation, mixed anion perovskite materials can be used, but are not limited to these. It is preferable to use one or more types of these perovskite materials. Furthermore, the material may contain a light absorbing agent other than the perovskite material.
本発明の光電変換素子の、光電変換層(ペロブスカイト層)を、塗布液を用いて被覆する方法としては任意の塗布方法を用いることができ、電子輸送層の製膜方法と同じ方法があげられる。 Any coating method can be used to coat the photoelectric conversion layer (perovskite layer) of the photoelectric conversion element of the present invention using a coating liquid, and examples thereof include the same method as the method for forming the electron transport layer. .
ペロブスカイト前駆体は、市販の材料を用いてもよく、本発明においては、鉛ハロゲン化物、メチルアンモニウムハロゲン化物、ホルムアミジンハロゲン化物、セシウムハロゲン化物からなる前駆体を任意の組成により用いることが好ましいが、これに限定されない。 Commercially available materials may be used as the perovskite precursor, and in the present invention, it is preferable to use a precursor consisting of lead halide, methylammonium halide, formamidine halide, or cesium halide with any composition. , but not limited to.
本発明のペロブスカイト前駆体溶液の溶媒は、前駆体の溶解性の観点から、N,N-ジメチルホルムアミド(DMF)、ジメチルスルホキシド(DMSO)、γ-ブチロラクトン等があげられるが、これらに限定されない。また、これらの溶媒は、1種または2種以上を混合して使用してもよく、N,N-ジメチルホルムアミドとジメチルスルホキシドの混合溶液を使用することが好ましい。 From the viewpoint of solubility of the precursor, the solvent for the perovskite precursor solution of the present invention includes, but is not limited to, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and γ-butyrolactone. Further, these solvents may be used alone or in combination of two or more, and it is preferable to use a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide.
本発明において、光電変換層(ペロブスカイト層)の製膜時の雰囲気は、水分の混入を防ぐことにより再現よく高効率ペロブスカイト型太陽電池を製造できる観点から、乾燥雰囲気下が好ましく、グローブボックス等の乾燥不活性気体雰囲気下がより好ましい。また、モレキュラーシーブ等で脱水を行い、水分含量が少ない溶媒を用いることが好ましい。 In the present invention, the atmosphere during film formation of the photoelectric conversion layer (perovskite layer) is preferably a dry atmosphere from the viewpoint of preventing moisture from entering and producing highly efficient perovskite solar cells with good reproducibility. A dry inert gas atmosphere is more preferred. Further, it is preferable to perform dehydration using a molecular sieve or the like and use a solvent with a low water content.
本発明において、光電変換層(ペロブスカイト層)をホットプレート等により加熱する際の温度は、前駆体よりペロブスカイト材料を生成する観点から、50~200℃が好ましく、70~150℃がより好ましい。また、加熱時間は、10~90分程度が好ましく、10~60分程度がより好ましい。 In the present invention, the temperature at which the photoelectric conversion layer (perovskite layer) is heated with a hot plate or the like is preferably 50 to 200°C, more preferably 70 to 150°C, from the viewpoint of producing a perovskite material from the precursor. Further, the heating time is preferably about 10 to 90 minutes, more preferably about 10 to 60 minutes.
本発明の光電変換層(ペロブスカイト層)の膜厚は、欠陥や剥離による性能劣化をより抑制する観点、および光電変換層が十分な光吸収率を持つとともに、素子抵抗が高くなりすぎないようにするために、50~1000nmが好ましく、300~700nmがより好ましい。 The film thickness of the photoelectric conversion layer (perovskite layer) of the present invention is determined from the viewpoint of further suppressing performance deterioration due to defects and peeling, and from the viewpoint of ensuring that the photoelectric conversion layer has sufficient light absorption rate and that the element resistance does not become too high. In order to achieve this, the wavelength is preferably 50 to 1000 nm, more preferably 300 to 700 nm.
〈正孔輸送層〉
本発明の光電変換素子において、図1に示す正孔輸送層4は、正孔を輸送する機能を有する層であり、光電変換層(ペロブスカイト層)3と対極5との間に位置する層である。正孔輸送層は、光電変換層から電極への正孔の移動効率を向上させ、また、電子の移動をブロックさせるために用いる。正孔輸送層には、例えば、導電体、半導体、有機正孔輸送材料などを用いることができ、正孔輸送特性をさらに向上させることを目的として、添加剤が含まれていてもよい。
<Hole transport layer>
In the photoelectric conversion element of the present invention, the hole transport layer 4 shown in FIG. 1 is a layer that has a function of transporting holes, and is a layer located between the photoelectric conversion layer (perovskite layer) 3 and the counter electrode 5. be. The hole transport layer is used to improve the efficiency of hole movement from the photoelectric conversion layer to the electrode and to block the movement of electrons. For example, a conductor, a semiconductor, an organic hole transport material, etc. can be used for the hole transport layer, and additives may be included for the purpose of further improving hole transport properties.
本発明の正孔輸送層は、前記一般式(1)で表される化合物を正孔輸送材料として含有する層である。本発明の正孔輸送層には、前記一般式(1)で表される化合物を1種または2種以上を併用してもよく、本発明に属さない他の正孔輸送材料等と併用することもできる。 The hole transport layer of the present invention is a layer containing the compound represented by the general formula (1) as a hole transport material. In the hole transport layer of the present invention, one or more compounds represented by the general formula (1) may be used in combination, or in combination with other hole transport materials that do not belong to the present invention. You can also do that.
本発明の正孔輸送材料に属さない他の正孔輸送材料の具体例としては、例えば、CuI、CuInSe2、CuS等の1価銅を含む化合物半導体;GaP、NiO、CoO、FeO、Bi2O3、MoO2、Cr2O3等の銅以外の金属を含む化合物があげられ、これらの酸化物金属は正孔輸送層中に混合してもよく、正孔輸送材料の上に積層されていてもよい。有機の正孔輸送材料としては、例えば、ポリ-3-ヘキシルチオフェン(P3HT)、ポリエチレンジオキシチオフェン(PEDOT)等のポリチオフェン誘導体;2,2’,7,7’-テトラキス-(N,N-ジ-p-メトキシフェニルアミン)-9,9’-スピロビフルオレン(Spiro-OMeTAD)等のフルオレン誘導体;ポリビニルカルバゾール等のカルバゾール誘導体;ポリ[ビス(4-フェニル)(2,4,6-トリメチルフェニル)アミン](PTAA)等のトリフェニルアミン誘導体;ジフェニルアミン誘導体;ポリシラン誘導体;ポリアニリン誘導体等があげられる。 Specific examples of other hole transport materials that do not belong to the hole transport materials of the present invention include compound semiconductors containing monovalent copper such as CuI, CuInSe 2 and CuS; GaP, NiO, CoO, FeO, Bi 2 Compounds containing metals other than copper such as O 3 , MoO 2 , and Cr 2 O 3 can be mentioned, and these oxide metals may be mixed in the hole transport layer or laminated on the hole transport material. You can leave it there. Examples of organic hole transport materials include polythiophene derivatives such as poly-3-hexylthiophene (P3HT) and polyethylenedioxythiophene (PEDOT); 2,2',7,7'-tetrakis-(N,N- Fluorene derivatives such as di-p-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-OMeTAD); Carbazole derivatives such as polyvinylcarbazole; Poly[bis(4-phenyl)(2,4,6-trimethyl Examples thereof include triphenylamine derivatives such as phenylamine] (PTAA); diphenylamine derivatives; polysilane derivatives; and polyaniline derivatives.
本発明の光電変換素子の正孔輸送層を、塗布液を用いて被覆する方法としては任意の塗布方法を用いることができ、電子輸送層の製膜方法と同じ方法をあげることができる。 Any coating method can be used to coat the hole transport layer of the photoelectric conversion element of the present invention using a coating liquid, and examples thereof include the same method as the method for forming the electron transport layer.
本発明において、製膜の際、正孔輸送層用塗布液に使用される溶媒は、ベンゼン、トルエン、キシレン、メシチレン、テトラリン(1,2,3,4‐テトラヒドロナフタレン)、モノクロロベンゼン(クロロベンゼン)、o-ジクロロベンゼン、m-ジクロロベンゼン、p-ジクロロベンゼン、ニトロベンゼン等の芳香族系有機溶媒;ジクロロメタン、クロロホルム、1,2-ジクロロエタン、1,1,2-トリクロロエタン、ジクロロメタン等のハロゲン化アルキル系有機溶媒;ベンゾニトリル、アセトニトリル等のニトリル系溶媒;テトラヒドロフラン、ジオキサン、ジイソプロピルエーテル、c-ペンチルメチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル等のエーテル系溶媒;酢酸エチル、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶媒;メタノール、イソプロパノール、n-ブタノール、プロピレングリコール、1,3-ブタンジオール、1,4-ブタンジオール、2,3-ブタンジオール、シクロヘキサノール、2-n-ブトキシエタノール等のアルコール系溶媒等があげられるが、これらに限定されない。また、上記溶媒は、1種または2種以上を混合して使用してもよく、構造により使用する溶媒を選択することができる。特に、芳香族系有機溶媒およびハロゲン化アルキル系有機溶媒を使用することが好ましい。 In the present invention, the solvent used in the coating solution for the hole transport layer during film formation is benzene, toluene, xylene, mesitylene, tetralin (1,2,3,4-tetrahydronaphthalene), monochlorobenzene (chlorobenzene). , o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, nitrobenzene, and other aromatic organic solvents; dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, dichloromethane, and other halogenated alkyl solvents Organic solvents; Nitrile solvents such as benzonitrile and acetonitrile; Ether solvents such as tetrahydrofuran, dioxane, diisopropyl ether, c-pentyl methyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol monomethyl ether; ethyl acetate, propylene glycol Ester solvents such as monomethyl ether acetate; methanol, isopropanol, n-butanol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, cyclohexanol, 2-n-butoxyethanol Examples include alcoholic solvents such as, but are not limited to. Further, the above-mentioned solvents may be used alone or in combination of two or more, and the solvent to be used can be selected depending on the structure. In particular, it is preferable to use aromatic organic solvents and halogenated alkyl organic solvents.
本発明において、正孔輸送層の膜厚は、光電変換効率をより向上させる観点から、5~500nmであることが好ましく、10nm~250nmであることがより好ましい。 In the present invention, the thickness of the hole transport layer is preferably from 5 to 500 nm, more preferably from 10 to 250 nm, from the viewpoint of further improving photoelectric conversion efficiency.
本発明において、正孔輸送層の製膜時の雰囲気は、水分の混入を防ぐことにより再現よく高効率ペロブスカイト型太陽電池を製造できる観点から、乾燥雰囲気下が好ましい。また、水分含有量が10ppm以下の脱水された溶媒を用いることが好ましい。 In the present invention, the atmosphere during film formation of the hole transport layer is preferably a dry atmosphere from the viewpoint of being able to manufacture highly efficient perovskite solar cells with good reproducibility by preventing moisture from entering. Further, it is preferable to use a dehydrated solvent having a water content of 10 ppm or less.
〈添加剤〉
本発明では、正孔輸送層の添加剤として、ドーパント(あるいは、酸化剤)や塩基性化合物(あるいは、塩基性添加剤)を含有していてもよい。正孔輸送層に添加剤を含有させ、正孔輸送層における正孔輸送材料のキャリア濃度を向上させること(ドーピング)は、光電変換素子の光電変換効率向上につながる。本発明において、正孔輸送層に添加剤であるドーパントおよび塩基性添加剤を含有する場合、正孔輸送材料1当量に対して、添加剤3.5当量以下であることが好ましい。
<Additive>
In the present invention, a dopant (or oxidizing agent) or a basic compound (or basic additive) may be contained as an additive for the hole transport layer. Incorporating an additive into the hole transport layer to improve the carrier concentration of the hole transport material in the hole transport layer (doping) leads to improvement in the photoelectric conversion efficiency of the photoelectric conversion element. In the present invention, when the hole transport layer contains a dopant and a basic additive as additives, it is preferable that the amount of the additive is 3.5 equivalents or less with respect to 1 equivalent of the hole transport material.
本発明において、ドーパントを含有させる場合、ドーパントの具体例としては、ビス(トリフルオロメチルスルホニル)イミドリチウム(LiTFSI)、ビス(トリフルオロメタンスルホニル)イミド銀、トリス(2-(1H-ピラゾール-1-イル)-4-tert-ブチルピリジン)コバルト(III)トリ[ビス(トリフルオロメタン)スルホンイミド](FK209)、NOSbF6、SbCl5、SbF5などをあげることができる。本発明において、ビス(トリフルオロメチルスルホニル)イミドリチウム(LiTFSI)を用いることが好ましいが、これに限定されない。 In the present invention, when a dopant is contained, specific examples of the dopant include lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), silver bis(trifluoromethanesulfonyl)imide, tris(2-(1H-pyrazole-1- Examples include cobalt(III) tri[bis(trifluoromethane)sulfonimide] (FK209), NOSbF 6 , SbCl 5 and SbF 5 . In the present invention, it is preferable to use lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), but the invention is not limited thereto.
本発明において、ドーパントを使用する場合、正孔輸送層に含有する正孔輸送材料1当量に対して、2.0当量以下が好ましく、0.5当量以下であることがより好ましい。正孔輸送層に添加剤を含有させることは、光電変換素子の光電変換効率向上につながる一方で、添加剤であるドーパントを使用することは、有機化合物を用いた光電変換素子の耐久性を下げ、素子全体の寿命を短くしてしまうことが懸念されている(例えば、非特許文献3)。このため、ドーパントの含有量を低減した正孔輸送層を有する光電変換素子の開発が望まれている。また、含有量を低減することができれば、添加剤コストの削減や、製造プロセスコストの削減が可能となる。 In the present invention, when a dopant is used, it is preferably 2.0 equivalents or less, more preferably 0.5 equivalents or less, per equivalent of the hole transport material contained in the hole transport layer. Including additives in the hole transport layer improves the photoelectric conversion efficiency of photoelectric conversion elements, but using dopants as additives reduces the durability of photoelectric conversion elements using organic compounds. There is a concern that the lifetime of the entire device may be shortened (for example, Non-Patent Document 3). Therefore, it is desired to develop a photoelectric conversion element having a hole transport layer with a reduced content of dopant. Furthermore, if the content can be reduced, it is possible to reduce additive costs and manufacturing process costs.
また、本発明において、正孔輸送層の添加剤として塩基性化合物(塩基性添加剤)を含有してもよい。本発明において、塩基性化合物を含有させる場合、具体例としては、4-tert-ブチルピリジン(tBP)、2-ピコリン、2,6-ルチジンなどがあげられる。塩基性化合物は、ドーパントを使用する際に併用して用いられることが多い。本発明においても、ドーパントを使用する際には併用することが望ましく、tert-ブチルピリジンを用いることが好ましい。 Further, in the present invention, a basic compound (basic additive) may be contained as an additive in the hole transport layer. In the present invention, when a basic compound is contained, specific examples include 4-tert-butylpyridine (tBP), 2-picoline, and 2,6-lutidine. A basic compound is often used in combination with a dopant. Also in the present invention, when using a dopant, it is desirable to use them together, and it is preferable to use tert-butylpyridine.
本発明において、塩基性化合物を使用する場合、本発明の正孔輸送材料1当量に対して、5当量以下であることが好ましく、3当量以下であることがさらに好ましい。 In the present invention, when a basic compound is used, it is preferably 5 equivalents or less, and more preferably 3 equivalents or less, based on 1 equivalent of the hole transport material of the present invention.
〈対極〉
本発明において、図1に示す対極5は、導電性支持体1に対向配置され、正孔輸送層4の上に形成されることで、正孔輸送層と電荷のやり取りが可能である。本発明の光電変換素子においては、正孔輸送層4上に対極として金属電極を備えることが好ましいが、正孔輸送層4と対極5との間に有機材料もしくは無機化合物半導体からなる電子ブロッキング層を追加することもできる。
<Opposite>
In the present invention, the counter electrode 5 shown in FIG. 1 is disposed opposite to the conductive support 1 and formed on the hole transport layer 4, so that it can exchange charges with the hole transport layer. In the photoelectric conversion element of the present invention, it is preferable to provide a metal electrode as a counter electrode on the hole transport layer 4, but between the hole transport layer 4 and the counter electrode 5 there is an electron blocking layer made of an organic material or an inorganic compound semiconductor. You can also add .
本発明において、対極に使用される材料としては具体的に、白金、チタン、ステンレス、アルミニウム、金、銀、ニッケル、マグネシウム、クロム、コバルト、銅などの金属又はこれらの合金があげられる。これらのなかでも、薄膜においても高い電気伝導性を示す点で金、銀または銀の合金を用いることが好ましい。なお、銀の合金としては、硫化又は塩素化の影響を受けにくく薄膜としての安定性を向上させるために、銀と金の合金、銀と銅の合金、銀とパラジウムの合金、銀と銅とパラジウムの合金、銀と白金の合金などがあげられる。 In the present invention, specific examples of the material used for the counter electrode include metals such as platinum, titanium, stainless steel, aluminum, gold, silver, nickel, magnesium, chromium, cobalt, and copper, or alloys thereof. Among these, it is preferable to use gold, silver, or a silver alloy because they exhibit high electrical conductivity even in thin films. In addition, silver alloys include silver and gold alloys, silver and copper alloys, silver and palladium alloys, and silver and copper alloys in order to be less susceptible to sulfidation or chlorination and improve the stability of thin films. Examples include alloys of palladium and alloys of silver and platinum.
本発明において対極は、蒸着等の方法で形成できる材料が好ましい。 In the present invention, the counter electrode is preferably made of a material that can be formed by a method such as vapor deposition.
対極として金属電極を用いる場合は、その膜厚は、良好な導電性を得るために10nm以上であることが好ましく、50nm以上であることがより好ましい。 When using a metal electrode as a counter electrode, the film thickness thereof is preferably 10 nm or more, more preferably 50 nm or more in order to obtain good conductivity.
本発明の光電変換素子においては、導電性支持体が陰極となり、対極が陽極となる。太陽光などの光は導電性支持体側から照射する方が好ましい。太陽光などの照射により、光電変換層(ペロブスカイト層)が光を吸収して励起状態となって電子と正孔が生成する。この電子が電子輸送層を、正孔が正孔輸送層を経由して電極へ移動することにより電流が流れ、光電変換素子として機能するようになる。 In the photoelectric conversion element of the present invention, the conductive support serves as a cathode, and the counter electrode serves as an anode. It is preferable to irradiate light such as sunlight from the conductive support side. When irradiated with sunlight or the like, the photoelectric conversion layer (perovskite layer) absorbs light and enters an excited state, generating electrons and holes. As the electrons move to the electrode via the electron transport layer and the holes move to the electrode via the hole transport layer, a current flows, and the device functions as a photoelectric conversion element.
本発明の光電変換素子の性能(特性)を評価する際には、短絡電流密度、開放電圧、フィルファクター、光電変換効率の測定を行う。短絡電流密度とは、出力端子を短絡させたときの両端子間に流れる1cm2あたりの電流を表し、開放電圧とは、出力端子を開放させたときの両端子間の電圧を表す。また、フィルファクターとは最大出力(電流と電圧の積)を、短絡電流密度と開放電圧の積で割った値であり、主に内部抵抗に左右される。光電変換効率は、最大出力(W)を1cm2あたりの光強度(W)で割った値に100を乗じてパーセント表示した値として求められる。 When evaluating the performance (characteristics) of the photoelectric conversion element of the present invention, short circuit current density, open circuit voltage, fill factor, and photoelectric conversion efficiency are measured. The short-circuit current density represents the current per 1 cm 2 that flows between both terminals when the output terminals are short-circuited, and the open-circuit voltage represents the voltage between the two terminals when the output terminals are opened. Fill factor is the value obtained by dividing the maximum output (the product of current and voltage) by the product of short-circuit current density and open circuit voltage, and is mainly influenced by internal resistance. The photoelectric conversion efficiency is determined as a value obtained by dividing the maximum output (W) by the light intensity (W) per 1 cm 2 and multiplying it by 100, expressed as a percentage.
本発明の光電変換素子は、太陽電池や各種光センサーなどに応用できる。本発明の太陽電池はペロブスカイト型太陽電池であると好ましく、ペロブスカイト型太陽電池は、前記一般式(1)で表される化合物を含有する正孔輸送材料を正孔輸送層として含む光電変換素子がセルとなり、そのセルを必要枚数配列してモジュール化し、所定の電気配線を設けることによって得られる。 The photoelectric conversion element of the present invention can be applied to solar cells, various optical sensors, and the like. The solar cell of the present invention is preferably a perovskite solar cell, and the perovskite solar cell has a photoelectric conversion element containing a hole transporting layer containing a hole transporting material containing the compound represented by the general formula (1). It can be obtained by arranging a required number of cells to form a module and providing predetermined electrical wiring.
以上、好ましい実施形態について説明したが、本発明はこれに限定されるものではなく、本発明を逸脱しない範囲内で適宜変更してもよい。 Although the preferred embodiments have been described above, the present invention is not limited thereto, and may be modified as appropriate without departing from the scope of the present invention.
以下、本発明を実施例により図面を参照しながら具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、合成実施例において得られた化合物の同定は、1H-NMR(1H-NMR(日本電子株式会社製核磁気共鳴装置、JNM-ECZ400S/L1型))により行った。 Hereinafter, the present invention will be specifically described by way of examples with reference to the drawings, but the present invention is not limited to the following examples. The compounds obtained in the synthesis examples were identified by 1 H-NMR (1H-NMR (Nuclear magnetic resonance apparatus, JNM-ECZ400S/L1 type, manufactured by JEOL Ltd.)).
[合成実施例1]化合物(A-1)の合成
反応容器に2,7-ジブロモチオキサントン(0.20g)、[4-[ビス(4-メトキシフェニル)アミノ]フェニル]ボロン酸(0.46g、東京化成社製)、テトラキス(トリフェニルホスフィン)パラジウム(0)(0.05g、関東化学社製)、炭酸カリウム(0.69g、関東化学社製)、トルエン(20mL)、水(5.0mL)を投入し、減圧下、脱気を行った。アルゴン雰囲気下、8時間加熱還流下で撹拌した。反応終了後、水(50mL)とトルエン(50mL)を投入し、分液した。有機層を硫酸マグネシウムで脱水し、ろ過した後、ろ液を減圧濃縮した。粗生成物をシリカゲルカラムクロマトグラフィー(トルエン:酢酸エチル=100:1)で精製し、再沈殿(酢酸エチル/メタノール)することで、下記式(A-1)で表される化合物を黄色固体(収量:0.36g、収率:81%)として得た。
[Synthesis Example 1] Synthesis of compound (A-1) 2,7-dibromothioxanthone (0.20 g) and [4-[bis(4-methoxyphenyl)amino]phenyl]boronic acid (0.46 g) , manufactured by Tokyo Kagaku Co., Ltd.), tetrakis(triphenylphosphine)palladium (0) (0.05 g, manufactured by Kanto Kagaku Co., Ltd.), potassium carbonate (0.69 g, manufactured by Kanto Kagaku Co., Ltd.), toluene (20 mL), water (5. 0 mL) and degassed under reduced pressure. The mixture was heated and stirred under reflux for 8 hours under an argon atmosphere. After the reaction was completed, water (50 mL) and toluene (50 mL) were added to separate the layers. The organic layer was dehydrated with magnesium sulfate and filtered, and then the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (toluene: ethyl acetate = 100:1) and reprecipitated (ethyl acetate/methanol) to convert the compound represented by the following formula (A-1) into a yellow solid ( Yield: 0.36 g, yield: 81%).
1H-NMR(400MHz、DMSO-d6):δ(ppm)=8.64(2H)、8.04(2H)、7.91(2H)、7.63(4H)、7.09(8H)、6.95(8H)、6.87(4H)、3.76(12H)。 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 8.64 (2H), 8.04 (2H), 7.91 (2H), 7.63 (4H), 7.09 ( 8H), 6.95 (8H), 6.87 (4H), 3.76 (12H).
[合成実施例2]化合物(A-21)の合成
反応容器に2,7-ジブロモチオキサントン(0.20g)、下記式(10)の化合物(1.1g)、テトラキス(トリフェニルホスフィン)パラジウム(0)(0.03g、関東化学社製)、炭酸カリウム(0.69g、関東化学社製)、トルエン(50mL)、エタノール(10mL)、水(5mL)を投入し、減圧下、脱気を行った。アルゴン雰囲気下、5時間加熱還流下で撹拌した。反応終了後、水(200mL)、メタノール(100mL)を投入した。これを分液し、有機層を硫酸マグネシウムで乾燥後、減圧下濃縮した。粗生成物をシリカゲルカラム(トルエン:酢酸エチル=30:1~20:1(体積比))にて精製し、下記式(A-21)で表される化合物を黄色粉末(収量:0.59g、収率:67%)として得た。
[Synthesis Example 2] Synthesis of compound (A-21) In a reaction vessel, 2,7-dibromothioxanthone (0.20 g), the compound of the following formula (10) (1.1 g), and tetrakis(triphenylphosphine)palladium ( 0) (0.03 g, Kanto Kagaku Co., Ltd.), potassium carbonate (0.69 g, Kanto Kagaku Co., Ltd.), toluene (50 mL), ethanol (10 mL), and water (5 mL), and degassed under reduced pressure. went. The mixture was heated and stirred under reflux for 5 hours under an argon atmosphere. After the reaction was completed, water (200 mL) and methanol (100 mL) were added. This was separated into layers, and the organic layer was dried over magnesium sulfate and then concentrated under reduced pressure. The crude product was purified using a silica gel column (toluene:ethyl acetate = 30:1 to 20:1 (volume ratio)), and the compound represented by the following formula (A-21) was obtained as a yellow powder (yield: 0.59 g). , yield: 67%).
1H-NMR(400MHz、DMSO-d6):δ(ppm)=8.84(2H)、8.25(2H)、8.08(6H)、7.80-7.75(8H)、7.40(4H)、7.12-7.09(4H)、6.90(16H)、6.83(16H)、3.70(24H)。 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 8.84 (2H), 8.25 (2H), 8.08 (6H), 7.80-7.75 (8H), 7.40 (4H), 7.12-7.09 (4H), 6.90 (16H), 6.83 (16H), 3.70 (24H).
[実施例1]光電変換素子の作製および電流-電圧特性評価
FLAT ITO膜付きガラス(導電性支持体1、ジオマテック社製)をイソプロピルアルコールで超音波洗浄後、UVオゾン処理した。
このITO膜上にTin(IV) oxide,15% in H2O colloidal dispersion(Alfa Aesar社製)と精製水を体積比で1:9とした酸化スズ分散液(電子輸送層用塗布液)をスピンコートにより塗布した。その後、ホットプレートで150℃にて30分加熱することで膜厚が約20nmの酸化スズ層(電子輸送層2)を形成した。
[Example 1] Production of photoelectric conversion element and evaluation of current-voltage characteristics FLAT ITO film-coated glass (conductive support 1, manufactured by Geomatec) was ultrasonically cleaned with isopropyl alcohol and then treated with UV ozone.
On this ITO film, a tin oxide dispersion (coating liquid for electron transport layer) containing 1:9 volume ratio of Tin(IV) oxide, 15% in H 2 O colloidal dispersion (manufactured by Alfa Aesar) and purified water was applied. It was applied by spin coating. Thereafter, a tin oxide layer (electron transport layer 2) having a thickness of about 20 nm was formed by heating at 150° C. for 30 minutes using a hot plate.
窒素気流下のグローブボックスにて、ホルムアミジンよう化水素酸塩(1M、東京化成工業社製)、よう化鉛(II)(1.1M、東京化成工業社製)、メチルアミン臭化水素酸塩(0.2M、東京化成工業社製)、および臭化鉛(II)(0.2M、東京化成工業社製)を、ジメチルホルムアミドとジメチルスルホキシドを体積比で4:1とした混合溶媒に溶解させた。そこへよう化セシウム(1.5M、東京化成工業社製)のジメチルスルホキシド溶液を、セシウムの仕込み量が組成比で5%となるよう添加し、ペロブスカイト前駆体溶液を調製した。
窒素雰囲気下のグローブボックスにて、調製したペロブスカイト前駆体溶液を酸化スズ層上に滴下、スピンコートし、スピンコート中にクロロベンゼンを0.3mL滴下することでペロブスカイト前駆体を製膜した。その後、ホットプレートを用いて100℃で1時間加熱することで、膜厚が約500nmのCs(MAFA)Pb(IBr)3層(光電変換層3)を形成した。
In a glove box under a nitrogen stream, formamidine hydroiodide (1M, Tokyo Kasei Kogyo Co., Ltd.), lead (II) iodide (1.1M, Tokyo Kasei Kogyo Co., Ltd.), and methylamine hydrobromide were added. Salt (0.2M, manufactured by Tokyo Kasei Kogyo Co., Ltd.) and lead (II) bromide (0.2M, manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed in a mixed solvent of dimethylformamide and dimethyl sulfoxide at a volume ratio of 4:1. Dissolved. A dimethyl sulfoxide solution of cesium iodide (1.5 M, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added thereto so that the amount of cesium was 5% in terms of composition ratio, to prepare a perovskite precursor solution.
In a glove box under a nitrogen atmosphere, the prepared perovskite precursor solution was dropped onto the tin oxide layer and spin coated, and 0.3 mL of chlorobenzene was dropped during the spin coating to form a film of the perovskite precursor. Thereafter, three layers of Cs(MAFA)Pb(IBr) (photoelectric conversion layer 3) having a film thickness of about 500 nm were formed by heating at 100° C. for 1 hour using a hot plate.
窒素気流下のグローブボックスにて、4-tert-ブチルピリジン、及びビス(トリフルオロメタンスルホニル)イミドリチウムをドーパントとしてクロロベンゼンに溶解させた。当該のクロロベンゼン溶液に合成実施例1で得た正孔輸送材料である化合物(A-1)を50mMで溶解させ、(A-1)に対して上記4-tert-ブチルピリジンが3当量、ビス(トリフルオロメタンスルホニル)イミドリチウムが0.5当量になるよう調製し、正孔輸送層用塗布溶液とした。
窒素雰囲気下のグローブボックスにて、Cs(MAFA)Pb(IBr)3層(光電変換層3)上に正孔輸送層用塗布溶液をスピンコートし、膜厚が約200nmの正孔輸送層4を形成した。
In a glove box under a nitrogen stream, 4-tert-butylpyridine and lithium bis(trifluoromethanesulfonyl)imide were dissolved in chlorobenzene as dopants. Compound (A-1), which is the hole transport material obtained in Synthesis Example 1, was dissolved in the chlorobenzene solution at 50 mM, and the above 4-tert-butylpyridine was added in an amount of 3 equivalents to (A-1), and (Trifluoromethanesulfonyl)imide lithium was prepared in an amount of 0.5 equivalent to form a coating solution for a hole transport layer.
In a glove box under a nitrogen atmosphere, a hole transport layer coating solution was spin-coated on the Cs(MAFA)Pb(IBr) 3 layer (photoelectric conversion layer 3) to form a hole transport layer 4 with a film thickness of about 200 nm. was formed.
正孔輸送層上に、真空蒸着法にて真空度1×10-4Pa程度で、金を80nm程度製膜することで金電極(対極5)を形成し、光電変換素子を作製した。 On the hole transport layer, a gold electrode (counter electrode 5) was formed by forming a gold film of about 80 nm using a vacuum evaporation method at a vacuum degree of about 1×10 −4 Pa to produce a photoelectric conversion element.
白色光照射装置(分光計器株式会社製、OTENTO-SUN SH型)で発生させた疑似太陽光(AM1.5、100mW/cm2)を前記光電変換素子の導電性支持体側から照射し、ソースメータ(KEITHLEY社製、Model 2400 Series SourceMeter)を用いて電流-電圧特性を測定することで初期光電変換効率を得た。 Simulated sunlight (AM1.5, 100 mW/cm 2 ) generated by a white light irradiation device (manufactured by Bunko Keiki Co., Ltd., OTENTO-SUN SH type) was irradiated from the conductive support side of the photoelectric conversion element, and the source meter The initial photoelectric conversion efficiency was obtained by measuring the current-voltage characteristics using a Model 2400 Series Source Meter (manufactured by KEITHLEY).
電流-電圧特性の測定後、前記光電変換素子を、シリカゲルを設置したデシケータ中で30日間保管し、疑似太陽光照射下において再び電流-電圧特性を測定することで30日後の光電変換効率を得た。30日後の光電変換効率である経時の光電変換効率を表1に示す。 After measuring the current-voltage characteristics, the photoelectric conversion element was stored for 30 days in a desiccator equipped with silica gel, and the photoelectric conversion efficiency after 30 days was obtained by measuring the current-voltage characteristics again under simulated sunlight irradiation. Ta. Table 1 shows the photoelectric conversion efficiency over time, which is the photoelectric conversion efficiency after 30 days.
得られた初期光電変換効率と30日後の光電変換効率である経時の光電変換効率を用いて、下記式(a-1)より算出した変化率(%)を表1に示す。 Table 1 shows the rate of change (%) calculated from the following formula (a-1) using the obtained initial photoelectric conversion efficiency and the photoelectric conversion efficiency over time, which is the photoelectric conversion efficiency after 30 days.
[比較例1]
化合物(A-1)に代えて上記式(B-1)で表される標準的な正孔輸送材料のSpiro-OMeTAD(Sigma-Aldrich社製)を50mMとなるよう上記ドーパントのクロロベンゼン溶液に溶解させ使用したこと以外は実施例1と同様に光電変換素子を作製し、実施例1と同様に初期光電変換効率、および30日後の光電変換効率を得た。得られた初期光電変換効率と30日後の光電変換効率である経時の光電変換効率を用いて、下記式(a-1)より算出した変化率(%)を表1に示す。
[Comparative example 1]
Instead of compound (A-1), Spiro-OMeTAD (manufactured by Sigma-Aldrich), a standard hole transport material represented by the above formula (B-1), was dissolved in the chlorobenzene solution of the above dopant to a concentration of 50 mM. A photoelectric conversion element was produced in the same manner as in Example 1, except that it was used, and the initial photoelectric conversion efficiency and the photoelectric conversion efficiency after 30 days were obtained in the same manner as in Example 1. Table 1 shows the rate of change (%) calculated from the following formula (a-1) using the obtained initial photoelectric conversion efficiency and the photoelectric conversion efficiency over time, which is the photoelectric conversion efficiency after 30 days.
表1の結果から、本発明のチオキサントン骨格を有する化合物(A-1)を正孔輸送材料として用いた光電変換素子が、標準的な正孔輸送材料を用いた光電変換素子と比較して充分な光電変換効率と高い耐久性を示すことがわかる。 From the results in Table 1, it can be seen that the photoelectric conversion device using the compound (A-1) having a thioxanthone skeleton of the present invention as a hole transport material is more effective than the photoelectric conversion device using a standard hole transport material. It can be seen that it exhibits high photoelectric conversion efficiency and high durability.
本発明による正孔輸送材料を用いた光電変換素子は、良好な光電変換効率を示し、太陽光エネルギーを電気エネルギーに効率よく変換できる太陽電池としてクリーンエネルギーを提供することができ、その他有機ELやイメージセンサーなどにも展開することが可能である。 The photoelectric conversion element using the hole transporting material according to the present invention exhibits good photoelectric conversion efficiency, and can provide clean energy as a solar cell that can efficiently convert sunlight energy into electrical energy. It can also be applied to image sensors, etc.
1 導電性支持体
2 電子輸送層
3 光電変換層
4 正孔輸送層
5 対極
1 Conductive support 2 Electron transport layer 3 Photoelectric conversion layer 4 Hole transport layer 5 Counter electrode
Claims (7)
水素原子、ハロゲン原子、カルボキシル基、トリメチルシリル基、
置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルキル基、
置換基を有していてもよい炭素原子数2~20の直鎖状もしくは分岐状のアルケニル基、
置換基を有していてもよい炭素原子数3~12のシクロアルキル基、
置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアルコキシ基、
置換基を有していてもよい炭素原子数3~10のシクロアルコキシ基、
置換基を有していてもよい炭素原子数1~20の直鎖状もしくは分岐状のアシル基、
置換基を有していてもよい炭素原子数1~18のチオ基、
置換基を有していてもよい炭素原子数1~20のアミノ基、
置換基を有する炭素原子数6~36の芳香族炭化水素基、または
置換基を有していてもよい環形成原子数5~36の複素環基を表し、
R1~R5、R6~R10、R11~R15、R16~R20は隣り合う基同士で互いに結合して環を形成していてもよく、R5とR6およびR15とR16は互いに結合して環を形成していてもよい。
X1およびX2は、2価基を表し、同一でも異なっていてもよい。
Y1は、酸素原子、硫黄原子またはCR21R22を表し、
R21およびR22は、それぞれ独立して、ニトリル基、
置換基を有していてもよい炭素原子数1~10の直鎖状もしくは分岐状のアシル基、
または、置換基を有していてもよい炭素原子数1~10の直鎖状もしくは分岐状のアルコキシカルボニル基を表し、R21とR22は、互いに結合して環を形成していてもよい。] A compound represented by the following general formula (1).
Hydrogen atom, halogen atom, carboxyl group, trimethylsilyl group,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent,
A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,
a cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent,
A linear or branched acyl group having 1 to 20 carbon atoms that may have a substituent,
a thio group having 1 to 18 carbon atoms which may have a substituent,
an amino group having 1 to 20 carbon atoms which may have a substituent,
Represents an aromatic hydrocarbon group having 6 to 36 carbon atoms having a substituent, or a heterocyclic group having 5 to 36 ring atoms which may have a substituent,
R 1 to R 5 , R 6 to R 10 , R 11 to R 15 , and R 16 to R 20 may be adjacent groups that are bonded to each other to form a ring, and R 5 and R 6 and R 15 and R 16 may be bonded to each other to form a ring.
X 1 and X 2 represent divalent groups and may be the same or different.
Y 1 represents an oxygen atom, a sulfur atom or CR 21 R 22 ,
R 21 and R 22 are each independently a nitrile group,
A linear or branched acyl group having 1 to 10 carbon atoms which may have a substituent,
Alternatively, it represents a linear or branched alkoxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, and R 21 and R 22 may be bonded to each other to form a ring. . ]
水素原子、
置換基を有していてもよい炭素原子数1~10の直鎖状もしくは分岐状のアルキル基、
置換基を有していてもよい炭素原子数2~10の直鎖状もしくは分岐状のアルケニル基、
置換基を有していてもよい炭素原子数3~12のシクロアルキル基、
置換基を有していてもよい炭素原子数6~18の芳香族炭化水素基、または
置換基を有していてもよい環形成原子数5~18の複素環基を表し、
R23とR24、R25とR26およびR27とR28は、互いに結合して環を形成していてもよい。
Z1は、酸素原子、硫黄原子またはセレン原子を表し、mおよびnはそれぞれ0~2の整数を表す。] The compound according to claim 1, wherein in the general formula (1), X 1 and X 2 are represented by the following general formula (2).
hydrogen atom,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent,
a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent,
Represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 18 ring atoms which may have a substituent,
R 23 and R 24 , R 25 and R 26 , and R 27 and R 28 may be bonded to each other to form a ring.
Z 1 represents an oxygen atom, a sulfur atom, or a selenium atom, and m and n each represent an integer of 0 to 2. ]
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