JP2016134415A - Organic photoelectric conversion element - Google Patents
Organic photoelectric conversion element Download PDFInfo
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- JP2016134415A JP2016134415A JP2015006465A JP2015006465A JP2016134415A JP 2016134415 A JP2016134415 A JP 2016134415A JP 2015006465 A JP2015006465 A JP 2015006465A JP 2015006465 A JP2015006465 A JP 2015006465A JP 2016134415 A JP2016134415 A JP 2016134415A
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- transport layer
- photoelectric conversion
- water
- organic photoelectric
- conversion element
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- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
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- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 229910052747 lanthanoid Inorganic materials 0.000 description 1
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 150000005041 phenanthrolines Chemical class 0.000 description 1
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- 125000005936 piperidyl group Chemical group 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
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- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical class C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
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- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Photovoltaic Devices (AREA)
Abstract
Description
本発明は、有機光電変換素子に関する。 The present invention relates to an organic photoelectric conversion element.
近年、光エネルギーを利用した有機光電変換素子（有機太陽電池及び光センサーなど）が注目されている。複数の活性層を積層すると高い起電力を得ることができるため、タンデム構造に代表される、２つ以上の活性層を積層したマルチ接合構造を有する素子が期待されている。マルチ接合構造を有する有機光電変換素子においては、活性層を単に積層した有機光電変換素子のみならず、活性層の間に接合体を設けた有機光電変換素子も検討されている。 In recent years, organic photoelectric conversion elements (such as organic solar cells and optical sensors) using light energy have attracted attention. Since a high electromotive force can be obtained by laminating a plurality of active layers, an element having a multi-junction structure in which two or more active layers are laminated, represented by a tandem structure, is expected. In an organic photoelectric conversion element having a multi-junction structure, not only an organic photoelectric conversion element in which active layers are simply stacked, but also an organic photoelectric conversion element in which a bonded body is provided between active layers has been studied.
接合体は、通常、電子輸送層、電荷再結合層及び正孔輸送層などの複数の層が積層されて構成される。マルチ接合構造を有する有機光電変換素子としては、２層の活性層と、該活性層の間に、界面活性剤を添加したＰＥＤＯＴ：ＰＳＳ｛ポリ（３，４−エチレンジオキシチオフェン）（ＰＥＤＯＴ）：ポリ（４−スチレンスルホン酸）（ＰＳＳ）｝からなる正孔輸送層と、ポリエチレンイミンエトキシド（ＰＥＩＥ）からなる電子輸送層とを含む接合体を有する有機光電変換素子が提案されている（非特許文献１）。 The joined body is usually formed by laminating a plurality of layers such as an electron transport layer, a charge recombination layer, and a hole transport layer. As an organic photoelectric conversion element having a multi-junction structure, two active layers and a PEDOT: PSS {poly (3,4-ethylenedioxythiophene) (PEDOT) in which a surfactant is added between the active layers : An organic photoelectric conversion element having a joined body including a hole transport layer made of poly (4-styrenesulfonic acid) (PSS)} and an electron transport layer made of polyethyleneimine ethoxide (PEIE) ( Non-patent document 1).
しかしながら、上述の非特許文献１では、光電変換効率が必ずしも充分ではなかった。
本発明の目的は、高い光電変換効率が得られる有機光電変換素子およびその製造方法を提供することにある。
However, in the above-mentioned Non-Patent Document 1, the photoelectric conversion efficiency is not always sufficient.
The objective of this invention is providing the organic photoelectric conversion element from which high photoelectric conversion efficiency is obtained, and its manufacturing method.
すなわち、本発明は、以下の発明を提供する。
［１］一対の電極間に２以上の活性層を有し、少なくとも１組の隣接する２つの活性層の間に正孔輸送層と電子輸送層とを有する有機光電変換素子であって、前記電子輸送層がアミンを有し、前記正孔輸送層が下記に示す水リンス処理後の残膜率測定において残膜率が８０％以上であることを特徴とする有機光電変換素子。
＜水リンス処理後の残膜率測定方法＞
一辺１インチの正方形の基板上に、有機光電変換素子において正孔輸送層として成膜する場合と同等の膜厚となるようにスピンコートにより塗布成膜した後、前記膜上にメニスカス状に水を載せ、３０秒静置後、４０００ｒｐｍでスピンさせて水を振り切ることで水リンス処理を行う。水リンス処理前後の膜厚を触針式膜厚計で測定し、水リンス処理後の膜厚／水リンス処理前の膜厚×１００（％）を水リンス処理後の残膜率とする。
［２］前記電子輸送層が、アミン及び水を含む塗布液を塗布することによって形成される層である請求項１に記載された有機光電変換素子。
［３］前記アミンが、エトキシ化ポリエチレンイミンである請求項１または２に記載された有機光電変換素子。
［４］陰極、前記正孔輸送層及び前記電子輸送層がこの順で積層される請求項１〜３のいずれかに記載された有機光電変換素子。
［５］前記正孔輸送層と前記電子輸送層との間にさらに電荷再結合層を有する請求項１〜４のいずれかに記載された有機光電変換素子。
［６］前記活性層が塗布法によって形成される請求項１〜５のいずれかに記載された有機光電変換素子。
［７］前記活性層が、フラーレン類及びフラーレン類の誘導体からなる群より選ばれる１種以上と、共役高分子化合物とを含む請求項１〜６のいずれかに記載された有機光電変換素子。
［８］請求項１〜７のいずれかに記載された有機光電変換素子を有する有機光センサー。
［９］一対の電極間に２以上の活性層を有し、少なくとも１組の隣接する２つの活性層の間に正孔輸送層と電子輸送層とを有する有機光電変換素子の製造方法であって、活性層上に正孔輸送層を形成する工程と、前記正孔輸送層を形成する工程後に、アミン及び水を含む塗布液を塗布することによって電子輸送層を形成する工程とを含み、前記正孔輸送層が下記に示す膜の水リンス処理後の残膜率測定において残膜率が８０％以上である層であることを特徴とする有機光電変換素子の製造方法。
＜水リンス処理後の残膜率測定方法＞
一辺１インチの正方形の基板上に、有機光電変換素子において正孔輸送層として成膜する場合と同等の膜厚となるようにスピンコートにより塗布成膜した後、前記膜上にメニスカス状に水を載せ、３０秒静置後、４０００ｒｐｍでスピンさせて水を振り切ることで水リンス処理を行う。水リンス処理前後の膜厚を触針式膜厚計で測定し、水リンス処理後の膜厚／水リンス処理前の膜厚×１００（％）を水リンス処理後の残膜率とする。
That is, the present invention provides the following inventions.
[1] An organic photoelectric conversion device having two or more active layers between a pair of electrodes, and having a hole transport layer and an electron transport layer between at least one pair of adjacent two active layers, An organic photoelectric conversion element, wherein the electron transport layer has an amine, and the hole transport layer has a remaining film ratio of 80% or more in the measurement of the remaining film ratio after water rinsing treatment described below.
<Method for measuring remaining film ratio after water rinse treatment>
On a square substrate having a side of 1 inch, a film is formed by spin coating so as to have a film thickness equivalent to that for forming a hole transport layer in an organic photoelectric conversion element, and then water is formed on the film in a meniscus shape. After standing for 30 seconds, spin water at 4000 rpm and shake off water to perform water rinsing treatment. The film thickness before and after the water rinse treatment is measured with a stylus-type film thickness meter, and the film thickness after the water rinse treatment / the film thickness before the water rinse treatment × 100 (%) is defined as the remaining film ratio after the water rinse treatment.
[2] The organic photoelectric conversion device according to [1], wherein the electron transport layer is a layer formed by applying a coating solution containing an amine and water.
[3] The organic photoelectric conversion element according to claim 1 or 2, wherein the amine is ethoxylated polyethyleneimine.
[4] The organic photoelectric conversion element according to any one of claims 1 to 3, wherein the cathode, the hole transport layer, and the electron transport layer are laminated in this order.
[5] The organic photoelectric conversion element according to any one of claims 1 to 4, further comprising a charge recombination layer between the hole transport layer and the electron transport layer.
[6] The organic photoelectric conversion element according to any one of claims 1 to 5, wherein the active layer is formed by a coating method.
[7] The organic photoelectric conversion element according to any one of [1] to [6], wherein the active layer includes one or more selected from the group consisting of fullerenes and derivatives of fullerenes and a conjugated polymer compound.
[8] An organic optical sensor having the organic photoelectric conversion element according to any one of claims 1 to 7.
[9] A method for producing an organic photoelectric conversion device having two or more active layers between a pair of electrodes, and having a hole transport layer and an electron transport layer between at least one pair of adjacent active layers. A step of forming a hole transport layer on the active layer, and a step of forming an electron transport layer by applying a coating solution containing amine and water after the step of forming the hole transport layer, The method for producing an organic photoelectric conversion element, wherein the hole transport layer is a layer having a remaining film ratio of 80% or more in measurement of a remaining film ratio after water rinsing treatment of the film shown below.
<Method for measuring remaining film ratio after water rinse treatment>
On a square substrate having a side of 1 inch, a film is formed by spin coating so as to have a film thickness equivalent to that for forming a hole transport layer in an organic photoelectric conversion element, and then water is formed on the film in a meniscus shape. After standing for 30 seconds, spin water at 4000 rpm and shake off water to perform water rinsing treatment. The film thickness before and after the water rinse treatment is measured with a stylus-type film thickness meter, and the film thickness after the water rinse treatment / the film thickness before the water rinse treatment × 100 (%) is defined as the remaining film ratio after the water rinse treatment.
本発明によれば、高い光電変換効率が得られる有機光電変換素子およびその製造方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the organic photoelectric conversion element from which high photoelectric conversion efficiency is obtained, and its manufacturing method are provided.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
有機光電変換素子の構成
本発明の有機光電変換素子は、複数の活性層と、該活性層間に位置する、正孔輸送層及び電子輸送層を有する接合体とが、一対の電極間に積層されるマルチ接合有機光電変換素子であって、前記電子輸送層がアミンを有し、前記正孔輸送層が、下記に示す水リンス処理後の残膜率測定において残膜率が８０％以上であることを特徴とする。
Configuration of Organic Photoelectric Conversion Device In the organic photoelectric conversion device of the present invention, a plurality of active layers and a joined body having a hole transport layer and an electron transport layer, which are located between the active layers, are laminated between a pair of electrodes. The electron transport layer has an amine, and the hole transport layer has a residual film ratio of 80% or more in the measurement of the residual film ratio after the water rinse treatment shown below. It is characterized by that.
本実施の形態の有機光電変換素子の素子構造の一例を示す。
（ａ）陰極／活性層／接合体／活性層／陽極
（ｂ）陰極／（繰り返し単位）ｍ／活性層／陽極
記号「／」は、該記号「／」を挟む層が隣接して積層されることを示し、以下同様とする。（ｂ）において、「（繰り返し単位）」は、活性層と接合体との積層体（活性層／接合体）を表し、記号「ｍ」は１以上の整数を表し、「（繰り返し単位）ｍ」は、ｍ個の積層体（活性層／接合体）が積層された積層体を表す。なお陰極と活性層との間には電子輸送層を設けてもよく、また活性層と陽極との間には、正孔輸送層を設けてもよい。
An example of the element structure of the organic photoelectric conversion element of this Embodiment is shown.
(A) Cathode / active layer / junction / active layer / anode (b) Cathode / (repeating unit) m / active layer / anode The symbol “/” is formed by adjoining layers sandwiching the symbol “/”. The same shall apply hereinafter. In (b), “(repeat unit)” represents a laminate (active layer / joint) of the active layer and the joined body, the symbol “m” represents an integer of 1 or more, and “(repeat unit) m "Represents a laminate in which m laminates (active layers / joints) are laminated. An electron transport layer may be provided between the cathode and the active layer, and a hole transport layer may be provided between the active layer and the anode.
（ａ）の素子は、いわゆるタンデム構造の素子であり、（ｂ）の素子は、接合体を介して（ｍ＋１）個の活性層が積層されたマルチ接合構造の素子である。ここで、接合体を介して２個の活性層が積層されたマルチ接合構造をタンデム構造という。 The element (a) is an element having a so-called tandem structure, and the element (b) is an element having a multi-junction structure in which (m + 1) active layers are stacked via a bonded body. Here, a multi-junction structure in which two active layers are laminated via a joined body is referred to as a tandem structure.
接合体は、複数の層が積層されており、少なくとも正孔輸送層と電子輸送層とを含む。接合体は、例えば、正孔輸送層と、電荷再結合層と、電子輸送層とがこの順で積層されている。
なお、接合体は、正孔輸送層と電子輸送層のみから構成されていてもよく、また前述の３層以外の層を備えていてもよい。接合体において、電子輸送層が陽極側に配置され、正孔輸送層が陰極側に配置されていてもよい。
The joined body includes a plurality of layers stacked, and includes at least a hole transport layer and an electron transport layer. In the joined body, for example, a hole transport layer, a charge recombination layer, and an electron transport layer are laminated in this order.
In addition, the joined body may be composed of only the hole transport layer and the electron transport layer, or may include a layer other than the three layers described above. In the joined body, the electron transport layer may be disposed on the anode side, and the hole transport layer may be disposed on the cathode side.
有機光電変換素子は、通常、基板上に、一対の電極と、活性層と、接合体とを、以下に説明する順序で順次積層することで形成される。 The organic photoelectric conversion element is usually formed by sequentially laminating a pair of electrodes, an active layer, and a bonded body in the order described below on a substrate.
例えば、前記（ａ）の素子は、基板上に、陰極、活性層、接合体、活性層、陽極を、この順序で順次積層することで形成することができる。前記（ｂ）の素子も、上記（ａ）の素子と同様に、基板上に、陰極、活性層、接合体、活性層、接合体、・・・活性層、陽極、をこの順序で順次積層することで形成することができる。 For example, the element (a) can be formed by sequentially laminating a cathode, an active layer, a bonded body, an active layer, and an anode in this order on a substrate. In the same manner as the element (a), the element (b) is formed by sequentially stacking a cathode, an active layer, a bonded body, an active layer, a bonded body,. By doing so, it can be formed.
本発明の有機光電変換素子で用いる基板は、電極を形成し、有機物の層を形成する際に化学的に変化しないものであればよい。基板の材料としては、例えば、ガラス、プラスチック、高分子フィルム、シリコンが挙げられる。不透明な基板を用いる場合には、反対の電極（即ち、基板から遠い方の電極）が透明又は半透明であることが好ましい。以下、有機光電変換素子の各構成要素及びそれらの製法について説明する。 The substrate used in the organic photoelectric conversion device of the present invention may be any substrate that does not chemically change when an electrode is formed and an organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent. Hereafter, each component of an organic photoelectric conversion element and those manufacturing methods are demonstrated.
（基板）
本発明の有機光電変換素子は、通常、基板上に形成される。基板には、有機光電変換素子を作製する際に化学的に変化しないものが好適に用いられる。基板としては、例えば、ガラス基板、プラスチック基板、高分子フィルム、シリコン板等が挙げられる。透明又は不透明な陰極から光を取り込む形態の有機光電変換素子の場合、基板には光透過性の高い基板が好適に用いられる。また不透明な基板上に有機光電変換素子を作製する場合には、陰極側から光を取り込むことができないため、陽極が透明又は半透明な電極から構成されることが好ましい。このような電極を用いることにより、たとえ不透明な基板を用いたとしても、基板側に設けられる陰極とは反対側の陽極から光を取り込むことができる。
(substrate)
The organic photoelectric conversion element of the present invention is usually formed on a substrate. A substrate that does not change chemically when an organic photoelectric conversion element is manufactured is preferably used. Examples of the substrate include a glass substrate, a plastic substrate, a polymer film, and a silicon plate. In the case of an organic photoelectric conversion element in which light is taken from a transparent or opaque cathode, a substrate having high light transmittance is preferably used. When an organic photoelectric conversion element is produced on an opaque substrate, it is preferable that the anode is composed of a transparent or translucent electrode because light cannot be taken in from the cathode side. By using such an electrode, even if an opaque substrate is used, light can be taken in from the anode on the side opposite to the cathode provided on the substrate side.
（陰極）
陰極には、導電性の金属酸化物膜、金属薄膜、および有機物を含む導電膜等が用いられる。具体的には、酸化インジウム、酸化亜鉛、酸化スズ、インジウムスズ酸化物（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ：略称ＩＴＯ）、インジウム亜鉛酸化物（Ｉｎｄｉｕｍ Ｚｉｎｃ Ｏｘｉｄｅ：略称ＩＺＯ）、金、白金、銀、銅、アルミニウム、ポリアニリン及びその誘導体、並びにポリチオフェン及びその誘導体等の薄膜が用いられる。これらのなかでも陰極には、ＩＴＯ、ＩＺＯ、酸化スズの薄膜が好適に用いられる。なお陰極から光を取り入れる構成の有機光電変換素子では、たとえば上述の陰極を構成する薄膜の膜厚を、光が透過する程度の厚さにした透明又は半透明な電極が陰極として用いられる。
(cathode)
As the cathode, a conductive metal oxide film, a metal thin film, a conductive film containing an organic substance, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, indium tin oxide (Indium Tin Oxide: abbreviated as ITO), indium zinc oxide (Indium Zinc Oxide: abbreviated as IZO), gold, platinum, silver, copper, aluminum, Thin films such as polyaniline and derivatives thereof, and polythiophene and derivatives thereof are used. Among these, a thin film of ITO, IZO, or tin oxide is preferably used for the cathode. In the organic photoelectric conversion element configured to take in light from the cathode, for example, a transparent or translucent electrode in which the film thickness of the above-described cathode is set to a thickness that allows light to pass therethrough is used as the cathode.
陰極は、オゾンＵＶ処理、コロナ処理、超音波処理等の表面処理が施されていてもよい。 The cathode may be subjected to surface treatment such as ozone UV treatment, corona treatment, ultrasonic treatment or the like.
（正孔輸送層）
本発明の接合体が、正孔輸送層、電子輸送層を陰極に対しこの順に含む場合、電子輸送層は、正孔輸送層を成膜した後に形成されるため、電子輸送層を成膜する際に、先に成膜された正孔輸送層に損傷を与えないことが望ましい。特に電子輸送層を成膜する際に、溶媒として水を含む場合は、正孔輸送層は水に不溶であることが好ましい。本発明において、正孔輸送層は成膜後に水に不溶な層である。本発明において、水に不溶な層とは、下記に示す水リンス処理後の残膜率測定において残膜率が８０％以上である層であることを意味する。残膜率は９０％以上であることがより好ましい。
(Hole transport layer)
When the joined body of the present invention includes a hole transport layer and an electron transport layer in this order with respect to the cathode, the electron transport layer is formed after the hole transport layer is formed. At this time, it is desirable that the previously formed hole transport layer is not damaged. In particular, when forming an electron transport layer, when water is included as a solvent, the hole transport layer is preferably insoluble in water. In the present invention, the hole transport layer is a layer insoluble in water after film formation. In the present invention, the layer insoluble in water means a layer having a residual film ratio of 80% or more in the measurement of the residual film ratio after the water rinsing treatment described below. The remaining film ratio is more preferably 90% or more.
本発明において、水リンス処理後の残膜率は以下の測定方法で求める。一辺１インチの正方形の基板上に、実際に有機光電変換素子において正孔輸送層として成膜する場合と同等の膜厚となるようにスピンコートにより塗布成膜した後、前記膜上にメニスカス状に水を載せ、３０秒静置後、４０００ｒｐｍでスピンさせて水を振り切ることで水リンス処理を行う。水リンス処理前後の膜厚を触針式膜厚計で測定し、水リンス処理後の膜厚／水リンス処理前の膜厚×１００（％）を水リンス処理後の残膜率とする。なお、本発明では、触針式膜厚計として、DEKTAK Bruker Nano社製の触針式膜厚計を用いて測定を行った。 In the present invention, the remaining film ratio after the water rinse treatment is determined by the following measuring method. On a square substrate with a side of 1 inch, a film is formed by spin coating so as to have a film thickness equivalent to that actually formed as a hole transport layer in an organic photoelectric conversion element, and then a meniscus shape is formed on the film. Water rinsing treatment is carried out by placing water on the plate and allowing it to stand for 30 seconds, spinning at 4000 rpm and shaking off the water. The film thickness before and after the water rinse treatment is measured with a stylus-type film thickness meter, and the film thickness after the water rinse treatment / the film thickness before the water rinse treatment × 100 (%) is defined as the remaining film ratio after the water rinse treatment. In the present invention, measurement was performed using a stylus thickness meter manufactured by DEKTAK Bruker Nano as a stylus thickness meter.
成膜後に水に不溶である正孔輸送層の構成材料としては、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体、ポリピロール及びその誘導体等の有機材料、ＣｕＳＣＮ、ＣｕＩ等の無機材料が挙げられる。 Examples of the constituent material of the hole transport layer that is insoluble in water after film formation include organic materials such as polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, and inorganic materials such as CuSCN and CuI.
正孔輸送層の形成方法はとくに限定されないが、製造工程の簡易化の観点からは塗布法によって形成することが好ましい。正孔輸送層は例えば前述した正孔輸送層の構成材料と溶媒とを含む塗布液を用いる塗布法により形成することができる。溶液からの成膜には、スピンコート法、キャスティング法、マイクログラビアコート法、グラビアコート法、バーコート法、ロールコート法、ワイアーバーコート法、ディップコート法、スプレーコート法、スクリーン印刷法、フレキソ印刷法、オフセット印刷法、インクジェット印刷法、ディスペンサー印刷法、ノズルコート法、キャピラリーコート法等の塗布法を用いることができ、スピンコート法、フレキソ印刷法、インクジェット印刷法、ディスペンサー印刷法が好ましい。 Although the formation method of a positive hole transport layer is not specifically limited, From a viewpoint of simplification of a manufacturing process, forming by a coating method is preferable. The hole transport layer can be formed, for example, by a coating method using a coating solution containing the constituent material of the hole transport layer and a solvent. For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method Coating methods such as a printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, a capillary coating method can be used, and a spin coating method, a flexographic printing method, an ink jet printing method, and a dispenser printing method are preferable.
正孔輸送層の厚さは、１０ｎｍ以上１０００ｎｍ以下の範囲が好ましい。 The thickness of the hole transport layer is preferably in the range of 10 nm to 1000 nm.
（正孔注入層）
正孔注入層の構成材料としては、前記正孔輸送層で用いられる材料と同様のものが挙げられる。
(Hole injection layer)
Examples of the constituent material of the hole injection layer include the same materials as those used in the hole transport layer.
（電子輸送層）
電子輸送層はアミンを含有する電子輸送性材料からなる。電子輸送性材料は、酸化亜鉛、酸化チタン、酸化ジルコニウム、酸化スズ、酸化インジウム、ＩＴＯ（インジウムスズ酸化物）、ＦＴＯ(フッ素ドープ酸化スズ)、ＧＺＯ（ガリウムドープ酸化亜鉛）、ＡＴＯ（アンチモンドープ酸化スズ）、ＡＺＯ（アルミニウムドープ酸化亜鉛）等を含んでいても良い。前記アミンは特にエトキシ化ポリエチレンイミンであることが好ましい。
(Electron transport layer)
The electron transport layer is made of an electron transport material containing an amine. The electron transporting materials are zinc oxide, titanium oxide, zirconium oxide, tin oxide, indium oxide, ITO (indium tin oxide), FTO (fluorine-doped tin oxide), GZO (gallium-doped zinc oxide), ATO (antimony-doped oxide). Tin), AZO (aluminum-doped zinc oxide), and the like. The amine is particularly preferably ethoxylated polyethyleneimine.
電子輸送性材料は、水等の溶媒で希釈してもよい。水で希釈する際、水は電子輸送性材料の固形分に対し、１重量倍以上、１０００００重量倍以下が好ましく、１０重量倍以上、１００００重量倍以下であることがより好ましい。また、前記エトキシ化ポリエチレンイミンは水で希釈することが好ましい。 The electron transporting material may be diluted with a solvent such as water. When diluted with water, the water content is preferably 1 to 100000 times by weight, more preferably 10 to 10000 times by weight, based on the solid content of the electron transporting material. The ethoxylated polyethyleneimine is preferably diluted with water.
電子輸送層の形成方法としては、とくに限定されないが、製造工程の簡易化の観点からは塗布法によって形成することが好ましい。電子輸送層は、例えば前述した電子輸送性構成材料と溶媒とを含む塗布液を塗布することにより形成することができる。電子輸送層は、さらに水等の溶媒でリンスして余分に付着したものを洗い流すと、光電変換効率の点でさらに好ましい。電子輸送性材料を含む塗布液の塗布法、及び溶媒でリンス処理する方法は、前述の正孔輸送層の塗布法と同様の方法が例示される。溶媒でリンス処理する方法としては、その他に溶媒を基板の上に流したり、基板を溶媒中に浸漬したりする方法が挙げられる。電子輸送層の形成後、または溶媒リンス後は、加熱処理、風乾処理、減圧処理、などによって溶媒を除くことが好ましい。 Although it does not specifically limit as a formation method of an electron carrying layer, It is preferable to form by the apply | coating method from a viewpoint of simplification of a manufacturing process. The electron transport layer can be formed, for example, by applying a coating liquid containing the above-described electron transporting constituent material and a solvent. It is more preferable in terms of photoelectric conversion efficiency that the electron transport layer is further rinsed with a solvent such as water and washed away excessively. Examples of the coating method of the coating liquid containing the electron transporting material and the method of rinsing with a solvent include the same method as the above-described coating method of the hole transport layer. As a method of rinsing with a solvent, other methods include flowing a solvent on the substrate and immersing the substrate in the solvent. After the formation of the electron transport layer or after the solvent rinsing, the solvent is preferably removed by heat treatment, air drying treatment, reduced pressure treatment, or the like.
電子輸送層の機能としては、電荷再結合層への電子の注入効率を高める機能、活性層からの正孔の注入を防ぐ機能、電子の輸送能を高める機能、活性層の劣化を抑制する機能等が挙げられる。 Functions of the electron transport layer include a function to increase the efficiency of electron injection into the charge recombination layer, a function to prevent the injection of holes from the active layer, a function to increase the electron transport capability, and a function to suppress deterioration of the active layer. Etc.
（電荷再結合層）
電荷再結合層は、接合体中に必ずしも設ける必要はないが、正孔輸送層と電子輸送層とのオーミックな接合の為に、正孔輸送層と電子輸送層との間に設けることが好ましい。電荷再結合層は、光を透過しやすいように、複数の微粒子が凝集した状態、又は薄膜状に形成されることが好ましい。
(Charge recombination layer)
The charge recombination layer is not necessarily provided in the joined body, but is preferably provided between the hole transport layer and the electron transport layer for ohmic junction between the hole transport layer and the electron transport layer. . The charge recombination layer is preferably formed in a state in which a plurality of fine particles are aggregated or in a thin film shape so as to easily transmit light.
電荷再結合層は、通常、金属を含む。電荷再結合層は、金属の酸化物、金属のハロゲン化物を含んでいてもよいが、金属の重量を１００とした場合に、金属の酸化物の重量と金属のハロゲン化物の重量の合計が１０以下であることが好ましく、実質的に金属のみからなることがより好ましい。金属としては、リチウム、ベリリウム、ナトリウム、マグネシウム、アルミニウム、カリウム、カルシウム、スカンジウム、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、ガリウム、ゲルマニウム、ルビジウム、ストロンチウム、イットリウム、ジルコニウム、ニオブ、モリブデン、ルテニウム、ロジウム、パラジウム、銀、カドニウム、インジウム、スズ、アンチモン、セシウム、バリウム、ランタン、ハフニウム、タンタル、タングステン、レニウム、オスミウム、イリジウム、白金、金、水銀、タリウム、鉛、ビスマス、ランタニド等が挙げられる。また、これら金属の合金や、グラファイト又はこれらの金属とグラファイトとの層間化合物等を電荷再結合層に用いることもできる。金属の中では、アルミニルム、マグネシウム、チタン、クロム、鉄、ニッケル、銅、亜鉛、ガリウム、ジルコニウム、モリブデン、銀、インジウム、スズ、金が好ましい。 The charge recombination layer typically includes a metal. The charge recombination layer may contain a metal oxide or a metal halide. However, when the weight of the metal is 100, the total of the weight of the metal oxide and the weight of the metal halide is 10. It is preferable that it is as follows, and it is more preferable that it consists essentially of a metal. The metals include lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, yttrium, zirconium, Niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, cesium, barium, lanthanum, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, A lanthanide etc. are mentioned. Further, an alloy of these metals, graphite, or an intercalation compound between these metals and graphite can be used for the charge recombination layer. Among metals, aluminium, magnesium, titanium, chromium, iron, nickel, copper, zinc, gallium, zirconium, molybdenum, silver, indium, tin, and gold are preferable.
電荷再結合層の成膜法としては特に制限はないが、粉末からの真空蒸着法が挙げられる。 The method for forming the charge recombination layer is not particularly limited, and examples thereof include a vacuum deposition method from powder.
（活性層）
活性層は、例えば、電子受容性化合物を含有する第一の層と、電子供与性化合物を含有する第二の層とが接して積層された積層体であってもよく、電子受容性化合物と電子供与性化合物とを含有する単一の層であってもよい。
(Active layer)
The active layer may be, for example, a laminate in which a first layer containing an electron-accepting compound and a second layer containing an electron-donating compound are in contact with each other. A single layer containing an electron donating compound may be used.
電子供与性化合物と電子受容性化合物の一方は、高分子化合物であることが好ましく、電子供与性化合物又は電子受容性化合物として、一種類の高分子化合物を単独で用いても、二種類以上の高分子化合物を用いてもよい。ヘテロ接合界面を多く含むという観点からは、電子受容性化合物がフラーレン誘導体であることが好ましい。中でも、活性層中に共役高分子化合物とフラーレン誘導体とを含むことが好ましい。
活性層としては、例えば、共役高分子化合物とフラーレン誘導体とを含有する有機薄膜を用いることができる。
活性層がフラーレン誘導体及び電子供与性化合物を含有する場合、活性層に含まれるフラーレン誘導体の重量は、電子供与性化合物１００重量部に対して、１０〜１０００重量部であることが好ましく、５０〜５００重量部であることがより好ましい。
One of the electron-donating compound and the electron-accepting compound is preferably a polymer compound. As the electron-donating compound or the electron-accepting compound, one kind of polymer compound may be used alone, or two or more kinds of compounds may be used. A high molecular compound may be used. From the viewpoint of including many heterojunction interfaces, the electron-accepting compound is preferably a fullerene derivative. Among these, it is preferable that the active layer contains a conjugated polymer compound and a fullerene derivative.
As the active layer, for example, an organic thin film containing a conjugated polymer compound and a fullerene derivative can be used.
When the active layer contains a fullerene derivative and an electron donating compound, the weight of the fullerene derivative contained in the active layer is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the electron donating compound, More preferably, it is 500 parts by weight.
有機光電変換素子に好適に用いられる電子受容性化合物は、電子受容性化合物のＨＯＭＯエネルギーが電子供与性化合物のＨＯＭＯエネルギーよりも高く、かつ、電子受容性化合物のＬＵＭＯエネルギーが電子供与性化合物のＬＵＭＯエネルギーよりも高くなる。 The electron-accepting compound suitably used for the organic photoelectric conversion element is such that the HOMO energy of the electron-accepting compound is higher than the HOMO energy of the electron-donating compound, and the LUMO energy of the electron-accepting compound is LUMO of the electron-donating compound. Higher than energy.
活性層に含まれる電子供与性化合物は、低分子化合物であっても高分子化合物であってもよい。低分子化合物としては、フタロシアニン、金属フタロシアニン、ポルフィリン、金属ポルフィリン、オリゴチオフェン、テトラセン、ペンタセン、ルブレン等が挙げられる。高分子化合物としては、ポリビニルカルバゾール及びその誘導体、ポリシラン及びその誘導体、側鎖又は主鎖に芳香族アミン残基を有するポリシロキサン誘導体、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体、ポリピロール及びその誘導体、ポリフェニレンビニレン及びその誘導体、ポリチエニレンビニレン及びその誘導体、ポリフルオレン及びその誘導体等が挙げられる。 The electron donating compound contained in the active layer may be a low molecular compound or a high molecular compound. Examples of the low molecular weight compound include phthalocyanine, metal phthalocyanine, porphyrin, metal porphyrin, oligothiophene, tetracene, pentacene, and rubrene. Examples of the polymer compound include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine residue in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene Examples include vinylene and its derivatives, polythienylene vinylene and its derivatives, polyfluorene and its derivatives, and the like.
活性層に含まれる電子受容性化合物は、低分子化合物であっても高分子化合物であってもよい。低分子化合物としては、オキサジアゾール誘導体、アントラキノジメタン及びその誘導体、ベンゾキノン及びその誘導体、ナフトキノン及びその誘導体、アントラキノン及びその誘導体、テトラシアノアントラキノジメタン及びその誘導体、フルオレノン誘導体、ジフェニルジシアノエチレン及びその誘導体、ジフェノキノン誘導体、８−ヒドロキシキノリン及びその誘導体の金属錯体、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、Ｃ60等のフラーレン及びその誘導体、２，９−ジメチル−４，７−ジフェニル−１，１０−フェナントロリン（バソクプロイン）等のフェナントロリン誘導体等が挙げられる。高分子化合物としては、ポリビニルカルバゾール及びその誘導体、ポリシラン及びその誘導体、側鎖又は主鎖に芳香族アミン残基を有するポリシロキサン誘導体、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体、ポリピロール及びその誘導体、ポリフェニレンビニレン及びその誘導体、ポリチエニレンビニレン及びその誘導体、ポリフルオレン及びその誘導体等が挙げられる。これらの中でもフラーレン及びその誘導体が好ましい。 The electron-accepting compound contained in the active layer may be a low molecular compound or a high molecular compound. Low molecular weight compounds include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and its derivatives, polyfluorene and its derivatives, fullerene and derivatives thereof such as C 60, 2,9-dimethyl - Examples thereof include phenanthroline derivatives such as 4,7-diphenyl-1,10-phenanthroline (basocuproin). Examples of the polymer compound include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine residue in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene Examples include vinylene and its derivatives, polythienylene vinylene and its derivatives, polyfluorene and its derivatives, and the like. Among these, fullerene and its derivatives are preferable.
フラーレン及びその誘導体としては、Ｃ60、Ｃ70、Ｃ84及びその誘導体が挙げられる。フラーレン誘導体とは、フラーレンの少なくとも一部が修飾された化合物を表す。 Fullerenes and derivatives thereof include C 60 , C 70 , C 84 and derivatives thereof. A fullerene derivative represents a compound in which at least a part of fullerene is modified.
フラーレン誘導体としては、例えば、式（Ｉ）で表される化合物、式（ＩＩ）で表される化合物、式（ＩＩＩ）で表される化合物、式（ＩＶ）で表される化合物が挙げられる。
（式（Ｉ）〜（ＩＶ）中、Ｒａは、アルキル基、アリール基、ヘテロアリール基又はエステル構造を有する基である。複数個あるＲａは、同一であっても異なってもよい。Ｒｂはアルキル基又はアリール基を表す。複数個あるＲｂは、同一であっても異なってもよい。）
Examples of the fullerene derivative include a compound represented by the formula (I), a compound represented by the formula (II), a compound represented by the formula (III), and a compound represented by the formula (IV).
(In formulas (I) to (IV), R a is an alkyl group, an aryl group, a heteroaryl group or a group having an ester structure. A plurality of R a may be the same or different. R b represents an alkyl group or an aryl group, and a plurality of R b may be the same or different.)
Ｒａ及びＲｂで表されるアルキル基としては、メチル基、エチル基、プロピル基、ｉｓｏ−プロピル基、ブチル基、ｉｓｏ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ヘキシル基、オクチル基等が挙げられる。Ｒａ及びＲｂで表されるアリール基としては、フェニル基、ナフチル基、アントリル基、フルオレニル基等が挙げられる。Ｒａ及びＲｂで表されるヘテロアリール基としては、チェニル基、ピロリル基、フリル基、ピリジル基、ピペリジル基、キノリル基、イソキノリル基等が挙げられる。 Examples of the alkyl group represented by R a and R b include a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a hexyl group, and an octyl group. Groups and the like. Examples of the aryl group represented by R a and R b include a phenyl group, a naphthyl group, an anthryl group, and a fluorenyl group. Examples of the heteroaryl group represented by R a and R b include a chenyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group.
Ｒａで表されるエステル構造を有する基は、例えば、式（Ｖ）で表される基が挙げられる。
（式中、ｕ１は、１〜６の整数を表す、ｕ２は、０〜６の整数を表す、Ｒｃは、アルキル基、アリール基又はヘテロアリール基を表す。）
Examples of the group having an ester structure represented by Ra include a group represented by the formula (V).
(In the formula, u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, and R c represents an alkyl group, an aryl group, or a heteroaryl group.)
Ｒｃは、アルキル基、アリール基又はヘテロアリール基を有する基である。Ｒｃで表されるアルキル基、アリール基及びヘテロアリール基の定義、具体例は、Ｒａ及びＲｂで表されるアルキル基、アリール基及びヘテロアリール基の定義、具体例と同じである。 R c is a group having an alkyl group, an aryl group or a heteroaryl group. The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R c are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R a and R b .
Ｃ６０の誘導体の具体例としては、以下のようなものが挙げられる。
Ｃ７０の誘導体の具体例としては、以下のようなものが挙げられる。
中でも活性層は、共役高分子化合物と、フラーレン類及びフラーレン類の誘導体からなる群より選ばれる１種以上とを含むことが好ましい。活性層に用いられる共役高分子化合物としては、ポリチオフェン及びその誘導体、ポリフェニレンビニレン及びその誘導体、ポリフルオレン及びその誘導体等があげられる。 In particular, the active layer preferably contains a conjugated polymer compound and at least one selected from the group consisting of fullerenes and fullerene derivatives. Examples of the conjugated polymer compound used in the active layer include polythiophene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, and the like.
共役高分子化合物としては、式（１）で表される構成単位を有する共役高分子化合物が好ましい。
式（Ｉ）中、Ｚは下記式（Ｚ−１）〜式（Ｚ−７）のうちのいずれか１つで表される基を表す。Ａｒ１及びＡｒ２は、同一でも異なっていてもよく、３価の芳香族複素環基を表す
式（Ｚ−１）〜式（Ｚ−７）中、Ｒは、水素原子、ハロゲン原子、アミノ基、シアノ基又は１価の有機基を表す。１価の有機基としては、例えば、置換されていてもよいアルキル基、置換されていてもよいアルコキシ基、置換されていてもよいアルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、置換されていてもよいアリールアルキル基、置換されていてもよいアリールアルコキシ基、置換されていてもよいアリールアルキルチオ基、置換されていてもよいアシル基、置換されていてもよいアシルオキシ基、置換されていてもよいアミド基、置換されていてもよい酸イミド基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、複素環オキシ基、複素環チオ基、アリールアルケニル基、アリールアルキニル基、カルボキシル基、が挙げられる。式（Ｚ−１）〜式（Ｚ−７）のそれぞれにおいて、Ｒが２つある場合、それらは同一でも異なってもよい。 In formula (Z-1) to formula (Z-7), R represents a hydrogen atom, a halogen atom, an amino group, a cyano group, or a monovalent organic group. Examples of the monovalent organic group include an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an aryl group, an aryloxy group, an arylthio group, and a substituted An optionally substituted arylalkyl group, an optionally substituted arylalkoxy group, an optionally substituted arylalkylthio group, an optionally substituted acyl group, an optionally substituted acyloxy group, an optionally substituted Good amide group, optionally substituted acid imide group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group , Arylalkenyl group, arylalkynyl group, and carboxyl group. In each of formula (Z-1) to formula (Z-7), when there are two Rs, they may be the same or different.
前記式（１）で表される構成単位としては、下記式（２）で表される化合物であることが好ましい。
式（２）で表される構成単位としては、例えば、式（５０１）〜式（５０５）で表される構成単位が挙げられる。 As a structural unit represented by Formula (2), the structural unit represented by Formula (501)-Formula (505) is mentioned, for example.
上記の式（５０１）〜式（５０５）で表される構成単位の中でも、高効率な光電変換素子を得る観点からは、式（５０１）、式（５０２）、式（５０３）、式（５０４）で表される構成単位が好ましく、式（５０１）、式（５０４）で表される構成単位がより好ましく、式（５０１）で表される構成単位がよりさらに好ましい。 Among the structural units represented by the above formulas (501) to (505), from the viewpoint of obtaining a highly efficient photoelectric conversion element, formula (501), formula (502), formula (503), formula (504) The structural unit represented by formula (501) is preferred, the structural unit represented by formula (504) is more preferred, and the structural unit represented by formula (501) is even more preferred.
式（１）で表される構成単位を有する共役高分子化合物は、国際公開番号ＷＯ２０１３／０５１６７６Ａ１に記載された方法で製造し用いることができる。 The conjugated polymer compound having the structural unit represented by the formula (1) can be produced and used by the method described in International Publication No. WO2013 / 051676A1.
本発明において、高分子化合物は、重量平均分子量が３０００以上の化合物を意味する。高分子化合物の重量平均分子量は、３０００〜１０００００００が好ましく、８０００〜５００００００がより好ましく、１００００〜１００００００がさらに好ましい。
高分子化合物の重量平均分子量が３０００より小さいと、素子の作製に用いたときに、塗布性が低下することがある。また、重量平均分子量が１０００００００より大きいと、素子の作製に用いたときに、溶媒への溶解性や塗布性が低下することがある。
高分子化合物の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定したポリスチレン換算の重量平均分子量を意味する。
In the present invention, the polymer compound means a compound having a weight average molecular weight of 3000 or more. The weight average molecular weight of the polymer compound is preferably 3,000 to 10,000,000, more preferably 8,000 to 5,000,000, and still more preferably 10,000 to 1,000,000.
When the weight average molecular weight of the polymer compound is less than 3000, the coatability may be lowered when used for the production of an element. On the other hand, if the weight average molecular weight is larger than 10000000, the solubility in a solvent and the coating property may be lowered when used in the production of an element.
The weight average molecular weight of a high molecular compound means the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).
高分子化合物のポリスチレン換算の数平均分子量としては、１０００〜１００００００００が好ましい。ポリスチレン換算の数平均分子量が１０００以上である場合には、強靭な薄膜が得られやすくなる。ポリスチレン換算の数平均分子量が１００００００００以下である場合には、高分子化合物の溶解性が高く、薄膜の作製が容易である。高分子化合物のポリスチレン換算の数平均分子量としては、３０００以上が好ましい。 The number average molecular weight in terms of polystyrene of the polymer compound is preferably 1000 to 100000000. When the number average molecular weight in terms of polystyrene is 1000 or more, a tough thin film is easily obtained. When the number average molecular weight in terms of polystyrene is 100000000 or less, the polymer compound has high solubility, and the production of a thin film is easy. The number average molecular weight in terms of polystyrene of the polymer compound is preferably 3000 or more.
活性層の膜厚は、通常、１ｎｍ〜１００μｍであり、好ましくは２ｎｍ〜１０００ｎｍであり、より好ましくは５ｎｍ〜５００ｎｍであり、さらに好ましくは２０ｎｍ〜２００ｎｍである。 The thickness of the active layer is usually 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.
活性層の形成方法としては、例えば、溶媒と共役高分子化合物とフラーレン誘導体とを含む組成物からの成膜による方法が挙げられる。溶媒としては、例えば、トルエン、キシレン、メシチレン、テトラリン、デカリン、ビシクロヘキシル、ｎ−ブチルベンゼン、ｓｅｃ−ブチルベゼン、ｔｅｒｔ−ブチルベンゼン等の不飽和炭化水素溶媒、四塩化炭素、クロロホルム、ジクロロメタン、ジクロロエタン、クロロブタン、ブロモブタン、クロロペンタン、ブロモペンタン、クロロヘキサン、ブロモヘキサン、クロロシクロヘキサン、ブロモシクロヘキサン等のハロゲン化飽和炭化水素溶媒、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン等のハロゲン化不飽和炭化水素溶媒、テトラヒドロフラン、テトラヒドロピラン等のエーテル類溶媒が挙げられる。成膜には、正孔輸送層を成膜する方法で説明した方法と同様の方法を用いることができる。 Examples of the method for forming the active layer include a method of forming a film from a composition containing a solvent, a conjugated polymer compound, and a fullerene derivative. Examples of the solvent include toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, unsaturated hydrocarbon solvents such as n-butylbenzene, sec-butylbezen, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, Halogenated saturated hydrocarbon solvents such as chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, tetrahydrofuran, tetrahydro Examples include ether solvents such as pyran. For the film formation, a method similar to the method described in the method for forming the hole transport layer can be used.
（電極）
本発明の有機光電変換素子は一対の電極を有する。該一対の電極の一方の電極は陽極であり、他方の電極は陰極である。該一対の電極のうち少なくとも一方の電極は、透明又は半透明であることが好ましい。透明又は半透明の電極の材料としては、導電性を有する金属酸化物膜、半透明の金属薄膜等が挙げられる。具体的には、酸化インジウム、酸化亜鉛、酸化スズ、インジウムスズ酸化物（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ：略称ＩＴＯ）、インジウム亜鉛酸化物（Ｉｎｄｉｕｍ Ｚｉｎｃ Ｏｘｉｄｅ：略称ＩＺＯ）、金、白金、銀、銅が挙げられ、ＩＴＯ、ＩＺＯ、酸化スズが好ましい。また、電極として、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体等の有機の透明導電膜を用いてもよい。
(electrode)
The organic photoelectric conversion element of the present invention has a pair of electrodes. One electrode of the pair of electrodes is an anode, and the other electrode is a cathode. At least one of the pair of electrodes is preferably transparent or translucent. Examples of the material for the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, indium oxide, zinc oxide, tin oxide, indium tin oxide (abbreviated as ITO), indium zinc oxide (abbreviated as IZO), gold, platinum, silver, and copper can be given. ITO, IZO and tin oxide are preferred. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode.
本発明の有機光電変換素子が有する一対の電極の一方の電極は、不透明であってもよい。不透明の電極として、例えば、光を透過しない程度の膜厚の金属薄膜を用いることができる。不透明な電極の材料としては、例えば、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、マグネシウム、カルシウム、ストロンチウム、バリウム、アルミニウム、スカンジウム、バナジウム、亜鉛、イットリウム、インジウム、セリウム、サマリウム、ユーロピウム、テルビウム、イッテルビウム、金、銀、白金、銅、マンガン、チタン、コバルト、ニッケル、タングステン、錫等の金属、及びそれらのうち２つ以上の合金、グラファイト又はグラファイト層間化合物が挙げられる。 One electrode of the pair of electrodes included in the organic photoelectric conversion element of the present invention may be opaque. As the opaque electrode, for example, a metal thin film having a thickness that does not transmit light can be used. Examples of opaque electrode materials include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, Examples include metals such as gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin, and alloys of two or more thereof, graphite, or graphite intercalation compounds.
電極の作製方法としては、真空蒸着法、スパッタリング法、イオンプレーティング法、メッキ法等が挙げられる。その他、金属インクや金属ペースト、低融点金属等を用いて、塗布法で金属電極を作製することもできる。 Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. In addition, a metal electrode can also be produced by a coating method using a metal ink, a metal paste, a low melting point metal, or the like.
前述した（ａ）の素子及び（ｂ）の素子において、陽極と活性層の間、活性層と陰極との間、又は、活性層と接合体との間に、さらに付加的な層を設けてもよい。付加的な層としては、電子輸送層、正孔輸送層などの電荷輸送層が挙げられる。付加的な層に含まれる材料としては、前述の電子供与性化合物、電子受容性化合物、フッ化リチウム等のアルカリ金属又はアルカリ土類金属のハロゲン化物、アルカリ金属又はアルカリ土類金属の酸化物、酸化チタン等の無機半導体の微粒子が挙げられる。 In the element (a) and the element (b) described above, an additional layer is further provided between the anode and the active layer, between the active layer and the cathode, or between the active layer and the joined body. Also good. Examples of the additional layer include charge transport layers such as an electron transport layer and a hole transport layer. Examples of the material included in the additional layer include the above-described electron donating compounds, electron accepting compounds, alkali metal or alkaline earth metal halides such as lithium fluoride, alkali metal or alkaline earth metal oxides, Fine particles of inorganic semiconductor such as titanium oxide can be mentioned.
本発明の有機光電変換素子は、透明又は半透明の電極に太陽光等の光を照射することにより、電極間に光起電力が発生し、有機薄膜太陽電池として動作させることができる。
また有機薄膜太陽電池を複数集積することにより有機薄膜太陽電池モジュールとして用いることもできる。
The organic photoelectric conversion element of the present invention can be operated as an organic thin-film solar cell by irradiating light such as sunlight to a transparent or translucent electrode to generate photovoltaic power between the electrodes.
Moreover, it can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.
また、本発明の有機光電変換素子は、電極間に電圧を印加した状態で、透明又は半透明の電極に光を照射することにより、光電流が流れ、有機光センサーとして動作させることができる。有機光センサーを複数集積することにより有機イメージセンサーとして用いることもできる。 In addition, the organic photoelectric conversion element of the present invention can be operated as an organic photosensor by irradiating light to a transparent or translucent electrode in a state where a voltage is applied between the electrodes, so that a photocurrent flows. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.
以下、本発明をさらに詳細に説明するために実施例を示すが、本発明はこれらに限定されるものではない。 Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
以下の実施例において、重合体の分子量として、ＧＰＣラボラトリー製ＧＰＣ（ＰＬ−ＧＰＣ２０００）を用いてポリスチレン換算の数平均分子量および重量平均分子量を求めた。重合体の濃度が約１重量％となるようにｏ−ジクロロベンゼンに重合体を溶解させた。ＧＰＣの移動相にはｏ−ジクロロベンゼンを用い、測定温度１４０℃で、１ｍＬ／分の流速で流した。カラムは、ＰＬＧＥＬ １０μｍ ＭＩＸＥＤ−Ｂ（ＰＬラボラトリー製）を３本直列で繋げた。 In the following examples, the number average molecular weight and weight average molecular weight in terms of polystyrene were determined using GPC (PL-GPC2000) manufactured by GPC Laboratory as the molecular weight of the polymer. The polymer was dissolved in o-dichlorobenzene so that the concentration of the polymer was about 1% by weight. As the mobile phase of GPC, o-dichlorobenzene was used and allowed to flow at a measurement temperature of 140 ° C. at a flow rate of 1 mL / min. As the column, three PLGEL 10 μm MIXED-B (manufactured by PL Laboratory) were connected in series.
合成例１
（化合物２の合成）
フラスコ内の気体をアルゴンで置換した２００ｍＬフラスコに、国際公開第２０１１／０５２７０９号の記載に従って合成した化合物１を２．００ｇ(３．７７ ｍｍｏｌ)、脱水テトラヒドロフランを１００ｍＬ入れて均一な溶液とした。該溶液を−７８℃に保ち、該溶液に１．６Ｍのｎ−ブチルリチウムのヘキサン溶液５．８９ｍＬ（９．４２ｍｍｏｌ）を１０分かけて滴下した。滴下後、反応液を−７８℃で３０分攪拌し、次いで、室温（２５℃）で２時間攪拌した。その後、フラスコを−７８℃に冷却し、反応液にトリブチルスズクロリドを３．３７ｇ（１０．４ｍｍｏｌ）加えた。添加後、反応液を−７８℃で３０分攪拌し、次いで、室温（２５℃）で３時間攪拌した。その後、反応液に水２００ｍｌを加えて反応を停止し、酢酸エチルを加えて反応生成物を含む有機層を抽出した。有機層を硫酸ナトリウムで乾燥させ、濾過後、濾液をエバポレーターで濃縮し、溶媒を留去した。得られたオイル状の物質を展開溶媒がヘキサンであるシリカゲルカラムで精製した。シリカゲルカラムのシリカゲルには、あらかじめ１０重量％のトリエチルアミンを含むヘキサンに５分間浸し、その後、ヘキサンで濯いだシリカゲルを用いた。精製後、化合物２を３．５５ｇ（３．２０ｍｍｏｌ）得た。
Synthesis example 1
(Synthesis of Compound 2)
In a 200 mL flask in which the gas in the flask was replaced with argon, 2.00 g (3.77 mmol) of Compound 1 synthesized according to the description of WO 2011/052709 and 100 mL of dehydrated tetrahydrofuran were added to obtain a uniform solution. The solution was kept at −78 ° C., and 5.89 mL (9.42 mmol) of a 1.6M n-butyllithium hexane solution was added dropwise to the solution over 10 minutes. After the addition, the reaction solution was stirred at -78 ° C for 30 minutes, and then stirred at room temperature (25 ° C) for 2 hours. Thereafter, the flask was cooled to −78 ° C., and 3.37 g (10.4 mmol) of tributyltin chloride was added to the reaction solution. After the addition, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 3 hours. Thereafter, 200 ml of water was added to the reaction solution to stop the reaction, and ethyl acetate was added to extract an organic layer containing the reaction product. The organic layer was dried over sodium sulfate and filtered, and then the filtrate was concentrated with an evaporator and the solvent was distilled off. The obtained oily substance was purified by a silica gel column whose developing solvent was hexane. As the silica gel of the silica gel column, silica gel previously immersed in hexane containing 10% by weight of triethylamine for 5 minutes and then rinsed with hexane was used. After purification, 3.55 g (3.20 mmol) of compound 2 was obtained.
合成例２
（高分子化合物１の合成）
フラスコ内の気体をアルゴンで置換した３００ｍＬフラスコに、国際公開第２０１１／０５２７０９号の記載に従って合成した化合物３を８００ｍｇ(０．７６０ ｍｍｏｌ)、化合物２を８４０ｍｇ（０．７５７ｍｍｏｌ）、国際公開第２０１１／０５２７０９号の記載に従って合成した化合物４を４７１ｍｇ（１．４３ｍｍｏｌ）、トルエンを１０７ｍｌ入れて均一な溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを１９．６ｍｇ（０．０２１４ｍｍｏｌ）、トリス(２−トルイル)ホスフィンを３９．１ｍｇ（０．１２８ｍｍｏｌ）加え、１００℃で６時間攪拌した。その後、反応液にフェニルブロミドを６６０ｍｇ加え、さらに５時間攪拌した。その後、フラスコを２５℃に冷却し、反応液をメタノール２０００ｍＬに注いだ。析出したポリマーを濾過して集め、得られたポリマーを円筒濾紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン及びヘキサンでそれぞれ５時間抽出した。円筒濾紙内に残ったポリマーを、ｏ−ジクロロベンゼン５３ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム１．２１ｇと水１２ｍＬとを加え、８時間還流下で攪拌を行った。水層を除去後、有機層を水２００ｍｌで２回洗浄し、次いで、３重量%の酢酸水溶液２００ｍＬで２回洗浄し、次いで、水２００ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーを濾過後、乾燥させ、得られたポリマーをｏ−ジクロロベンゼン６２ｍＬに再度溶解させ、アルミナ／シリカゲルカラムに通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーを濾過後、乾燥させ、精製された重合体８０２ｍｇを得た。以下、この重合体を高分子化合物１と呼称する。
Synthesis example 2
(Synthesis of polymer compound 1)
In a 300 mL flask in which the gas in the flask was replaced with argon, 800 mg (0.760 mmol) of compound 3 synthesized according to the description of WO 2011/052709, 840 mg (0.757 mmol) of compound 2, and WO 2011 / 052709, 471 mg (1.43 mmol) of Compound 4 synthesized in accordance with the description of No. 052709 and 107 ml of toluene were made into a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 19.6 mg (0.0214 mmol) of tris (dibenzylideneacetone) dipalladium and 39.1 mg (0.128 mmol) of tris (2-toluyl) phosphine were added to the toluene solution, and the mixture was stirred at 100 ° C. for 6 hours. Thereafter, 660 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 5 hours. Thereafter, the flask was cooled to 25 ° C., and the reaction solution was poured into 2000 mL of methanol. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and extracted with methanol, acetone and hexane for 5 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 53 mL of o-dichlorobenzene, 1.21 g of sodium diethyldithiocarbamate and 12 mL of water were added, and the mixture was stirred under reflux for 8 hours. After removing the aqueous layer, the organic layer is washed twice with 200 ml of water, then twice with 200 mL of a 3% by weight aqueous acetic acid solution and then twice with 200 mL of water, and the resulting solution is poured into methanol. To precipitate the polymer. The polymer was filtered and dried, and the resulting polymer was redissolved in 62 mL of o-dichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 802 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound 1.
（組成物１の製造）
電子受容性化合物のフラーレン類の誘導体として１２重量部の[６，６]−フェニルＣ７１−酪酸メチルエステル（Ｃ７０ＰＣＢＭ）（アメリカンダイソース社製ＡＤＳ７１ＢＦＡ）と、電子供与性化合物として、下記構造式で表される１−Ｍａｔｅｒｉａｌ社製のＰＣＥ−１０（Ｍｗ＝１１５０００）を６重量部と、溶媒として１０００重量部のｏ−ジクロロベンゼンとを混合した。次に、混合した溶液を、孔径１．０μmのテフロン（登録商標）フィルターで濾過して組成物１を調製した。
12 parts by weight of [6,6] -phenyl C71-butyric acid methyl ester (C70PCBM) (ADS71BFA manufactured by American Dye Source) as an electron-accepting compound fullerene derivative and an electron-donating compound represented by the following structural formula 6 parts by weight of PCE-10 (Mw = 15000) manufactured by 1-Material and 1000 parts by weight of o-dichlorobenzene as a solvent were mixed. Next, the mixed solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 1.0 μm to prepare a composition 1.
（組成物２の製造）
電子受容性化合物のフラーレン類の誘導体として１０重量部の[６，６]−フェニルＣ７１−酪酸メチルエステル（Ｃ７０ＰＣＢＭ）（アメリカンダイソース社製ＡＤＳ７１ＢＦＡ）と、電子供与性化合物として５重量部の重合体１と、溶媒として１０００重量部のｏ−ジクロロベンゼンとを混合した。次に、混合した溶液を、孔径１．０μmのテフロン（登録商標）フィルターで濾過して組成物２を調製した。
(Production of Composition 2)
10 parts by weight of [6,6] -phenyl C71-butyric acid methyl ester (C70PCBM) (ADS71BFA manufactured by American Dye Source) as a fullerene derivative of an electron-accepting compound, and 5 parts by weight of a polymer as an electron-donating compound 1 and 1000 parts by weight of o-dichlorobenzene as a solvent were mixed. Next, the mixed solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 1.0 μm to prepare a composition 2.
実施例１
（有機薄膜太陽電池の作製、評価）
太陽電池の陰極として機能するＩＴＯ薄膜が形成されたガラス基板を用意した。ＩＴＯ薄膜はスパッタ法によって形成されたものであり、その厚みは１５０ｎｍであった。このＩＴＯ薄膜が形成されたガラス基板をオゾンＵＶ処理し、ＩＴＯ薄膜の表面処理を行った。次に、８０％エトキシ化ポリエチレンイミン（３５〜４０重量％水溶媒、Ｍｗ≒７万）（ＰＥＩＥ）を５０重量倍量の水で希釈した溶液を４０００ｒｐｍ１０秒の条件でスピンコートした。その後、水を垂らして４０００ｒｐｍ１０秒の条件でリンスを行い、大気中１２０℃で１０分間加熱することにより電子輸送層を形成した。ＰＥＩＥの膜厚は１０ｎｍ以下であった。この電子輸送層上に、前記組成物１をスピンコートにより塗布し、第一の活性層（膜厚約７０ｎｍ）を形成した。
Example 1
(Production and evaluation of organic thin-film solar cells)
A glass substrate on which an ITO thin film functioning as a cathode of a solar cell was formed was prepared. The ITO thin film was formed by sputtering, and the thickness was 150 nm. The glass substrate on which the ITO thin film was formed was subjected to ozone UV treatment, and surface treatment of the ITO thin film was performed. Next, a solution obtained by diluting 80% ethoxylated polyethyleneimine (35 to 40% by weight water solvent, Mw≈70,000) (PEIE) with 50 parts by weight of water was spin-coated under the condition of 4000 rpm for 10 seconds. Then, water was dripped, rinsed on the conditions of 4000 rpm for 10 seconds, and the electron carrying layer was formed by heating at 120 degreeC in air | atmosphere for 10 minutes. The film thickness of PEIE was 10 nm or less. On the electron transport layer, the composition 1 was applied by spin coating to form a first active layer (film thickness of about 70 nm).
次に、Ｐｌｅｘｃｏｒｅ ＰＶ２０００ Ｈｏｌｅ Ｔｒａｎｓｐｏｒｔ Ｉｎｋ（シグマ・アルドリッチ社より購入。Ｓｕｌｆｏｎａｔｅｄ ｐｏｌｙｔｈｉｏｐｈｅｎｅ(thiophene-3-[2-(2-methoxyethoxy)ethoxy]-2,5-diyl) (S-P3MEET) １．８％ ｉｎ ２−ｂｕｔｏｘｙｅｔｈａｎｏｌ：ｗａｔｅｒ (２：３)）をスピンコートにより活性層上に塗布し、膜厚５０ｎｍの、水に不溶である正孔輸送層を形成した。 Next, Plexcore PV2000 Hole Transport Ink (purchased from Sigma-Aldrich. Sulfonated polythiophene (thiophene-3- [2- (2-methoxyethoxy) ethoxy] -2,5-diyl) (S-P3MEET) 1.8% in 2-butoxyethanol: water (2: 3)) was applied onto the active layer by spin coating to form a 50 nm thick hole transport layer insoluble in water.
次に、８０％エトキシ化ポリエチレンイミン（３５〜４０重量％水溶媒、Ｍｗ≒７万）（ＰＥＩＥ）を５０重量倍量の水で希釈した溶液を４０００ｒｐｍ１０秒の条件でスピンコートした。その後、水を垂らして４０００ｒｐｍ１０秒の条件でリンスを行い、大気中１２０℃で１０分間加熱することにより電子輸送層を形成した。ＰＥＩＥの膜厚は１０ｎｍ以下であった。この電子輸送層上に、前記組成物２をスピンコートにより塗布し、第二の活性層（膜厚約１００ｎｍ）を形成した。 Next, a solution obtained by diluting 80% ethoxylated polyethyleneimine (35 to 40% by weight water solvent, Mw≈70,000) (PEIE) with 50 parts by weight of water was spin-coated under the condition of 4000 rpm for 10 seconds. Then, water was dripped, rinsed on the conditions of 4000 rpm for 10 seconds, and the electron carrying layer was formed by heating at 120 degreeC in air | atmosphere for 10 minutes. The film thickness of PEIE was 10 nm or less. On the electron transport layer, the composition 2 was applied by spin coating to form a second active layer (film thickness of about 100 nm).
次に、Ｐｌｅｘｃｏｒｅ ＰＶ２０００ Ｈｏｌｅ Ｔｒａｎｓｐｏｒｔ Ｉｎｋ（シグマ・アルドリッチ社より購入。Ｓｕｌｆｏｎａｔｅｄ ｐｏｌｙｔｈｉｏｐｈｅｎｅ(thiophene-3-[2-(2-methoxyethoxy)ethoxy]-2,5-diyl) (S-P3MEET) １．８％ ｉｎ ２−ｂｕｔｏｘｙｅｔｈａｎｏｌ：ｗａｔｅｒ (２：３)）をスピンコートにより活性層上に塗布し、膜厚５０ｎｍの正孔注入層を形成した。 Next, Plexcore PV2000 Hole Transport Ink (purchased from Sigma-Aldrich. Sulfonated polythiophene (thiophene-3- [2- (2-methoxyethoxy) ethoxy] -2,5-diyl) (S-P3MEET) 1.8% in 2-butoxyethanol: water (2: 3)) was applied onto the active layer by spin coating to form a 50-nm thick hole injection layer.
その後、真空蒸着機により陽極の銀を膜厚１００ｎｍで蒸着することにより、有機薄膜太陽電池を作製した。蒸着のときの真空度は、すべて１〜９×１０-3Ｐａであった。その後、ＵＶ硬化封止剤を用いて、有機薄膜太陽電池素子をガラス板で封止した。得られた有機薄膜太陽電池の形状は、２ｍｍ×２ｍｍの正四角形であった。ソーラシミュレーター(分光計器製、商品名OTENTO-SUNII：AM1.5Gフィルター、放射照度100mW/cm2)を用いて、得られた有機薄膜太陽電池に一定の光を照射し、発生する電流と電圧を測定することによって光電変換効率を測定した。光電変換効率は８．３９％、短絡電流密度は９．３３ｍＡ／ｃｍ2、開放端電圧は１．４１Ｖ、ＦＦ（フィルファクター）は０．６４であった。 Then, the organic thin-film solar cell was produced by vapor-depositing silver of an anode with a film thickness of 100 nm with a vacuum evaporation machine. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 −3 Pa in all cases. Then, the organic thin film solar cell element was sealed with a glass plate using a UV curable sealant. The shape of the obtained organic thin film solar cell was a regular square of 2 mm × 2 mm. Using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm 2 ), the obtained organic thin film solar cell is irradiated with a certain amount of light, and the generated current and voltage are The photoelectric conversion efficiency was measured by measuring. The photoelectric conversion efficiency was 8.39%, the short-circuit current density was 9.33 mA / cm 2 , the open-circuit voltage was 1.41 V, and the FF (fill factor) was 0.64.
比較例１
（有機薄膜太陽電池の作製、評価）
（有機薄膜太陽電池の作製、評価）
太陽電池の陰極として機能するＩＴＯ薄膜が形成されたガラス基板を用意した。ＩＴＯ薄膜はスパッタ法によって形成されたものであり、その厚みは１５０ｎｍであった。このＩＴＯ薄膜が形成されたガラス基板をオゾンＵＶ処理し、ＩＴＯ薄膜の表面処理を行った。次に、８０％エトキシ化ポリエチレンイミン（３５〜４０重量％水溶媒、Ｍｗ≒７万）（ＰＥＩＥ）を５０重量倍量の水で希釈した溶液を４０００ｒｐｍ１０秒の条件でスピンコートした。その後、水を垂らして４０００ｒｐｍ１０秒の条件でリンスを行い、大気中１２０℃で１０分間加熱することにより電子輸送層を形成した。ＰＥＩＥの膜厚は１０ｎｍ以下であった。この電子輸送層上に、前記組成物１をスピンコートにより塗布し、第一の活性層（膜厚約７０ｎｍ）を形成した。
Comparative Example 1
(Production and evaluation of organic thin-film solar cells)
(Production and evaluation of organic thin-film solar cells)
A glass substrate on which an ITO thin film functioning as a cathode of a solar cell was formed was prepared. The ITO thin film was formed by sputtering, and the thickness was 150 nm. The glass substrate on which the ITO thin film was formed was subjected to ozone UV treatment, and surface treatment of the ITO thin film was performed. Next, a solution obtained by diluting 80% ethoxylated polyethyleneimine (35 to 40% by weight water solvent, Mw≈70,000) (PEIE) with 50 parts by weight of water was spin-coated under the condition of 4000 rpm for 10 seconds. Then, water was dripped, rinsed on the conditions of 4000 rpm for 10 seconds, and the electron carrying layer was formed by heating at 120 degreeC in air | atmosphere for 10 minutes. The film thickness of PEIE was 10 nm or less. On the electron transport layer, the composition 1 was applied by spin coating to form a first active layer (film thickness of about 70 nm).
次に、ヘレウス製ＰＥＤＯＴ：ＰＳＳのＡＩ４０８３に界面活性剤Ｚｏｎｙｌ ＦＳ−３００を１重量％添加した溶液を、スピンコートにより活性層上に塗布し、膜厚５０ｎｍの正孔輸送層を形成した。 Next, a solution obtained by adding 1% by weight of surfactant Zonyl FS-300 to AI4083 of PEDOT: PSS manufactured by Heraeus was applied onto the active layer by spin coating to form a hole transport layer having a thickness of 50 nm.
次に、８０％エトキシ化ポリエチレンイミン（３５〜４０重量％水溶媒、Ｍｗ≒７万）（ＰＥＩＥ）を５０重量倍量の水で希釈した溶液を４０００ｒｐｍ１０秒の条件でスピンコートした。その後、水を垂らして４０００ｒｐｍ１０秒の条件でリンスを行い、大気中１２０℃で１０分間加熱することにより電子輸送層を形成した。ＰＥＩＥの膜厚は１０ｎｍ以下であった。この電子輸送層上に、前記組成物２をスピンコートにより塗布し、第二の活性層（膜厚約１００ｎｍ）を形成した。 Next, a solution obtained by diluting 80% ethoxylated polyethyleneimine (35 to 40% by weight water solvent, Mw≈70,000) (PEIE) with 50 parts by weight of water was spin-coated under the condition of 4000 rpm for 10 seconds. Then, water was dripped, rinsed on the conditions of 4000 rpm for 10 seconds, and the electron carrying layer was formed by heating at 120 degreeC in air | atmosphere for 10 minutes. The film thickness of PEIE was 10 nm or less. On the electron transport layer, the composition 2 was applied by spin coating to form a second active layer (film thickness of about 100 nm).
次に、Ｐｌｅｘｃｏｒｅ ＰＶ２０００ Ｈｏｌｅ Ｔｒａｎｓｐｏｒｔ Ｉｎｋ（シグマ・アルドリッチ社より購入。Ｓｕｌｆｏｎａｔｅｄ ｐｏｌｙｔｈｉｏｐｈｅｎｅ(thiophene-3-[2-(2-methoxyethoxy)ethoxy]-2,5-diyl) (S-P3MEET) １．８％ ｉｎ ２−ｂｕｔｏｘｙｅｔｈａｎｏｌ：ｗａｔｅｒ (２：３)）をスピンコートにより活性層上に塗布し、膜厚５０ｎｍの正孔注入層を形成した。 Next, Plexcore PV2000 Hole Transport Ink (purchased from Sigma-Aldrich. Sulfonated polythiophene (thiophene-3- [2- (2-methoxyethoxy) ethoxy] -2,5-diyl) (S-P3MEET) 1.8% in 2-butoxyethanol: water (2: 3)) was applied onto the active layer by spin coating to form a 50-nm thick hole injection layer.
その後、真空蒸着機により陽極の銀を膜厚１００ｎｍで蒸着することにより、有機薄膜太陽電池を作製した。蒸着のときの真空度は、すべて１〜９×１０-3Ｐａであった。その後、ＵＶ硬化封止剤を用いて、有機薄膜太陽電池素子をガラス板で封止した。得られた有機薄膜太陽電池の形状は、２ｍｍ×２ｍｍの正四角形であった。ソーラシミュレーター(分光計器製、商品名OTENTO-SUNII：AM1.5Gフィルター、放射照度100mW/cm2)を用いて、得られた有機薄膜太陽電池に一定の光を照射し、発生する電流と電圧を測定することによって光電変換効率を測定した。光電変換効率は７．５９％、短絡電流密度は１８．８ｍＡ／ｃｍ2、開放端電圧は０．６７Ｖ、ＦＦ（フィルファクター）は０．６０であった。 Then, the organic thin-film solar cell was produced by vapor-depositing silver of an anode with a film thickness of 100 nm with a vacuum evaporation machine. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 −3 Pa in all cases. Then, the organic thin film solar cell element was sealed with a glass plate using a UV curable sealant. The shape of the obtained organic thin film solar cell was a regular square of 2 mm × 2 mm. Using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm 2 ), the obtained organic thin film solar cell is irradiated with a certain amount of light, and the generated current and voltage are The photoelectric conversion efficiency was measured by measuring. The photoelectric conversion efficiency was 7.59%, the short-circuit current density was 18.8 mA / cm 2 , the open-circuit voltage was 0.67 V, and the FF (fill factor) was 0.60.
（残膜率の測定）
一辺１インチの正方形の基板上に、Ｐｌｅｘｃｏｒｅ ＰＶ２０００ Ｈｏｌｅ Ｔｒａｎｓｐｏｒｔ Ｉｎｋ（シグマ・アルドリッチ社より購入）をスピンコートにより塗布し、真空中で乾燥させることで、膜厚５０ｎｍの塗布膜を形成した。次に、この塗布膜上にメニスカス状に水を載せ、３０秒後に４０００ｒｐｍでスピンさせて振り切った。塗布膜の残膜率は、１００％であった。
(Measurement of remaining film rate)
Plexcore PV2000 Hole Transport Ink (purchased from Sigma-Aldrich) was applied by spin coating on a 1-inch square substrate, and dried in vacuum to form a coating film having a thickness of 50 nm. Next, water was placed on the coating film in a meniscus shape and spun off by spinning at 4000 rpm after 30 seconds. The remaining film ratio of the coating film was 100%.
一辺１インチの正方形の基板上にヘレウス製ＰＥＤＯＴ：ＰＳＳのＡＩ４０８３に界面活性剤Ｚｏｎｙｌ ＦＳ−３００を１重量％添加した溶液を、スピンコートにより塗布し、真空中で乾燥させることで、膜厚５０ｎｍの塗布膜を形成した。次に、この塗布膜上にメニスカス状に水を載せ、３０秒後に４０００ｒｐｍでスピンさせて振り切った。塗布膜の残膜率は、０％であった。ＰＥＤＯＴを正孔輸送層に採用した場合、ＰＥＤＯＴが水に可溶であるため、水溶媒を含むＰＥＩＥ等の電子輸送層を安定的に塗布したり水リンスしたりすることができず、高い光電変換効率を得ることができないと考えられる。 A solution obtained by adding 1% by weight of a surfactant Zonyl FS-300 to PEDOT: PSS AI4083 made by Heraeus on a square substrate having a side of 1 inch is applied by spin coating, and dried in vacuum to obtain a film thickness of 50 nm. The coating film was formed. Next, water was placed on the coating film in a meniscus shape and spun off by spinning at 4000 rpm after 30 seconds. The remaining film ratio of the coating film was 0%. When PEDOT is used for the hole transport layer, since PEDOT is soluble in water, an electron transport layer such as PEIE containing an aqueous solvent cannot be stably applied or rinsed with water. It is considered that conversion efficiency cannot be obtained.
本発明の、水に不溶な正孔輸送層と、アミンを有する電子輸送層を接合体として用いた、マルチ接合有機光電変換素子は、高い光電変換効率を得ることができる。 The multi-junction organic photoelectric conversion element using the hole transport layer insoluble in water and the electron transport layer having amine as the joined body of the present invention can obtain high photoelectric conversion efficiency.
Claims (9)
＜水リンス処理後の残膜率測定方法＞
一辺１インチの正方形の基板上に、有機光電変換素子において正孔輸送層として成膜する場合と同等の膜厚となるようにスピンコートにより塗布成膜した後、前記膜上にメニスカス状に水を載せ、３０秒静置後、４０００ｒｐｍでスピンさせて水を振り切ることで水リンス処理を行う。水リンス処理前後の膜厚を触針式膜厚計で測定し、水リンス処理後の膜厚／水リンス処理前の膜厚×１００（％）を水リンス処理後の残膜率とする。 An organic photoelectric conversion device having two or more active layers between a pair of electrodes, and having a hole transport layer and an electron transport layer between at least one pair of adjacent active layers, the electron transport layer Has an amine, and the hole transport layer has a remaining film ratio of 80% or more in the measurement of the remaining film ratio after the water rinsing treatment described below.
<Method for measuring remaining film ratio after water rinse treatment>
On a square substrate having a side of 1 inch, a film is formed by spin coating so as to have a film thickness equivalent to that for forming a hole transport layer in an organic photoelectric conversion element, and then water is formed on the film in a meniscus shape. After standing for 30 seconds, spin water at 4000 rpm and shake off water to perform water rinsing treatment. The film thickness before and after the water rinse treatment is measured with a stylus-type film thickness meter, and the film thickness after the water rinse treatment / the film thickness before the water rinse treatment × 100 (%) is defined as the remaining film ratio after the water rinse treatment.
＜水リンス処理後の残膜率測定方法＞
一辺１インチの正方形の基板上に、有機光電変換素子において正孔輸送層として成膜する場合と同等の膜厚となるようにスピンコートにより塗布成膜した後、前記膜上にメニスカス状に水を載せ、３０秒静置後、４０００ｒｐｍでスピンさせて水を振り切ることで水リンス処理を行う。水リンス処理前後の膜厚を触針式膜厚計で測定し、水リンス処理後の膜厚／水リンス処理前の膜厚×１００（％）を水リンス処理後の残膜率とする。 A method for producing an organic photoelectric conversion element having two or more active layers between a pair of electrodes, and having a hole transport layer and an electron transport layer between at least one pair of adjacent two active layers, A step of forming a hole transport layer on the layer, and a step of forming an electron transport layer by applying a coating solution containing amine and water after the step of forming the hole transport layer, A method for producing an organic photoelectric conversion element, wherein the transport layer is a layer having a remaining film ratio of 80% or more in the measurement of the remaining film ratio after water rinsing treatment of the film shown below.
<Method for measuring remaining film ratio after water rinse treatment>
On a square substrate having a side of 1 inch, a film is formed by spin coating so as to have a film thickness equivalent to that for forming a hole transport layer in an organic photoelectric conversion element, and then water is formed on the film in a meniscus shape. After standing for 30 seconds, spin water at 4000 rpm and shake off water to perform water rinsing treatment. The film thickness before and after the water rinse treatment is measured with a stylus-type film thickness meter, and the film thickness after the water rinse treatment / the film thickness before the water rinse treatment × 100 (%) is defined as the remaining film ratio after the water rinse treatment.
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