JP2015170782A - Organic device and method of manufacturing organic device - Google Patents
Organic device and method of manufacturing organic device Download PDFInfo
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- JP2015170782A JP2015170782A JP2014045716A JP2014045716A JP2015170782A JP 2015170782 A JP2015170782 A JP 2015170782A JP 2014045716 A JP2014045716 A JP 2014045716A JP 2014045716 A JP2014045716 A JP 2014045716A JP 2015170782 A JP2015170782 A JP 2015170782A
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- organic
- carbon atoms
- organic semiconductor
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- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 144
- 239000004065 semiconductor Substances 0.000 claims abstract description 116
- 239000012044 organic layer Substances 0.000 claims abstract description 43
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- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
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- 125000004414 alkyl thio group Chemical group 0.000 claims description 7
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- 238000003756 stirring Methods 0.000 description 7
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- GKWNSDLPVLPKNM-UHFFFAOYSA-N 2-(4-thiophen-2-ylbutoxy)oxane Chemical compound C1CCCOC1OCCCCC1=CC=CS1 GKWNSDLPVLPKNM-UHFFFAOYSA-N 0.000 description 6
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- 125000003118 aryl group Chemical group 0.000 description 6
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
本発明は、有機デバイスおよび有機デバイスの製造方法に関する。 The present invention relates to an organic device and a method for manufacturing the organic device.
材料として有機化合物を含む発光層や光学活性層となる有機層を有する有機デバイスは、シリコン等の無機化合物からなる従来のデバイスに比べて、より軽量化することができ、より可撓性および透明性に富んだ構造とすることができ、さらにはより低コストで製造することができるなどの特徴を有していることから、新しいデバイスとして注目されている。 An organic device having a light emitting layer containing an organic compound as a material and an organic layer serving as an optically active layer can be reduced in weight, more flexible and transparent than a conventional device made of an inorganic compound such as silicon. It has attracted attention as a new device because it has a feature that it can be a structure rich in properties and can be manufactured at a lower cost.
かかる有機デバイスにおいて、高い特性を実現するためには、有機層中のp型半導体材料の相とn型半導体材料の相とを数十nmオーダーで相分離させた構造を生成させ、かつp型半導体材料の相と、n型半導体材料の相とをそれぞれ互いに異なる電極に接触させて電気的に接続させるように、p型半導体材料とn型半導体材料とが形成する相分離構造を最適化することが重要であると考えられている。 In such an organic device, in order to realize high characteristics, a structure in which the phase of the p-type semiconductor material and the phase of the n-type semiconductor material in the organic layer are phase-separated on the order of several tens of nm is generated, and the p-type is formed. The phase separation structure formed by the p-type semiconductor material and the n-type semiconductor material is optimized so that the phase of the semiconductor material and the phase of the n-type semiconductor material are in contact with each other and electrically connected to each other. Is considered important.
より最適な構造を有する有機層を形成するため、例えば有機光電変換素子では、p型半導体材料とn型半導体材料とのいずれかに、結晶性を有する材料や成膜時に自己組織化する材料などのその構造が周期性を有する材料を用いて、ナノ構造体を構築し、かかるナノ構造体をテンプレートとして光学活性層を形成する技術が検討されている。(非特許文献1、2および3参照。) In order to form an organic layer having a more optimal structure, for example, in an organic photoelectric conversion element, either a p-type semiconductor material or an n-type semiconductor material, a material having crystallinity, a material that self-organizes during film formation, etc. A technique for constructing a nanostructure using a material having a periodic structure and forming an optically active layer using the nanostructure as a template has been studied. (See Non-Patent Documents 1, 2, and 3.)
また、有機発光素子では、電子輸送材料(n型半導体材料)と正孔輸送材料(p型半導体材料)の界面に、微小混合層を設けることによって両方の接触界面が増大し、素子特性を向上させることが検討されている。(非特許文献4参照。) Also, in organic light-emitting devices, providing a micro-mixed layer at the interface between an electron transport material (n-type semiconductor material) and a hole transport material (p-type semiconductor material) increases both contact interfaces and improves device characteristics. It is being considered to do. (See Non-Patent Document 4.)
しかしながら、上記非特許文献が開示している有機光電変換素子や有機発光素子などの有機デバイスにおいては、有機層中のp型半導体材料とn型半導体材料とが形成するナノ構造体の最適化が十分ではなく、その結果として、光電変換効率や発光効率などの特性が必ずしも満足できるものではなかった。 However, in the organic devices such as the organic photoelectric conversion element and the organic light emitting element disclosed in the above non-patent literature, the nanostructure formed by the p-type semiconductor material and the n-type semiconductor material in the organic layer is not optimized As a result, the characteristics such as the photoelectric conversion efficiency and the light emission efficiency are not always satisfactory.
本発明は上記問題点に鑑みてなされたものであって、その目的とするところは、規則性の高いナノ構造体を含む有機層を有しており、光電変換効率や発光効率が高い有機デバイスとその製造方法を提供することにある。 The present invention has been made in view of the above problems, and the object thereof is an organic device having an organic layer containing a highly ordered nanostructure and having high photoelectric conversion efficiency and light emission efficiency. And providing a manufacturing method thereof.
本発明は、下記[1]〜[20]を提供する。
[1] 第1の電極と、第2の電極と、該第1の電極と該第2の電極との間に設けられた有機層とを有しており、
前記有機層が、電子供与性及び電子受容性のうちのいずれか一方の整流特性の有機半導体部位と絶縁性部位とこれらを結合する結合部位とを有しており分子量分散が1.6以下である第1の化合物から絶縁性部位が除去された化合物と、前記有機半導体部位とは異なる整流特性の有機半導体部位を有する第2の化合物とを含む、有機デバイス。
[2] 前記第1の化合物の有機半導体部位が電子供与性である、[1]に記載の有機デバイス。
[3] 前記第1の化合物の有機半導体部位が複素5員環を含む、[1]または[2]に記載の有機デバイス。
[4] 前記第1の化合物の有機半導体部位が置換基を有していてもよいチオフェンジイル基を含む、[1]〜[3]のいずれか1つに記載の有機デバイス。
[5] 前記第1の化合物の有機半導体部位が下記式(1)で示される構造である、[1]〜[4]のいずれか1つに記載の有機デバイス。
[6] 前記第1の化合物の有機半導体部位が下記式(2)または下記式(3)で示される構造である、[1]〜[5]のいずれか1つに記載の有機デバイス。
[7] 前記第1の化合物の有機半導体部位が前記式(2)で示される構造であり、前記Zがn−ブチル基である、[6]に記載の有機デバイス。
[8] 前記第1の化合物の有機半導体部位が前記式(3)で示される構造であり、前記Zが塩素原子または臭素原子であり、かつ前記R0、R1、R2、R3およびR4がいずれも直鎖のアルキル基である、[6]に記載の有機デバイス。
[9] 前記R0、R1、R2、R3およびR4がいずれもn−ヘキシル基である、[8]に記載の有機デバイス。
[10] 前記第1の化合物の有機半導体部位が疎水性を有する1価の基であり、絶縁性部位が親水性を有するポリマーに由来する1価の基である、[1]〜[9]のいずれか1つに記載の有機デバイス。
[11] 前記親水性を有するポリマーに由来する1価の基がポリエチレンオキサイド鎖を有する1価の基である、[10]に記載の有機デバイス。
[12] 前記結合部位が光、熱、酸またはアルカリによる処理によって分解する構造を含む、[1]〜[11]のいずれか1つに記載の有機デバイス。
[13] 前記結合部位の前記構造が、アセタール結合、エステル結合、エーテル結合のいずれかの結合を含む、[12]に記載の有機デバイス。
[14] 前記第1の化合物が下記式(4)、下記式(5)または下記式(6)で示される化合物である、[1]〜[13]のいずれか1つに記載の有機デバイス。
[15] 下記式(6)で示される高分子化合物。
[16] 第1の電極と、第2の電極と、該第1の電極と該第2の電極との間に設けられた有機層を有する有機デバイスの製造方法において、
電子供与性及び電子受容性のうちのいずれか一方の整流特性を有する有機半導体部位と絶縁性部位とこれらを結合する結合部位を有しており、分子量分散が1.6以下である第1の化合物を含む層を形成した後に、該層中の第1の化合物の結合部位を分解することで第1の化合物から絶縁性部位を除去し、次いで前記有機半導体部位とは異なる整流特性の有機半導体部位を有する第2の化合物を、前記層に接触するように添加し、前記絶縁性部位の除去により生じた前記層中の空隙に充填することで有機層を形成する、有機デバイスの製造方法。
[17] 電子供与性及び電子受容性のうちのいずれか一方の整流特性の有機半導体部位と絶縁性部位とこれらを結合する結合部位を有しており、分子量分散が1.6以下である第1の化合物を含む層を形成し、前記層中の前記第1の化合物から絶縁性部を除去し、前記有機半導体部位とは異なる整流特性の有機半導体部位を有する第2の化合物を、前記層に接触するように添加することにより得られる薄膜。
[18] [17]に記載の薄膜を含む光電変換素子。
[19] [17]に記載の薄膜を含む発光素子。
[20] [17]に記載の薄膜を含むセンサー。
The present invention provides the following [1] to [20].
[1] having a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode;
The organic layer has an organic semiconductor site having one of rectifying properties of electron donating property and electron accepting property, an insulating site, and a binding site for binding them, and the molecular weight dispersion is 1.6 or less. An organic device comprising: a compound obtained by removing an insulating part from a first compound; and a second compound having an organic semiconductor part having a rectifying characteristic different from that of the organic semiconductor part.
[2] The organic device according to [1], wherein the organic semiconductor portion of the first compound is electron-donating.
[3] The organic device according to [1] or [2], wherein the organic semiconductor portion of the first compound includes a hetero 5-membered ring.
[4] The organic device according to any one of [1] to [3], wherein the organic semiconductor portion of the first compound includes a thiophenediyl group which may have a substituent.
[5] The organic device according to any one of [1] to [4], wherein the organic semiconductor portion of the first compound has a structure represented by the following formula (1).
[6] The organic device according to any one of [1] to [5], wherein the organic semiconductor portion of the first compound has a structure represented by the following formula (2) or the following formula (3).
[7] The organic device according to [6], wherein the organic semiconductor portion of the first compound has a structure represented by the formula (2), and the Z is an n-butyl group.
[8] The organic semiconductor portion of the first compound has a structure represented by the formula (3), the Z is a chlorine atom or a bromine atom, and the R 0 , R 1 , R 2 , R 3 and The organic device according to [6], wherein each R 4 is a linear alkyl group.
[9] The organic device according to [8], wherein R 0, R 1 , R 2 , R 3 and R 4 are all n-hexyl groups.
[10] The organic semiconductor part of the first compound is a monovalent group having hydrophobicity, and the insulating part is a monovalent group derived from a hydrophilic polymer. [1] to [9] Organic device as described in any one of these.
[11] The organic device according to [10], wherein the monovalent group derived from the hydrophilic polymer is a monovalent group having a polyethylene oxide chain.
[12] The organic device according to any one of [1] to [11], including a structure in which the binding site is decomposed by treatment with light, heat, acid, or alkali.
[13] The organic device according to [12], wherein the structure of the binding site includes any one of an acetal bond, an ester bond, and an ether bond.
[14] The organic device according to any one of [1] to [13], wherein the first compound is a compound represented by the following formula (4), the following formula (5), or the following formula (6). .
[15] A polymer compound represented by the following formula (6).
[16] In a method of manufacturing an organic device having a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode,
The organic semiconductor part having an rectifying property of either one of electron donating property and electron accepting property, an insulating part, and a binding part for bonding them, and having a molecular weight dispersion of 1.6 or less After forming the layer containing the compound, the insulating portion is removed from the first compound by decomposing the binding site of the first compound in the layer, and then the organic semiconductor having a rectifying characteristic different from that of the organic semiconductor portion The manufacturing method of the organic device which adds the 2nd compound which has a site | part so that the said layer may be contacted, and forms the organic layer by filling the space | gap in the said layer produced by the removal of the said insulating site | part.
[17] An organic semiconductor portion having one of rectifying characteristics of either electron donating property or electron accepting property, an insulating portion, and a binding site for binding them, and having a molecular weight dispersion of 1.6 or less Forming a layer containing one compound, removing an insulating portion from the first compound in the layer, and adding a second compound having an organic semiconductor portion having a rectifying characteristic different from the organic semiconductor portion to the layer A thin film obtained by adding so as to come into contact.
[18] A photoelectric conversion element comprising the thin film according to [17].
[19] A light emitting device comprising the thin film according to [17].
[20] A sensor comprising the thin film according to [17].
本発明によれば、規則性の高いナノ構造を含む有機層を有し、発光効率や光電変換効率に優れた有機デバイスを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, it has an organic layer containing a highly regular nanostructure, and can provide the organic device excellent in luminous efficiency and photoelectric conversion efficiency.
以下、本発明の有機デバイスおよびその製造方法について詳細に説明する。 Hereinafter, the organic device and the manufacturing method thereof of the present invention will be described in detail.
(光電変換素子)
本発明の有機デバイスは、第1の電極と、第2の電極と、該第1の電極と該第2の電極との間に設けられた有機層とを有しており、有機層が、電子供与性及び電子受容性のうちのいずれか一方の整流特性を有する有機半導体部位と絶縁性部位とこれらを結合する結合部位とを有しており分子量分散が1.6以下である第1の化合物から絶縁性部位が除去された化合物と、第1の化合物の有機半導体部位とは異なる整流特性の有機半導体部位を有する第2の化合物とを含む。
(Photoelectric conversion element)
The organic device of the present invention includes a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode. A first organic semiconductor portion having an rectifying property of any one of electron donating properties and electron accepting properties, an insulating portion, and a binding site for bonding them, and having a molecular weight dispersion of 1.6 or less The compound from which the insulating part was removed from the compound and the 2nd compound which has the organic-semiconductor site | part of a rectification characteristic different from the organic-semiconductor site | part of a 1st compound are included.
本発明の有機デバイスを構成する構成要素について具体的に説明する。 The component which comprises the organic device of this invention is demonstrated concretely.
(基板)
本発明の有機デバイスは、通常、基板を含んでいる。用いられ得る基板としては、電極を形成する際、および有機層を形成する際に熱的または化学的に変化しない板状体であればよい。基板の材料としては、例えば、ガラス、プラスチック、高分子フィルムおよびシリコンが挙げられる。基板が不透明である場合には、基板とは反対側に位置する電極(すなわち、基板から遠い側の電極)が透明または不透明であることが好ましい。
(substrate)
The organic device of the present invention usually includes a substrate. The substrate that can be used may be a plate-like body that does not change thermally or chemically when the electrode is formed and when the organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. When the substrate is opaque, it is preferable that the electrode located on the opposite side of the substrate (that is, the electrode far from the substrate) is transparent or opaque.
(電極)
有機デバイスは、互いに対向する第1の電極および第2の電極を備えている。第1の電極および第2の電極のうちの少なくとも一方の電極は、透明または半透明の電極とされる。第1の電極および第2の電極のうちの一方の電極は陽極として機能し、他方の電極は陰極として機能する。
(electrode)
The organic device includes a first electrode and a second electrode facing each other. At least one of the first electrode and the second electrode is a transparent or translucent electrode. One of the first electrode and the second electrode functions as an anode, and the other electrode functions as a cathode.
陽極として機能する電極の材料としては、例えば、金属および導電性酸化物が挙げられる。当該金属の具体例としては、Al、Au、Pt、Sn、Zn、Cu、Ag、MoおよびTiが挙げられる。電極の安定性を高めるために、前記金属にに加えて、異種金属をさらに添加してもよい。陽極として機能する電極の材料である導電性酸化物としては、常温(25℃)付近で高い導電性を有する導電性酸化物が挙げられる。導電性酸化物の例としては、具体的には、ITO、SnO2、ZnO、FTO(フッ素が添加された酸化スズ)、IZO(酸化インジウムが添加された酸化亜鉛)、AlドープZnO(AZO)、GaドープZnO(GZO)、およびATO(アンチモンが添加された酸化スズ)が挙げられる。電極の形成方法としては、例えば、真空蒸着法、スパッタリング法、イオンプレーティング法およびメッキ法が挙げられる。 Examples of the material of the electrode functioning as the anode include metals and conductive oxides. Specific examples of the metal include Al, Au, Pt, Sn, Zn, Cu, Ag, Mo, and Ti. In order to increase the stability of the electrode, a different metal may be further added in addition to the metal. Examples of the conductive oxide that is a material of the electrode functioning as the anode include a conductive oxide having high conductivity near normal temperature (25 ° C.). Specific examples of the conductive oxide include ITO, SnO 2 , ZnO, FTO (tin oxide added with fluorine), IZO (zinc oxide added with indium oxide), and Al-doped ZnO (AZO). , Ga-doped ZnO (GZO), and ATO (antimony-added tin oxide). Examples of the electrode forming method include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
陽極として機能する電極の材料として、ポリアニリンおよびその誘導体、ポリチオフェンおよびその誘導体等の有機材料、モリブデン酸化物、バナジウム酸化物等のp型半導体金属酸化物材料を用いてもよい。 As an electrode material that functions as an anode, polyaniline and derivatives thereof, organic materials such as polythiophene and derivatives thereof, and p-type semiconductor metal oxide materials such as molybdenum oxide and vanadium oxide may be used.
陰極としては透明または半透明の導電性薄膜を用いることができる。陰極を形成し得る金属材料の例としては、アルミニウム、スカンジウム、バナジウム、亜鉛、銀、Pt、Sn、CuおよびTiなどが挙げられ、陰極を透明電極とする場合の材料しては、ITO、SnO2、ZnO、FTO、IZO、AZO、GZO、およびATOが挙げられる。 A transparent or translucent conductive thin film can be used as the cathode. Examples of the metal material that can form the cathode include aluminum, scandium, vanadium, zinc, silver, Pt, Sn, Cu, and Ti. Materials for the case where the cathode is a transparent electrode include ITO, SnO. 2 , ZnO, FTO, IZO, AZO, GZO, and ATO.
(有機層)
本発明の有機層は、第1の電極と該第2の電極との間に設けられており、電子供与性及び電子受容性のうちのいずれか一方の整流特性の有機半導体部位と絶縁性部位とこれらを結合する結合部位とを有しており分子量分散が1.6以下である第1の化合物から絶縁性部位が除去された化合物と、第1の化合物の有機半導体部位とは異なる整流特性の有機半導体部位を有する第2の化合物とを含む。
有機層は、例えば、入射した光により光起電力効果を得ることができる光学活性層であってもよい。光学活性層は、さらには例えば入射した光によって配向性を制御することができ、これにより電気的特性、光学的特性などを制御することができる層であってもよい。
(Organic layer)
The organic layer of the present invention is provided between the first electrode and the second electrode, and has an organic semiconductor part and an insulating part having a rectifying characteristic of either electron donating property or electron accepting property. And a rectifying characteristic that is different from the organic semiconductor part of the first compound and the compound from which the insulating part is removed from the first compound having a molecular weight dispersion of 1.6 or less And a second compound having an organic semiconductor moiety.
The organic layer may be, for example, an optically active layer that can obtain a photovoltaic effect by incident light. Further, the optically active layer may be a layer whose orientation can be controlled by incident light, for example, and which can control electrical characteristics, optical characteristics, and the like.
<第1の化合物>
第1の化合物は、有機半導体部位と絶縁性部位とこれらを結合する結合部位とを有しており、かつ分子量分散が1.6以下である化合物である。第1の化合物は、その有機半導体部位が長尺な構造を含む化合物であり、塗布成膜された際に自己組織化により有機半導体部位及び絶縁性部位により規則性の高いナノ構造を発現し、その後の工程で絶縁性部位が除去された後も有機半導体部位により構成された規則性の高いナノ構造を維持することができる化合物である。
<First compound>
The first compound is a compound having an organic semiconductor site, an insulating site, and a binding site for bonding them, and having a molecular weight dispersion of 1.6 or less. The first compound is a compound in which the organic semiconductor part has a long structure, and when the coating film is formed, the organic semiconductor part and the insulating part exhibit a highly ordered nanostructure by self-organization, It is a compound that can maintain a highly ordered nanostructure composed of organic semiconductor sites even after the insulating sites are removed in the subsequent steps.
第1の化合物における有機半導体部位と絶縁性部位との組み合わせは、自己組織化によって後述するようなナノ構造を形成することができることを条件として特に限定されない。第1の化合物は、有機半導体部位が疎水性を有し、絶縁性部位が親水性を有していることが好ましい。 The combination of the organic semiconductor site and the insulating site in the first compound is not particularly limited on the condition that a nanostructure as described later can be formed by self-assembly. In the first compound, it is preferable that the organic semiconductor portion has hydrophobicity and the insulating portion has hydrophilicity.
また、より規則性の高いナノ構造を形成させる観点から、第1の化合物は液晶性または結晶性を有することが好ましい。配向性、形成されるナノ構造を外力によって制御可能とする観点からは、第1の化合物のうちの少なくとも有機半導体部位は液晶性のみを有することがより好ましい。 Further, from the viewpoint of forming a nano structure having higher regularity, the first compound preferably has liquid crystallinity or crystallinity. From the viewpoint of enabling the orientation and the formed nanostructure to be controlled by external force, it is more preferable that at least the organic semiconductor portion of the first compound has only liquid crystallinity.
第1の化合物により形成され得るナノ構造の例としては、有機半導体部位が自己組織化によりネマチック相状に配列して形成されるナノポーラス構造、有機半導体部位が自己組織化によりスメクチック相状に配列して形成されるナノシリンダー配列、ナノロッド配列などが挙げられる。電荷の輸送経路を確保する観点からは、ナノポーラス構造、ナノシリンダー配列が好ましく、ナノシリンダー配列がより好ましい。 Examples of nanostructures that can be formed by the first compound include nanoporous structures formed by arranging organic semiconductor sites in a nematic phase by self-organization, and organic semiconductor sites arranged in a smectic phase by self-organization. And nanocylinder arrays and nanorod arrays formed by From the viewpoint of securing a charge transport route, a nanoporous structure and a nanocylinder arrangement are preferable, and a nanocylinder arrangement is more preferable.
ナノポーラス構造、ナノシリンダー配列を形成することができる第1の化合物は、電極に電荷を輸送しやすくする観点から、自己組織化された有機半導体部位の長軸が基板面に対して30°〜90°の角度をなすことが好ましい。この角度は、より好ましくは45°〜90°であり、80°〜90°であることが特に好ましい。 The first compound capable of forming a nanoporous structure and a nanocylinder arrangement is such that the major axis of the self-organized organic semiconductor site is 30 ° to 90 ° with respect to the substrate surface from the viewpoint of facilitating transport of charge to the electrode. It is preferable to make an angle of °. This angle is more preferably 45 ° to 90 °, and particularly preferably 80 ° to 90 °.
ナノポーラス構造、ナノシリンダー配列を構成する略円柱状の有機半導体部位の直径は、光電荷分離の観点から、10nm〜50nmが好ましい。さらに好ましくは、10nm〜20nmである。 The diameter of the substantially cylindrical organic semiconductor portion constituting the nanoporous structure and the nanocylinder arrangement is preferably 10 nm to 50 nm from the viewpoint of photocharge separation. More preferably, it is 10 nm-20 nm.
第1の化合物は、有機半導体部位、絶縁性部位および結合部位を有しており、有機半導体部位と絶縁性部位とが結合部位により結合されているブロック共重合体であることが好ましい。 The first compound has an organic semiconductor site, an insulating site, and a binding site, and is preferably a block copolymer in which the organic semiconductor site and the insulating site are bonded by a binding site.
有機半導体部位の整流特性は限定されず、p型(電子供与性)であってもn型(電子受容性)であってもよい。
有機半導体部位は、合成のしやすさの観点から、前記の通り疎水性であって、かつ電子供与性である有機半導体部位とすることが好ましい。
The rectifying property of the organic semiconductor portion is not limited, and may be p-type (electron donating property) or n-type (electron accepting property).
From the viewpoint of ease of synthesis, the organic semiconductor site is preferably an organic semiconductor site that is hydrophobic and has an electron donating property as described above.
電子供与性の有機半導体部位は、複素5員環を含むことが好ましい。電子供与性の有機半導体部位の例としては、ピラゾリン誘導体、アリールアミン誘導体、スチルベン誘導体、トリフェニルジアミン誘導体、オリゴチオフェンおよびその誘導体、ポリビニルカルバゾールおよびその誘導体、ポリシランおよびその誘導体、側鎖また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、ポリアニリンおよびその誘導体、ポリチオフェンおよびその誘導体、ポリピロールおよびその誘導体、ポリフェニレンビニレンおよびその誘導体、ポリチエニレンビニレンおよびその誘導体等に由来する1価の基が挙げられる。 The electron-donating organic semiconductor site preferably contains a hetero 5-membered ring. Examples of electron-donating organic semiconductor sites include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophenes and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilanes and derivatives thereof, side chains or main chains. And monovalent groups derived from polysiloxane derivatives having aromatic amine residues, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, and the like. .
電子供与性の有機半導体部位は、単環構造を含んでいてよく、縮合環構造を含んでいてもよい。また、電子供与性の有機半導体部位は、2個の単環構造同士あるいは2個の縮合環構造同士または単環構造および縮合環構造が直接結合で結合した構造を有していてもよい。該単環構造および縮合環構造は、芳香環を含んでいてもよい。芳香環は、ベンゼン環などの芳香族炭素環であってよく、芳香族複素環であってもよい。 The electron-donating organic semiconductor portion may contain a monocyclic structure or a condensed ring structure. In addition, the electron-donating organic semiconductor portion may have a structure in which two monocyclic structures or two condensed ring structures or a monocyclic structure and a condensed ring structure are bonded by a direct bond. The monocyclic structure and the condensed ring structure may contain an aromatic ring. The aromatic ring may be an aromatic carbocyclic ring such as a benzene ring or an aromatic heterocyclic ring.
電子供与性の有機半導体部位としては、例えば、2価の芳香族基、単環の芳香環または多環の芳香環が直接結合で連結した構造を含む1価の基、環構造を形成するように結合した1価の基が挙げられる。有機半導体部位に含まれる2価の芳香族基は、6員環以外にπ電子を供給して6π電子系、10π電子系、14π電子系を形成することができるのであれば、炭素原子以外の原子と−C=C−で表される基とが置換した構造を含んでいてもよい。 Examples of the electron-donating organic semiconductor moiety include a divalent aromatic group, a monovalent group including a structure in which a monocyclic aromatic ring or a polycyclic aromatic ring is connected by a direct bond, or a ring structure. And a monovalent group bonded to. The divalent aromatic group contained in the organic semiconductor region is capable of forming a 6π electron system, a 10π electron system, or a 14π electron system by supplying π electrons in addition to the six-membered ring. A structure in which an atom and a group represented by —C═C— are substituted may be included.
電子供与性である有機半導体部位の例としては、具体的には、置換基を有していてもよいフルオレンジイル基、置換基を有していてもよいベンゾフルオレンジイル基、置換基を有していてもよいジベンゾフランジイル基、置換基を有していてもよいジベンゾチオフェンジイル基、置換基を有していてもよいベンゾジチオフェンジイル基、置換基を有していてもよいチオフェンジイル基、置換基を有していてもよいシクロペンタジチオフェンジイル基、置換基を有していてもよいカルバゾールジイル基、置換基を有していてもよいチオフェンジイル基、置換基を有していてもよいフランジイル基、置換基を有していてもよいピロールジイル基、置換基を有していてもよいベンゾチアジアゾールジイル基、および置換基を有していてもよいトリフェニルアミンジイル基からなる群から選ばれる1種または2種以上の2価の基を構成単位として含み、該構成単位同士が直接結合で結合しているかまたは連結基を介して結合した構造を含む1価の基が挙げられる。 Specific examples of the electron-donating organic semiconductor moiety include a fluorenediyl group which may have a substituent, a benzofluorenediyl group which may have a substituent, and a substituent. Dibenzofurandiyl group which may have, dibenzothiophenediyl group which may have substituent, benzodithiophenediyl group which may have substituent, thiophene diyl which may have substituent Group, an optionally substituted cyclopentadithiophenediyl group, an optionally substituted carbazolediyl group, an optionally substituted thiophenediyl group, and a substituent. An optionally substituted frangyl group, an optionally substituted pyrrole diyl group, an optionally substituted benzothiadiazole diyl group, and an optionally substituted trif A monovalent group comprising one or two or more divalent groups selected from the group consisting of nylaminediyl groups as a structural unit, wherein the structural units are bonded directly by a bond or bonded via a linking group. The group of is mentioned.
なお、本明細書において、「置換基を有していてもよい」場合の置換基の例としては、ハロゲン原子、1個以上の水素原子がハロゲン原子で置換されていてもよい炭素原子数が1〜20であるアルキル基、1個以上の水素原子がハロゲン原子で置換されていてもよい炭素原子数が3〜20であるシクロアルキル基、1個以上の水素原子がハロゲン原子で置換されていてもよい炭素原子数が1〜20であるアルコキシ基および1個以上の水素原子がハロゲン原子で置換されていてもよい炭素原子数が3〜20であるシクロアルコキシ基が挙げられる。 In the present specification, examples of the substituent in the case of “may have a substituent” include a halogen atom, the number of carbon atoms in which one or more hydrogen atoms may be substituted with a halogen atom. 1 to 20 alkyl groups, one or more hydrogen atoms optionally substituted with a halogen atom, a cycloalkyl group having 3 to 20 carbon atoms, one or more hydrogen atoms substituted with a halogen atom Examples thereof include an alkoxy group having 1 to 20 carbon atoms and a cycloalkoxy group having 3 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a halogen atom.
アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、イソペンチル基、ヘキシル基、ヘプチル基、オクチル基、2−エチルヘキシル基、ノニル基、デシル基、3,7−ジメチルオクチル基、ドデシル基等が挙げられる。1個以上の水素原子がハロゲン原子で置換されているアルキル基としては、フッ素原子で置換されているアルキル基が好ましい。フッ素原子で置換されているアルキル基としては、例えば、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロブチル基、パーフルオロヘキシル基、パーフルオロオクチル基等が挙げられる。シクロアルキル基の具体例としては、シクロヘキシル基が挙げられる。1個以上の水素原子がハロゲン原子で置換されているシクロアルキル基としては、フッ素原子で置換されているシクロアルキル基が好ましい。 Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group. 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, dodecyl group and the like. The alkyl group in which one or more hydrogen atoms are substituted with a halogen atom is preferably an alkyl group substituted with a fluorine atom. Examples of the alkyl group substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group. Specific examples of the cycloalkyl group include a cyclohexyl group. The cycloalkyl group in which one or more hydrogen atoms are substituted with a halogen atom is preferably a cycloalkyl group substituted with a fluorine atom.
アルコキシ基中のアルキル部は鎖状でも環状でもよく、アルコキシ基の具体例としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、sec−ブトキシ基、tert−ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、、ヘプチルオキシ基、オクチルオキシ基、2−エチルヘキシルオキシ基、ノニルオキシ基、デシルオキシ基、3,7−ジメチルオクチルオキシ基及びラウリルオキシ基が挙げられる。1個以上の水素原子がハロゲン原子で置換されているアルコキシ基としては、フッ素原子で置換されているアルコキシ基が好ましい。フッ素原子で置換されているアルコキシ基としては、例えば、トリフルオロメトキシ基、ペンタフルオロエトキシ基、パーフルオロブトキシ基、パーフルオロヘキシルオキシ基およびパーフルオロオクチルオキシ基が挙げられる。シクロアルコキシ基の具体例としては、シクロヘキシルオキシ基が挙げられる。1個以上の水素原子がハロゲン原子で置換されているアルコキシ基としては、フッ素原子で置換されているアルコキシ基が好ましい。 The alkyl part in the alkoxy group may be linear or cyclic. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. Pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group and lauryloxy group. As the alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom, an alkoxy group substituted with a fluorine atom is preferable. Examples of the alkoxy group substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group. Specific examples of the cycloalkoxy group include a cyclohexyloxy group. As the alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom, an alkoxy group substituted with a fluorine atom is preferable.
電荷輸送性を高める観点と、より規則性の高いナノ構造を発現しやすくする観点から、有機半導体部位は前記構成単位が3つ以上連結した構造を含むことが好ましい。構成単位としては、置換基を有していてもよいチオフェンジイル基またはビチオフェンの3位の炭素原子と3’位の炭素原子とが、硫黄原子、酸素原子または窒素原子を介して結合した渡環構造を含むことが好ましく、置換基を有していてもよいチオフェンジイル基を含むことがより好ましい。 From the viewpoint of enhancing the charge transporting property and from the viewpoint of facilitating the expression of a more regular nanostructure, the organic semiconductor portion preferably includes a structure in which three or more structural units are connected. As the structural unit, a thiophene diyl group or bithiophene which may have a substituent, a 3rd-position carbon atom and a 3′-position carbon atom bonded via a sulfur atom, an oxygen atom or a nitrogen atom It preferably includes a structure, and more preferably includes a thiophenediyl group which may have a substituent.
有機半導体部位は、具体的には、下記式(1)で示される構造であることが好ましい。 Specifically, the organic semiconductor part preferably has a structure represented by the following formula (1).
式(1)中、Xは−C=C−で示される基、−C≡C−で示される基または−N=N−で示される基を表す。mは0または1である。nは1以上の整数である。R0、R1、R2、R3、R4およびZはそれぞれ独立に、水素原子、ハロゲン原子、炭素原子数1〜20のアルキル基、炭素原子数3〜20のシクロアルキル基、炭素原子数2〜20の1価の脂肪族不飽和炭化水素基、炭素原子数1〜20のアルコキシ基、炭素原子数3〜20のシクロアルコキシ基、炭素原子数1〜20のアルキルチオ基、炭素原子数3〜20のシクロアルキルチオ基、置換基を有していてもよい1価の芳香族炭化水素基または置換基を有していてもよい1価の複素環基を表す。 In formula (1), X represents a group represented by —C═C—, a group represented by —C≡C—, or a group represented by —N═N—. m is 0 or 1. n is an integer of 1 or more. R 0 , R 1 , R 2 , R 3 , R 4 and Z are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a carbon atom. A monovalent aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and the number of carbon atoms 3 to 20 cycloalkylthio groups, a monovalent aromatic hydrocarbon group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
R0、R1、R2、R3、R4およびZで表される炭素原子数1〜20のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、tert−ブチル基、ヘキシル基、オクチル基、およびシクロヘキシル基が挙げられ、炭素原子数3〜20のシクロアルキル基としては、例えば、シクロヘキシル基が挙げられる。 Examples of the alkyl group having 1 to 20 carbon atoms represented by R 0 , R 1 , R 2 , R 3 , R 4 and Z include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a tert-butyl group. , A hexyl group, an octyl group, and a cyclohexyl group. Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclohexyl group.
R0、R1、R2、R3、R4およびZで表される炭素原子数2〜20の1価の脂肪族不飽和炭化水素基としては、例えば、ビニル基、2−プロペニル基、エチニル基、および2−プロピニル基が挙げられる。 Examples of the monovalent aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms represented by R 0 , R 1 , R 2 , R 3 , R 4 and Z include, for example, a vinyl group, a 2-propenyl group, Examples include ethynyl group and 2-propynyl group.
R0、R1、R2、R3、R4およびZで表される炭素原子数1〜20のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ヘキシルオキシ基およびオクチルオキシ基が挙げられ、炭素原子数3〜20のシクロアルコキシ基としては、例えば、シクロヘキシルオキシ基が挙げられる。 Examples of the alkoxy group having 1 to 20 carbon atoms represented by R 0 , R 1 , R 2 , R 3 , R 4 and Z include, for example, methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group and An octyloxy group is mentioned, As a C3-C20 cycloalkoxy group, a cyclohexyloxy group is mentioned, for example.
R0、R1、R2、R3、R4およびZで表される炭素原子数1〜20のアルキルチオ基としては、例えば、メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基、ヘキシルチオ基、およびオクチルチオ基が挙げられ、炭素原子数3〜20のシクロアルキルチオ基としては、例えば、シクロヘキシルチオ基が挙げられる。 Examples of the alkylthio group having 1 to 20 carbon atoms represented by R 0 , R 1 , R 2 , R 3 , R 4 and Z include, for example, methylthio group, ethylthio group, propylthio group, butylthio group, hexylthio group, and An octylthio group is mentioned, As a C3-C20 cycloalkylthio group, a cyclohexylthio group is mentioned, for example.
R0、R1、R2、R3、R4およびZで表される置換基を有していてもよい1価の芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、アントラセニル基、およびペリレン−イル基が挙げられる。 Examples of the monovalent aromatic hydrocarbon group optionally having a substituent represented by R 0 , R 1 , R 2 , R 3 , R 4 and Z include a phenyl group, a naphthyl group, and an anthracenyl group. And perylene-yl groups.
R0、R1、R2、R3、R4およびZで表される置換基を有していてもよい1価の複素環基としては、例えば、チエニル基、ピリジル基、フリル基、チアゾリル基、ピリミジル基、トリアジニル基、キノリル基およびイソキノリル基が挙げられる。 Examples of the monovalent heterocyclic group optionally having a substituent represented by R 0 , R 1 , R 2 , R 3 , R 4 and Z include a thienyl group, pyridyl group, furyl group, thiazolyl Group, pyrimidyl group, triazinyl group, quinolyl group and isoquinolyl group.
式(1)で示される構造において、nは1から100であることが好ましい。 In the structure represented by the formula (1), n is preferably 1 to 100.
有機半導体部位は、前記nが1である場合、配向性の観点から、具体的には下記式(2)で示される構造であることが好ましい。 In the case where n is 1, the organic semiconductor portion preferably has a structure specifically represented by the following formula (2) from the viewpoint of orientation.
式(2)中、Zは前記定義の通りである。 In formula (2), Z is as defined above.
有機半導体部位が前記式(2)で示される構造である場合には、Zがn−ブチル基であることが好ましい。 When the organic semiconductor site has a structure represented by the formula (2), Z is preferably an n-butyl group.
有機半導体部位は、式(1)で表される構造においてnが2以上の整数である場合、配向性と合成のしやすさとの観点から、具体的には、下記式(3)で示される構造であることが好ましい。 When n is an integer of 2 or more in the structure represented by the formula (1), the organic semiconductor site is specifically represented by the following formula (3) from the viewpoint of orientation and ease of synthesis. A structure is preferred.
式(3)中、R0、R1、R2、R3、R4およびZは、前記定義の通りである。nは2以上の整数である。
有機半導体部位が式(3)で示される構造を有する場合、結晶性、液晶性などの配向性を高める観点から、R0、R1、R2、R3およびR4は全て同一の基であることが好ましい。さらに、溶解性を高める観点から、R0、R1、R2、R3およびR4はアルキル基であることが好ましく、中でも分岐を有しない直鎖のアルキル基であることがより好ましい。R0、R1、R2、R3およびR4はさらに好ましくはn−デシル基、n−オクチル基、n−ヘキシル基、n−ブチル基であり、n−ヘキシル基であることが特に好ましい。
In formula (3), R 0 , R 1 , R 2 , R 3 , R 4 and Z are as defined above. n is an integer of 2 or more.
When the organic semiconductor portion has the structure represented by the formula (3), R 0 , R 1 , R 2 , R 3 and R 4 are all the same group from the viewpoint of enhancing the orientation such as crystallinity and liquid crystallinity. Preferably there is. Furthermore, from the viewpoint of enhancing solubility, R 0 , R 1 , R 2 , R 3 and R 4 are preferably alkyl groups, and more preferably linear alkyl groups having no branches. R 0 , R 1 , R 2 , R 3 and R 4 are more preferably an n-decyl group, an n-octyl group, an n-hexyl group and an n-butyl group, and particularly preferably an n-hexyl group. .
有機半導体部位が式(3)で表される構造を有する場合、分子同士の相互作用を高める観点から、Zは水素原子またはハロゲン原子であることが好ましい。合成のしやすさからはハロゲン原子であることがより好ましく、中でも、臭素がさらに好ましい。 When the organic semiconductor site has a structure represented by the formula (3), Z is preferably a hydrogen atom or a halogen atom from the viewpoint of enhancing the interaction between molecules. In view of ease of synthesis, a halogen atom is more preferable, and bromine is more preferable.
有機半導体部位が式(3)で示される構造を有する場合、Zが塩素原子または臭素原子であり、かつR0、R1、R2、R3およびR4がいずれも直鎖のアルキル基であることが好ましく、R0、R1、R2、R3およびR4がいずれもn−ヘキシル基であることがより好ましい。 When the organic semiconductor portion has a structure represented by the formula (3), Z is a chlorine atom or a bromine atom, and R 0 , R 1 , R 2 , R 3 and R 4 are all linear alkyl groups. It is preferable that R 0, R 1 , R 2 , R 3 and R 4 are all n-hexyl groups.
[絶縁性部位]
第1の化合物の絶縁性部位は、溶解性を高める観点から、主鎖が非共役構造であるポリマーであることが好ましい。また、有機半導体部位と自発的に相分離、自己集積してナノ構造を発現させる観点から、有機半導体部位が疎水性を有する1価の基であり、絶縁性部位が親水性を有する1価の基であることが好ましく、さらに絶縁性部位は親水性を有するポリマーに由来する1価の基であることがより好ましい。
[Insulating part]
The insulating portion of the first compound is preferably a polymer whose main chain has a non-conjugated structure from the viewpoint of improving solubility. In addition, from the viewpoint of spontaneously phase-separating and self-integrating with an organic semiconductor site to develop a nanostructure, the organic semiconductor site is a monovalent group having hydrophobicity, and the insulating site is a monovalent group having hydrophilicity. It is preferably a group, and the insulating part is more preferably a monovalent group derived from a hydrophilic polymer.
絶縁性部位の例としては、具体的には、ポリアクリル酸、ポリビニルアルコール、ポリエチレンオキサイド、ポリアクリルアミド、ポリエチレンイミン、ポリビニルピロリドンなど親水性を有するポリマーに由来する1価の基が挙げられる。ナノ構造を発現させる観点からは、さらに前記の絶縁性部位を構成し得るポリマーの分子量分散が小さいものが好ましい。さらには入手しやすさの観点から、絶縁性部位を構成し得る親水性を有するポリマーに由来する1価の基としては、ポリエチレンオキサイド鎖を有する1価の基であることが好ましい。用いられ得るポリエチレンオキサイドの分子量は、2000〜100000であることが好ましく、1000〜50000であることがより好ましい。 Specific examples of the insulating site include monovalent groups derived from hydrophilic polymers such as polyacrylic acid, polyvinyl alcohol, polyethylene oxide, polyacrylamide, polyethyleneimine, and polyvinylpyrrolidone. From the viewpoint of developing the nanostructure, a polymer having a small molecular weight dispersion that can constitute the insulating portion is preferable. Furthermore, from the viewpoint of easy availability, the monovalent group derived from a hydrophilic polymer that can form an insulating site is preferably a monovalent group having a polyethylene oxide chain. The molecular weight of polyethylene oxide that can be used is preferably 2000 to 100,000, more preferably 1000 to 50,000.
ポリエチレンオキサイド鎖を有する1価の基としては、具体的には下記式(A)で示される構造であることが好ましい。 Specifically, the monovalent group having a polyethylene oxide chain is preferably a structure represented by the following formula (A).
式(A)中、yは1以上の整数であり、50〜5000であることが好ましく、100〜2000であることがより好ましい。 In the formula (A), y is an integer of 1 or more, preferably 50 to 5000, and more preferably 100 to 2000.
[結合部位]
第1の化合物の結合部位は、酸、アルカリなどによる化学的処理、熱、光などによる物理的処理またはこれらを組み合わせた処理によって、容易に分解し、有機半導体部位と絶縁性部位とを分離できる構造を有している。なお有機半導体部位と絶縁性部位とが分離された際には、有機半導体部位および絶縁性部位のうちの一方又は両方に結合部位の一部分に由来する構造が残存する場合がある。
結合部位としては、具体的には、アセタール結合、エステル結合、エーテル結合、チオエーテル結合などを含む構造が挙げられる。結合部位は、合成のしやすさの観点から、アセタール結合を含む構造を有することが好ましい。
[Binding site]
The binding site of the first compound can be easily decomposed by chemical treatment with acid, alkali, etc., physical treatment with heat, light, etc., or a combination thereof, and the organic semiconductor site and the insulating site can be separated. It has a structure. When the organic semiconductor portion and the insulating portion are separated, a structure derived from a part of the binding portion may remain in one or both of the organic semiconductor portion and the insulating portion.
Specific examples of the binding site include structures containing an acetal bond, an ester bond, an ether bond, a thioether bond, and the like. The binding site preferably has a structure containing an acetal bond from the viewpoint of ease of synthesis.
結合部位の例としては、下記の構造を有する2価の基が挙げられる。 Examples of the binding site include a divalent group having the following structure.
合成のしやすさの観点から、第1の化合物は、有機半導体部位、絶縁体部位、結合部位以外の部位を含んでいてもよい。有機半導体部位、絶縁体部位、結合部位以外の部位の具体的な例としては、エチレン、プロピレンなどの飽和炭化水素基、2価の芳香族炭化水素基、2価の複素環基などが挙げられ、好ましくはエチレン、トリアジンである。 From the viewpoint of ease of synthesis, the first compound may include a portion other than the organic semiconductor portion, the insulator portion, and the binding portion. Specific examples of sites other than organic semiconductor sites, insulator sites, and bond sites include saturated hydrocarbon groups such as ethylene and propylene, divalent aromatic hydrocarbon groups, and divalent heterocyclic groups. Of these, ethylene and triazine are preferable.
第1の化合物の好ましい構造としては、下記式(4)、下記式(5)および下記式(6)で示される構造を有するブロック共重合体が挙げられる。 A preferred structure of the first compound includes a block copolymer having a structure represented by the following formula (4), the following formula (5) and the following formula (6).
式(4)中、X2は水素原子、ハロゲン原子、炭素原子数1〜20のアルキル基、炭素原子数3〜20のシクロアルキル基、炭素原子数2〜20の1価の脂肪族不飽和炭化水素基、炭素原子数1〜20のアルコキシ基、炭素原子数3〜20のシクロアルコキシ基、炭素原子数1〜20のアルキルチオ基、炭素原子数3〜20のシクロアルキルチオ基、置換基を有していてもよい1価の芳香族炭化水素基または置換基を有していてもよい1価の複素環基を表す。合成上の観点から、X2はハロゲン原子、炭素原子数1〜20のアルキル基、置換基を有していてもよい1価の芳香族炭化水素基が好ましい。その中でも、ハロゲン原子、メチル基、エチル基、プロピル基がより好ましく、ハロゲン原子がさらに好ましい。q、sは1以上の整数である。sは1〜100であることが好ましく、1〜50であることがより好ましい。式(5)中、pおよびnは、それぞれ独立に1以上の整数である。q及びpはそれぞれ独立に、50〜5000であることが好ましく、100〜2000であることがより好ましい。式(6)中、rは2以上の整数である。rは5〜200であることが好ましく、10〜100であることがより好ましい。 In formula (4), X 2 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent aliphatic unsaturated group having 2 to 20 carbon atoms. It has a hydrocarbon group, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a cycloalkylthio group having 3 to 20 carbon atoms, and a substituent. Represents a monovalent aromatic hydrocarbon group which may be substituted or a monovalent heterocyclic group which may have a substituent. From the viewpoint of synthesis, X 2 is preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group which may have a substituent. Among these, a halogen atom, a methyl group, an ethyl group, and a propyl group are more preferable, and a halogen atom is more preferable. q and s are integers of 1 or more. s is preferably 1 to 100, and more preferably 1 to 50. In formula (5), p and n are each independently an integer of 1 or more. q and p are each independently preferably 50 to 5000, and more preferably 100 to 2000. In formula (6), r is an integer of 2 or more. r is preferably 5 to 200, and more preferably 10 to 100.
第1の化合物は、数平均分子量(Mn)と重量平均分子量(Mw)との割合である分子量分散(Mw/Mn)がより小さいことが好ましい。数平均分子量(Mn)および重量平均分子量(Mw)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分子量を意味する。 The first compound preferably has a smaller molecular weight dispersion (Mw / Mn), which is a ratio between the number average molecular weight (Mn) and the weight average molecular weight (Mw). The number average molecular weight (Mn) and the weight average molecular weight (Mw) mean a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
第1の化合物の分子量分散は、1.6以下であり、1.5以下であることが好ましく、1.3以下であることがより好ましく、1.2以下であることがさらに好ましい。 The molecular weight dispersion of the first compound is 1.6 or less, preferably 1.5 or less, more preferably 1.3 or less, and even more preferably 1.2 or less.
第1の化合物の分子量分散を上記のようにより小さくすることにより、得られるナノ構造の配列の規則性(周期性)をより高めることができるので第1の化合物の相と第2の化合物の相との相分離をより好適な態様に最適化することができる。結果として、有機デバイスの特性をより高めることができる。 By reducing the molecular weight dispersion of the first compound as described above, it is possible to further increase the regularity (periodicity) of the arrangement of the obtained nanostructures, so the phase of the first compound and the phase of the second compound Can be optimized in a more preferred manner. As a result, the characteristics of the organic device can be further improved.
<第2の化合物>
第2の化合物は、第1の化合物の有機半導体部位とは異なる整流特性の有機半導体部位を有する化合物である。第2の化合物の有機半導体部位は、n型(電子受容性)の整流特性を有することが好ましい。よって、第2の化合物の有機半導体部位がn型の整流特性を有する場合には、第1の化合物の有機半導体部位はp型の整流特性を有することとなる。n型の特性を有する第2の化合物の有機半導体部位としては、具体的には、フラーレン誘導体、ペリレンジイミド誘導体、ナフタレンジイミド誘導体に由来する1価の基などが挙げられる。第2の化合物の有機半導体部位は、電子受容性の観点から、フラーレン誘導体に由来する1価の基であることが好ましい。
<Second compound>
The second compound is a compound having an organic semiconductor portion having a rectifying characteristic different from the organic semiconductor portion of the first compound. The organic semiconductor portion of the second compound preferably has n-type (electron accepting) rectification characteristics. Therefore, when the organic semiconductor part of the second compound has an n-type rectifying characteristic, the organic semiconductor part of the first compound has a p-type rectifying characteristic. Specific examples of the organic semiconductor portion of the second compound having n-type characteristics include monovalent groups derived from fullerene derivatives, perylene diimide derivatives, and naphthalene diimide derivatives. The organic semiconductor portion of the second compound is preferably a monovalent group derived from a fullerene derivative from the viewpoint of electron accepting properties.
フラーレン誘導体の中でも、C60フラーレン、C70フラーレン、フェニルC61酪酸メチルエステル、フェニルC71酪酸メチルエステル、またはインデンC60ビス付加体、インデンC70ビス付加体などのフラーレン誘導体が好ましい。なかでもC70フラーレン、フェニルC61酪酸メチルエステル、フェニルC71酪酸メチルエステル、またはインデンC60ビス付加体、インデンC70ビス付加体がより好ましい。 Among the fullerene derivatives, fullerene derivatives such as C 60 fullerene, C 70 fullerene, phenyl C 61 butyric acid methyl ester, phenyl C 71 butyric acid methyl ester, or indene C 60 bis adduct and indene C 70 bis adduct are preferable. Among these, C 70 fullerene, phenyl C 61 butyric acid methyl ester, phenyl C 71 butyric acid methyl ester, indene C 60 bis adduct, and indene C 70 bis adduct are more preferable.
(中間層)
本発明の有機デバイスは、有機層と電極との間に、電荷の注入、および/または輸送の効率を高める特性を有する中間層、電極を形成する際の成膜性、電極を形成する際の電極より下層へのダメージを低減する特性を有する中間層など、発電特性、製造工程における耐久性などを高める機能を有する中間層を有していてもよい。
(Middle layer)
The organic device of the present invention includes an intermediate layer having characteristics that enhance the efficiency of charge injection and / or transport between an organic layer and an electrode, film formability when forming an electrode, and when forming an electrode. You may have an intermediate | middle layer which has a function which improves a power generation characteristic, durability in a manufacturing process, etc., such as an intermediate | middle layer which has the characteristic which reduces the damage to a lower layer from an electrode.
中間層の材料としては有機材料または金属酸化物材料を用いることができる。中間層は、蒸着法、スパッタリング法、レーザーアブレーション法などの気相法、ゾルゲル法、スプレーコート法、印刷法、塗布法などの湿式法などを用いて形成することができる。正孔の注入および/または輸送の効率を高める特性を有する層の例としては、ポリ(エチレンジオキシチオフェン)(PEDOT)/ポリスチレンスルホン酸複合体を含む層などが挙げられる。 As the material of the intermediate layer, an organic material or a metal oxide material can be used. The intermediate layer can be formed using a vapor phase method such as an evaporation method, a sputtering method, or a laser ablation method, a wet method such as a sol-gel method, a spray coating method, a printing method, or a coating method. Examples of the layer having the property of increasing the efficiency of hole injection and / or transport include a layer containing poly (ethylenedioxythiophene) (PEDOT) / polystyrene sulfonic acid complex.
(有機デバイスの製造方法)
本発明の有機デバイスの製造方法は、第1の電極と、第2の電極と、該第1の電極と該第2の電極との間に設けられた有機層を有する有機デバイスの製造方法であって、電子供与性および電子受容性のうちのいずれか一方の整流特性を有する有機半導体部位と絶縁性部位とこれらを結合する結合部位を有しており、分子量分散が1.6以下である第1の化合物を含む層を形成した後に、層中の第1の化合物の結合部位を分解することで絶縁性部位を除去し、次いで第1の化合物の有機半導体部位とは異なる整流特性の有機半導体部位を有する第2の化合物を、絶縁性部位を除去した前記層に接触するように添加し、絶縁性部位の除去により生じた層中の空隙に充填することで、絶縁性部位が除去された第1の化合物および第2の化合物を含む有機層を形成することを特徴とする製造方法である。ここで接触するように添加するとは、例えば第2の有機化合物を真空蒸着するか、または第2の化合物を含む溶液を塗布法により塗布することなどをいう。
(Organic device manufacturing method)
The organic device manufacturing method of the present invention is a method of manufacturing an organic device having a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode. And having an organic semiconductor portion having one of rectifying properties of electron donating property and electron accepting property, an insulating portion, and a binding portion for binding them, and having a molecular weight dispersion of 1.6 or less. After forming the layer containing the first compound, the insulating portion is removed by decomposing the binding site of the first compound in the layer, and then the organic compound having a rectifying characteristic different from the organic semiconductor portion of the first compound A second compound having a semiconductor site is added so as to contact the layer from which the insulating site has been removed, and the insulating site is removed by filling the voids in the layer generated by the removal of the insulating site. Including a first compound and a second compound Is a manufacturing method characterized by forming the machine layer. Here, adding to contact means, for example, vacuum-depositing the second organic compound or applying a solution containing the second compound by a coating method.
第1の電極および第2の電極(陰極および陽極)の形成方法については既に説明した通りであるのでここでは有機層の形成工程について説明する。 Since the method for forming the first electrode and the second electrode (cathode and anode) has already been described, the organic layer forming step will be described here.
有機層は、まず第1の電極、または第1の電極と第1の電極に接合する中間層が設けられた基板上に第1の化合物を含む溶液または分散液(以下、単に「液」という。)を塗布して塗布層を形成し、形成された塗布層を乾燥処理により乾燥させて有機半導体部位と絶縁性部位とを自己組織化させて規則的なナノ構造を発現させることにより、既に説明したようなナノシリンダー配列などを含むナノ構造を含む層を形成する。 The organic layer is a solution or dispersion liquid (hereinafter simply referred to as “liquid”) containing the first compound on a substrate provided with an intermediate layer bonded to the first electrode or the first electrode and the first electrode. .) Is applied to form a coating layer, and the formed coating layer is dried by a drying process to self-organize the organic semiconductor portion and the insulating portion to develop a regular nanostructure. A layer including a nanostructure including a nanocylinder arrangement as described is formed.
続いて、既に説明した酸処理などの処理により結合部位を分解して有機半導体部位と絶縁性部位とを分離して、第1の化合物から絶縁性部位を除去する。その後、第1の化合物から絶縁性部位を除去した層上に第2の有機化合物を含む溶液を塗布することによって、前記層中の、絶縁性部位を除去したことによって生じた空隙に第2の化合物を充填することにより製造することができる。 Subsequently, the binding site is decomposed by the treatment such as the acid treatment already described to separate the organic semiconductor site and the insulating site, and the insulating site is removed from the first compound. Thereafter, by applying a solution containing the second organic compound on the layer from which the insulating portion has been removed from the first compound, the second gap is formed in the void generated by removing the insulating portion in the layer. It can be produced by filling with a compound.
第1の化合物を含む層は、前記の通り第1の化合物を含む液を用いて塗布法により形成することができる。第1の化合物を含む層を形成する際に用いられ得る塗布法としては、例えばスリットコート法、キャピラリーコート法、グラビアコート法、マイクログラビアコート法、バーコート法、ナイフコート法、ノズルコート法、インクジェットコート法およびスピンコート法が挙げられる。 As described above, the layer containing the first compound can be formed by a coating method using the liquid containing the first compound. Examples of the coating method that can be used when forming the layer containing the first compound include a slit coating method, a capillary coating method, a gravure coating method, a micro gravure coating method, a bar coating method, a knife coating method, a nozzle coating method, Examples thereof include an ink jet coating method and a spin coating method.
第1の化合物を含む層には、塗布膜を乾燥させる工程で、含まれる多数の第1の化合物のうちの例えば疎水性である有機半導体部位と例えば親水性である絶縁性部位とが、それぞれ同じ性質を有する部位同士が規則的に集積(配列)して自己組織化する結果としてナノ構造が形成される。この観点から、第1の化合物を含む溶液を形成するために用いられ得る溶媒としては、疎水性部位に対して良好な溶解性を示す溶媒を選択することが好ましい。このような溶媒としては、具体的には、トルエン、キシレンなどの芳香族炭化水素溶媒や、クロロホルム、クロロベンゼン、オルトジクロロベンゼンなどのハロゲン化炭化水素溶媒、ヘキサン、オクタンなどの飽和炭化水素溶媒が挙げられる。形成される層の厚さの均一性、形成されるナノ構造のさらなる微細化の観点から、用いられ得る溶媒としては、芳香族炭化水素溶媒とハロゲン化炭化水素溶媒がより好ましい。用いられ得る溶媒としては、さらに好ましくは、トルエン、キシレン、クロロベンゼン、オルトジクロロベンゼンである。 In the layer containing the first compound, in the step of drying the coating film, for example, an organic semiconductor site that is hydrophobic and an insulating site that is hydrophilic, for example, among the multiple first compounds included, Nanostructures are formed as a result of regular accumulation (arrangement) of sites having the same properties and self-organization. From this point of view, as a solvent that can be used to form a solution containing the first compound, it is preferable to select a solvent that exhibits good solubility in a hydrophobic site. Specific examples of such solvents include aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chloroform, chlorobenzene, and orthodichlorobenzene, and saturated hydrocarbon solvents such as hexane and octane. It is done. From the viewpoint of uniformity of the thickness of the formed layer and further refinement of the formed nanostructure, the solvent that can be used is more preferably an aromatic hydrocarbon solvent or a halogenated hydrocarbon solvent. As the solvent that can be used, toluene, xylene, chlorobenzene, and orthodichlorobenzene are more preferable.
より高次のナノ構造を得るため、形成された第1の化合物を含む層に対して熱処理をさらに行ってもよい。 In order to obtain a higher-order nanostructure, heat treatment may be further performed on the formed layer containing the first compound.
第1の化合物を含む層のうちの絶縁性部位は、酸、アルカリ、光、熱などによる処理により結合部位を分解させることで有機半導体部位とは分離され、層中の第1の化合物から絶縁性部位が除去される。有機デバイスの特性低下を抑える観点から、酸性溶液、アルカリ溶液による処理が好ましく、より好ましくは、酸性水溶液、アルカリ水溶液による処理である。 The insulating part in the layer containing the first compound is separated from the organic semiconductor part by decomposing the bonding part by treatment with acid, alkali, light, heat, etc., and is insulated from the first compound in the layer. Sex sites are removed. From the viewpoint of suppressing deterioration in characteristics of the organic device, treatment with an acidic solution or an alkaline solution is preferable, and treatment with an acidic aqueous solution or an alkaline aqueous solution is more preferable.
酸性溶液の例としては、塩酸、硝酸、硫酸の原液もしくは希釈液、酢酸、パラトルエンスルホン酸、トリフルオロメタンスルホン酸、トリフルオロ酢酸などの有機酸の溶液が挙げられる。絶縁性部位の除去後に層中に残存する有機半導体部位の特性維持の観点からは、酸性溶液としては塩酸の希釈液、有機酸の溶液が好ましい。 Examples of the acidic solution include a solution of an organic acid such as hydrochloric acid, nitric acid, sulfuric acid stock solution or diluted solution, acetic acid, paratoluenesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid. From the viewpoint of maintaining the characteristics of the organic semiconductor portion remaining in the layer after the removal of the insulating portion, the acidic solution is preferably a dilute hydrochloric acid solution or an organic acid solution.
アルカリ溶液の例としては、カリウム、ナトリウムなどのアルカリ金属のハロゲン化物、炭酸塩、水酸化物、アンモニア、トリアルキルアミン、ジメチルホルムアミド、ジメチルスルホキシドなどの溶液が挙げられる。絶縁性部位の除去後に層中に残存する有機半導体部位の特性維持の観点からは、無機塩類の溶液を用いることが好ましく、より好ましくは無機塩類の水溶液である。 Examples of the alkali solution include solutions of alkali metal halides such as potassium and sodium, carbonates, hydroxides, ammonia, trialkylamines, dimethylformamide, dimethylsulfoxide and the like. From the viewpoint of maintaining the characteristics of the organic semiconductor portion remaining in the layer after removal of the insulating portion, it is preferable to use a solution of an inorganic salt, and more preferably an aqueous solution of an inorganic salt.
結合部位が分解され、有機半導体部位から分離された絶縁性部位は、それが可溶な溶媒に第1の化合物を含む層を浸漬したり、かかる溶媒を流すことによって第1の化合物の層から除去することができる。第1の化合物の層のナノ構造を維持する観点から、有機半導体部位から分離された絶縁性部位を除去するための溶媒としては、水、アルコール、カルボン酸などの親水性溶媒を用いることが好ましい。 The insulating part separated from the organic semiconductor part is decomposed from the first compound layer by immersing the layer containing the first compound in a solvent in which the binding part is soluble or flowing the solvent. Can be removed. From the viewpoint of maintaining the nanostructure of the first compound layer, it is preferable to use a hydrophilic solvent such as water, alcohol or carboxylic acid as the solvent for removing the insulating portion separated from the organic semiconductor portion. .
本発明の薄膜である有機層は、ナノ構造を有し、絶縁性部位が除去された第1の化合物の層に、第2の化合物が接触するように添加され、絶縁性部位が除去されたことによって生じた第1の化合物の層中の空隙に第2の化合物を充填することにより形成される。
有機層を形成するにあたり第2の化合物を含む溶液を用いる場合、第1の化合物の層のナノ構造を維持する観点から、溶媒としては水、アルコール、カルボン酸などの親水性溶媒を用いることが好ましい。有機層を形成するにあたり有機半導体部位に熱処理、レーザー照射処理を行い、有機半導体部位を不溶化させたのちに第2の化合物の溶液を塗布してもよい。
The organic layer which is a thin film of the present invention has a nanostructure and is added so that the second compound is brought into contact with the first compound layer from which the insulating site has been removed, and the insulating site is removed. It is formed by filling the voids in the layer of the first compound generated by this with the second compound.
When a solution containing the second compound is used in forming the organic layer, a hydrophilic solvent such as water, alcohol or carboxylic acid is used as the solvent from the viewpoint of maintaining the nanostructure of the first compound layer. preferable. In forming the organic layer, the organic semiconductor site may be subjected to heat treatment and laser irradiation treatment to insolubilize the organic semiconductor site, and then the second compound solution may be applied.
(有機デバイスの使用態様)
本発明の有機デバイスは、透明または半透明である電極側から太陽光などの光を入射させることにより、電極間に光起電力を発生させ、光電変換素子として動作させることができる。光電変換素子を複数個集積することにより光電変換モジュールとして用いることもできる。
(Usage mode of organic device)
The organic device of the present invention can be operated as a photoelectric conversion element by generating photovoltaic power between the electrodes by making light such as sunlight enter from the transparent or translucent electrode side. It can also be used as a photoelectric conversion module by integrating a plurality of photoelectric conversion elements.
光電変換素子は、従来の光電変換モジュール(太陽電池モジュール)と基本的には同様のモジュール構造として用い得る。光電変換モジュールは、一般的には金属、セラミック等の支持基板の上に光電変換素子が形成され、その上を充填樹脂、保護ガラスで覆い、支持基板の反対側から光を取り込む構造をとるが、支持基板に強化ガラス等の透明材料を用い、その上に光電変換素子を形成してその透明の支持基板側から光を取り込む構造とすることも可能である。具体的には、スーパーストレートタイプ、サブストレートタイプ、ポッティングタイプと呼ばれるモジュール構造、アモルファスシリコン太陽電池などで用いられる基板一体型モジュール構造等が知られている。本発明の光電変換素子を適用した光電変換モジュールでも使用目的、使用場所および環境により適宜これらのモジュール構造を選択することができる。 The photoelectric conversion element can be used as a module structure basically similar to a conventional photoelectric conversion module (solar cell module). In general, a photoelectric conversion module has a structure in which a photoelectric conversion element is formed on a support substrate such as metal or ceramic, and the photoelectric conversion element is covered with a filling resin or a protective glass to capture light from the opposite side of the support substrate. A transparent material such as tempered glass may be used for the support substrate, and a photoelectric conversion element may be formed thereon to take light from the transparent support substrate side. Specifically, a module structure called a super straight type, a substrate type, and a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known. Even in the photoelectric conversion module to which the photoelectric conversion element of the present invention is applied, these module structures can be appropriately selected depending on the purpose of use, the place of use, and the environment.
本発明の光電変換素子は、電極同士間に電圧を印加した状態で、透明または半透明である電極側から光を入射させて光電流を生じさせることにより、センサー(有機光センサー)として動作させることができる。さらに、この有機光センサーを受光部とし、有機光センサーが生じさせる信号電流により出力を検知し、その信号電荷を読み出す駆動回路部と、有機光センサーと駆動回路とを電気的に接続する配線とを備える、有機イメージセンサーとして用いることができる。 The photoelectric conversion element of the present invention operates as a sensor (organic optical sensor) by causing light to enter from a transparent or translucent electrode side in a state where a voltage is applied between the electrodes, thereby generating a photocurrent. be able to. Furthermore, the organic photosensor is used as a light receiving unit, an output is detected by a signal current generated by the organic photosensor, and a drive circuit unit that reads the signal charge, and a wiring that electrically connects the organic photosensor and the drive circuit, Can be used as an organic image sensor.
また、本発明の薄膜である有機層は、発光素子の機能層(発光層、電荷輸送層、電荷注入層など)として用いることもできる。 The organic layer which is a thin film of the present invention can also be used as a functional layer (e.g., a light emitting layer, a charge transport layer, a charge injection layer) of the light emitting element.
以下、本発明を更に詳細に説明するため実施例を示す。本発明は下記実施例に限定されるものではない。 Examples are given below to illustrate the present invention in more detail. The present invention is not limited to the following examples.
(合成例1)α−[1−(2−Chloroethoxy)ethyl]−ω−methoxypoly(oxy−1,2−ethanediyl)(PEO−acetal−Cl)の合成
下記のスキームに従ってPEO−acetal−Clを合成した。
Synthesis Example 1 Synthesis of α- [1- (2-Chloroethoxy) ethyl] -ω-methoxypoly (oxy-1,2-ethanediyl) (PEO-acetal-Cl) According to the following scheme, PEO-acetal-Cl was synthesized. did.
Poly(ethylene oxide) methyl ether(PEO−OH、Aldrich、6g)をジクロロメタン/テトラヒドロフラン(v/v=1/1、20mL)に溶解させ、ヘキサン(180mL)中に滴下して沈澱させることによって精製した。ナスフラスコ(容量100mL)に精製したPEO−OH(Mn(NMR)=6.04×103、5.00g、0.828mmol)とPyridinium p−toluenesulfonate(PPTS、25mg、0.10mmol)とを入れて内部の雰囲気を窒素ガスで置換した後、脱水トルエン(20mL)との共沸蒸留(常圧、170℃)を3回行った。脱水ジクロロメタン(25mL)を加え、得られた溶液を氷冷後、シリンジを用いて2−Chloroethyl vinyl ether(CEVE、0.55mL、0.58g、5.4mmol)を滴下し、窒素ガス雰囲気下、0℃で1時間撹拌した。5wt%炭酸ナトリウム水溶液(6mL)で反応を停止させた後、有機層を純水(10mL)で洗浄し、引き続いて飽和食塩水(20mL)で洗浄した。それぞれの洗浄により得られた水層から目的物をジクロロメタン(8mL)で更に抽出し、無水硫酸マグネシウムで乾燥させてろ過した。残留溶媒をエバポレーターでさらに留去し、析出した固体をジクロロメタン/テトラヒドロフラン(v/v=1/1、16mL)に溶解させた後、ヘキサン(150mL)に滴下することによって白色固体を沈澱させた。得られた白色固体を吸引ろ過により回収し、デシケーター中で減圧乾燥させることによってPEO−acetal−Cl(白色粉末;Mn(NMR)=6.08×103、収量4.70g、反応率96%、収率90%)を得た。1H NMRの測定結果を以下に示す。 Poly (ethyl oxide) methyl ether (PEO-OH, Aldrich, 6 g) was dissolved in dichloromethane / tetrahydrofuran (v / v = 1/1, 20 mL) and purified by precipitation dropwise in hexane (180 mL). . Purified PEO-OH (M n (NMR) = 6.04 × 10 3 , 5.00 g, 0.828 mmol) and pyridinium p-toluenesulfate (PPTS, 25 mg, 0.10 mmol) in an eggplant flask (volume 100 mL). After the inside atmosphere was replaced with nitrogen gas, azeotropic distillation (normal pressure, 170 ° C.) with dehydrated toluene (20 mL) was performed three times. Dehydrated dichloromethane (25 mL) was added, and the resulting solution was ice-cooled, and 2-chlorovinyl ether (CEVE, 0.55 mL, 0.58 g, 5.4 mmol) was added dropwise using a syringe, under a nitrogen gas atmosphere. Stir at 0 ° C. for 1 hour. After stopping the reaction with 5 wt% aqueous sodium carbonate solution (6 mL), the organic layer was washed with pure water (10 mL) and subsequently washed with saturated brine (20 mL). The target product was further extracted with dichloromethane (8 mL) from the aqueous layer obtained by each washing, dried over anhydrous magnesium sulfate, and filtered. The residual solvent was further distilled off with an evaporator, and the precipitated solid was dissolved in dichloromethane / tetrahydrofuran (v / v = 1/1, 16 mL) and then added dropwise to hexane (150 mL) to precipitate a white solid. The obtained white solid was collected by suction filtration and dried under reduced pressure in a desiccator to obtain PEO-acetal-Cl (white powder; M n (NMR) = 6.08 × 10 3 , yield 4.70 g, reaction rate 96). %, Yield 90%). The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 4.84 (q, 1H, >CHCH3), 3.85 (m, 1H, −CH2Cl), 3.74 (m, 1H, −CH2Cl), 3.80-3.48 (br, 542H, −(OCH2CH2)m−, −CH2CH2Cl), 3.38 (s, 3H, CH3O−), 1.35 (d, 3H, >CHCH3). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 4.84 (q, 1H,> CHCH 3 ), 3.85 (m, 1H, —CH 2 Cl), 3.74 (m, 1H, -CH 2 Cl), 3.80-3.48 (br , 542H, - (OCH 2 CH 2) m -, -CH 2 CH 2 Cl), 3.38 (s, 3H, CH 3 O-), 1.35 (d, 3H,> CHCH 3 ).
(合成例2)α−[1−(2−Azidoethoxy)ethyl]−ω−methoxypoly(oxy−1,2−ethanediyl)(PEO−acetal−N3)の合成
下記のスキームに従ってPEO−acetal−N3を合成した。
(Synthesis Example 2) Synthesis of α- [1- (2-Azidoethoxy) ethyl] -ω-methoxypoly (oxy-1,2-ethanediyl) (PEO-acetal-N 3 ) PEO-acetal-N 3 according to the following scheme Was synthesized.
ナスフラスコ(容量30mL)にPEO−acetal−Cl(Mn(NMR)=6.08×103、3.00g、0.493mmol)とアジ化ナトリウム(NaN3、393mg、6.05mmol)とを入れて内部の雰囲気を窒素ガスで置換後、脱水N,N−ジメチルホルムアミド(12mL)を加えて80℃で24時間撹拌した。溶媒を減圧留去した後、残渣を純水(15mL)に溶解させた。目的物をジクロロメタン(10mL)で2回抽出し、得られた有機層を飽和食塩水(15mL)で洗浄した後、得られた水層から目的物をジクロロメタン(10mL)でさらにもう1回抽出した後、無水硫酸マグネシウムで乾燥させ、ろ過をした。得られた溶液を総量が6mLになるまで濃縮し、ヘキサン/ジエチルエーテル(v/v=1/1、120mL)に滴下した。得られた白色沈澱を吸引ろ過により回収し、ジエチルエーテルで洗浄した後、ジクロロメタン(7mL)に溶かしてヘキサン(120mL)中に再沈澱させた。吸引ろ過によって回収した沈澱をヘキサンで洗浄後、デシケーター中で減圧乾燥させることによって、PEO−acetal−N3(白色粉末;Mn(NMR)=6.17×103、収量2.31g、反応率〜100%、収率76%)を得た。1H NMRの測定結果を以下に示す。 PEO-acetal-Cl (M n (NMR) = 6.08 × 10 3 , 3.00 g, 0.493 mmol) and sodium azide (NaN 3 , 393 mg, 6.05 mmol) were added to an eggplant flask (volume 30 mL). The atmosphere inside was replaced with nitrogen gas, dehydrated N, N-dimethylformamide (12 mL) was added, and the mixture was stirred at 80 ° C. for 24 hours. After the solvent was distilled off under reduced pressure, the residue was dissolved in pure water (15 mL). The target product was extracted twice with dichloromethane (10 mL), and the obtained organic layer was washed with saturated brine (15 mL). Then, the target product was extracted once more with dichloromethane (10 mL) from the obtained aqueous layer. Then, it dried with anhydrous magnesium sulfate and filtered. The resulting solution was concentrated to a total volume of 6 mL and added dropwise to hexane / diethyl ether (v / v = 1/1, 120 mL). The resulting white precipitate was collected by suction filtration, washed with diethyl ether, dissolved in dichloromethane (7 mL), and reprecipitated in hexane (120 mL). The precipitate collected by suction filtration was washed with hexane, and then dried under reduced pressure in a desiccator, whereby PEO-acetal-N 3 (white powder; M n (NMR) = 6.17 × 10 3 , yield 2.31 g, reaction) To 100%, yield 76%). The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 4.83 (q, 1H, >CHCH3), 3.85-3.45 (br, 548H, −(OCH2CH2)m−, −CH2CH2N3), 3.44-3.35 (m, 2H, −CH2N3), 3.38 (s, 3H, CH3O−), 1.35 (d, 3H, >CHCH3). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 4.83 (q, 1H,> CHCH 3 ), 3.85-3.45 (br, 548H, — (OCH 2 CH 2 ) m −, -CH 2 CH 2 N 3), 3.44-3.35 (m, 2H, -CH 2 N 3), 3.38 (s, 3H, CH 3 O-), 1.35 (d, 3H, > CHCH 3 ).
(合成例3)α−Ethynyl−ω−bromopoly(3−hexyl−2,5−thiophenediyl)(P3HT−C≡CH)の合成
下記のスキームに従ってP3HT−C≡CHを合成した。
(Synthesis Example 3) Synthesis of α-Ethynyl-ω-bromopoly (3-hexyl-2,5-thiophenedyl) (P3HT-C≡CH) P3HT-C≡CH was synthesized according to the following scheme.
ナスフラスコ(容量50mL)に三方コックを取り付けてflame−dryした後、2−Bromo−3−hexyl−5−iodothiophene(I−3HT−Br、東京化成、1.00g、2.68mmol)を入れ、内部の雰囲気を窒素ガスで置換した。窒素気流中で脱水テトラヒドロフラン(THF、13mL)を加えて氷冷した後、2.0M Isopropylmagnesium chloride THF溶液(i−PrMgCl、Aldrich、1.34mL、2.68mmol)を窒素気流下でゆっくりと滴下し、0℃で1時間撹拌した。次に[1,3−Bis(diphenyl−phosphino)propane]nickel(II) dichloride(Ni(dppp)Cl2、東京化成、14.7mg、0.0271mmol、1.0mol%)の脱水THF(13mL)分散液を窒素気流下、0℃の反応溶液に素早く加え、室温に戻して2時間撹拌した。その後0.5M Bromoethynylmagnesium THF溶液(HC≡CMgBr、Aldrich、1.0mL、0.5mmol)を窒素気流下で滴下して室温で20分間撹拌し、最後にメタノール(26mL)を加えて10分間撹拌した。析出した紫色固体を吸引ろ過により回収し、得られた紫色固体をメタノール、アセトン、ヘキサンをこの順に用いてよく洗浄した後、紫色固体をクロロホルムに溶解させ、不溶物を吸引ろ過によって除去した。得られたろ液をエバポレーターで5mLになるまで濃縮し、ヘキサン(100mL)中に再沈澱させた。得られた沈澱を吸引ろ過により回収し、デシケーター中で減圧乾燥させることによって、光沢のある緑色固体としてP3HT−C≡CH(Mn(NMR)=1.91×104、Mn(GPC)=1.85×104、Mw(GPC)=2.24×104、Mw/Mn(GPC)=1.21、収量212mg、収率48%)を得た。1H NMRの測定結果を以下に示す。 After attaching a three-way cock to an eggplant flask (capacity 50 mL) and frame-drying, 2-Bromo-3-hexyl-5-iodothiophene (I-3HT-Br, Tokyo Kasei, 1.00 g, 2.68 mmol) was added, The internal atmosphere was replaced with nitrogen gas. After adding dehydrated tetrahydrofuran (THF, 13 mL) in a nitrogen stream and cooling with ice, 2.0M Isopropylmagnesium chloride THF solution (i-PrMgCl, Aldrich, 1.34 mL, 2.68 mmol) was slowly added dropwise under a nitrogen stream. And stirred at 0 ° C. for 1 hour. Next, dehydrated THF (13 mL) of [1,3-Bis (diphenyl-phosphino) propane] nickel (II) dichloride (Ni (dppp) Cl 2 , Tokyo Kasei, 14.7 mg, 0.0271 mmol, 1.0 mol%) The dispersion was quickly added to the reaction solution at 0 ° C. under a nitrogen stream, returned to room temperature, and stirred for 2 hours. Then, 0.5M Bromoethylnymagnesium THF solution (HC≡CMgBr, Aldrich, 1.0 mL, 0.5 mmol) was added dropwise under a nitrogen stream and stirred at room temperature for 20 minutes, and finally methanol (26 mL) was added and stirred for 10 minutes. . The deposited purple solid was collected by suction filtration, and the resulting purple solid was thoroughly washed with methanol, acetone and hexane in this order, and then the purple solid was dissolved in chloroform, and insoluble matter was removed by suction filtration. The obtained filtrate was concentrated to 5 mL with an evaporator and reprecipitated in hexane (100 mL). The resulting precipitate was collected by suction filtration and dried under reduced pressure in a desiccator to give P3HT-C≡CH (M n (NMR) = 1.91 × 10 4 , M n (GPC) as a glossy green solid. = 1.85 × 10 4 , M w (GPC) = 2.24 × 10 4 , M w / M n (GPC) = 1.21, yield 212 mg, yield 48%). The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 6.98 (s, 1H, Th−H), 6.89 (s, Th(−C≡CH)−H), 6.82 (d, Th(−Br)−H), 3.52 (s, −C≡CH), 2.81 (t, J = 7.73 Hz, 2H, Th−CH2−), 2.70 (t, Th(−C≡CH)−CH2−), 2.57 (t, Th(−Br)−CH2−), 1.71 (quint, J = 7.56 Hz, 2H, Th−CH2−CH2−), 1.44 (quint, J = 6.93 Hz, 2H, Th−(CH2)2−CH2−), 1.35 (m, 4H, −(CH2)2−CH3), 0.92 (t, J = 6.99 Hz, 3H, −CH3). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 6.98 (s, 1H, Th—H), 6.89 (s, Th (—C≡CH) —H), 6.82 (d , Th (-Br) -H), 3.52 (s, -C≡CH), 2.81 (t, J = 7.73 Hz, 2H, Th-CH 2 -), 2.70 (t, Th (-C≡CH) -CH 2 -) , 2.57 (t, Th (-Br) -CH 2 -), 1.71 (quint, J = 7.56 Hz, 2H, Th-CH 2 - CH 2 -), 1.44 (quint , J = 6.93 Hz, 2H, Th- (CH 2) 2 -CH 2 -), 1.35 (m, 4H, - (CH 2) 2 -CH 3 ), 0.92 (t, J = 6.99 Hz, 3H, -CH 3).
(実施例1)Poly(3−hexyl−2,5−thiophenediyl)−acetal−poly(ethylene oxide)(P3HT−acetal−PEO)の合成
下記のスキームに従ってP3HT−acetal−PEOを合成した。
Example 1 Synthesis of Poly (3-hexyl-2,5-thiophenedyl) -acetal-poly (ethyl oxide) (P3HT-acetal-PEO) P3HT-acetal-PEO was synthesized according to the following scheme.
ナスフラスコ(容量20mL)にP3HT−C≡CH(Mn(NMR)=1.91×104、180mg、0.00942mmol)、PEO−acetal−N3(Mn(NMR)=6.17×103、120mg、0.0194mmol)、臭化銅(I)(CuBr、31mg、0.22mmol)、N,N,N’,N’’,N’’−Pentamethyldiethylenetriamine(PMDETA、0.10mL、0.48mmol)および脱水THF(6mL)を入れ、液体窒素を用いる凍結処理、脱気処理および解凍処理を1サイクルとしてこのサイクルを3回繰り返した後、窒素ガス雰囲気下で20時間還流撹拌した。溶媒をエバポレーターで留去し、析出した水およびメタノールに不溶な目的成分を含む粗生成物に純水(30mL)を加えて洗浄した。残存した固体を吸引ろ過により回収し、純水、メタノールを用いてこの順に洗浄した後、減圧乾燥することによって、緑褐色の固体であるP3HT−acetal−PEO(Mn(GPC)=2.43×104、Mw(GPC)=3.05×104、Mw/Mn(GPC)=1.26、収量199mg)を得た。1H NMRの測定結果を以下に示す。 P3HT-C≡CH (M n (NMR) = 1.91 × 10 4 , 180 mg, 0.00942 mmol), PEO-acetal-N 3 (M n (NMR) = 6.17 ×) in an eggplant flask (volume 20 mL). 10 3 , 120 mg, 0.0194 mmol), copper (I) bromide (CuBr, 31 mg, 0.22 mmol), N, N, N ′, N ″, N ″ -Pentamethyldiethylenediamine (PMDETA, 0.10 mL, 0 .48 mmol) and dehydrated THF (6 mL) were added, and this cycle was repeated three times with one cycle of freezing treatment using liquid nitrogen, degassing treatment, and thawing treatment, followed by stirring under reflux for 20 hours under a nitrogen gas atmosphere. The solvent was distilled off with an evaporator, and pure water (30 mL) was added to the precipitated crude product containing the target component insoluble in water and methanol and washed. The remaining solid was collected by suction filtration, washed in this order with pure water and methanol, and then dried under reduced pressure, whereby P3HT-acetal-PEO (M n (GPC) = 2.43), which is a greenish brown solid. × 10 4 , M w (GPC) = 3.05 × 10 4 , M w / M n (GPC) = 1.26, yield 199 mg). The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 7.80 (s, triazole), 6.98 (s, Th−H), 6.82 (d, Th(−Br)−H), 4.78 (q, >CHCH3), 3.80-3.48 (br, −(OCH2CH2)m−), 3.38 (s, −OCH3), 2.80 (t, Th−CH2−), 2.57 (t, Th(−Br)−CH2−), 1.71 (quint, Th−CH2−CH2−), 1.44 (quint, Th−(CH2)2−CH2−), 1.35 (m, −(CH2)2−CH3), 0.91 (t, −CH2CH3). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.80 (s, triazole), 6.98 (s, Th-H), 6.82 (d, Th (-Br) -H), 4.78 (q,> CHCH 3 ), 3.80-3.48 (br,-(OCH 2 CH 2 ) m- ), 3.38 (s, -OCH 3 ), 2.80 (t, Th -CH 2 -), 2.57 (t , Th (-Br) -CH 2 -), 1.71 (quint, Th-CH 2 -CH 2 -), 1.44 (quint, Th- (CH 2 ) 2 -CH 2 -), 1.35 (m, - (CH 2) 2 -CH 3), 0.91 (t, -CH 2 CH 3).
(実施例2)
(1)P3HT−acetal−PEOの薄膜の形成
ガラス基板(Matsunami Glass Ind., Ltd.;22×26mm、厚さ0.12mm〜0.17mm)に対して、中性洗剤を用いる超音波洗浄を20分間、流水洗浄を20分間、純水を用いる超音波洗浄を20分間、流水洗浄を20分間、2−プロパノールを用いる超音波洗浄を20分間、この順で実施した。次いで、乾燥(65℃、60分間)後にUV−O3処理(30分間)を行った。次に、ガラス基板上にP3HT−acetal−PEOの1wt%トルエン溶液をスピンコート法(2000rpm、30秒間)により塗布して塗布膜を形成した。デシケーター中で減圧乾燥後、真空中でアニール処理(230℃で6時間、昇温速度0.5℃/分)を行ってガラス基板上にP3HT−acetal−PEOの薄膜を形成した。
(Example 2)
(1) Formation of P3HT-acetal-PEO thin film Ultrasonic cleaning using a neutral detergent is performed on a glass substrate (Matsunami Glass Ind., Ltd .; 22 × 26 mm, thickness 0.12 mm to 0.17 mm). Washing with running water for 20 minutes, washing with ultrasonic water using pure water for 20 minutes, washing with running water for 20 minutes, and washing with ultrasonic water using 2-propanol for 20 minutes were performed in this order. Next, UV-O 3 treatment (30 minutes) was performed after drying (65 ° C., 60 minutes). Next, a 1 wt% toluene solution of P3HT-acetal-PEO was applied onto a glass substrate by a spin coating method (2000 rpm, 30 seconds) to form a coating film. After drying under reduced pressure in a desiccator, annealing was performed in vacuum (230 ° C. for 6 hours, heating rate 0.5 ° C./min) to form a P3HT-acetal-PEO thin film on the glass substrate.
得られた薄膜についてAFM(Atomic Force Microscope)測定を実施した。AFM測定はAgilent Technologies 5500 AFM(探針:Olympus OMCL−AC160TS−C3(共振周波数:300kHz))を用い、大気中ACモード(ダイナミックモード)で測定した。走査範囲は500nm×500nm(256×256points)、走査速度1.0line/secであった。 The obtained thin film was subjected to AFM (Atomic Force Microscope) measurement. The AFM measurement was performed in an atmospheric AC mode (dynamic mode) using an Agilent Technologies 5500 AFM (probe: Olympus OMCL-AC160TS-C3 (resonance frequency: 300 kHz)). The scanning range was 500 nm × 500 nm (256 × 256 points), and the scanning speed was 1.0 line / sec.
結果を図1に示す。図1は、AFM像を示す写真図である。図1から明らかな通り、写真図において白っぽく示されている明部(有機半導体部位であるP3HT部位)と黒っぽく示されている暗部(絶縁性部位であるポリエチレンオキサイド部位:PEO部位)との相分離により、規則性の高いナノ構造が確認できた。 The results are shown in FIG. FIG. 1 is a photograph showing an AFM image. As is clear from FIG. 1, the phase separation between the bright part (P3HT part which is an organic semiconductor part) shown whitish in the photograph and the dark part (polyethylene oxide part: PEO part which is an insulating part) shown blackish As a result, a highly ordered nanostructure was confirmed.
(2)P3HT−acetal−PEOの薄膜からのPEO部位の除去
第1のサンプル管(容量50mL)中に水を満たした第2のサンプル管(容量10mL)を格納し、第1のサンプル管内であって第2のサンプル管外にトリフルオロ酢酸(最大15mL)を入れた。そこにP3HT−acetal−PEOの薄膜が形成された基板を浸漬し、3時間静置してアセタール結合を切断した。その後、P3HT−acetal−PEOの薄膜が形成された基板を第3のサンプル管(容量50mL)に入れたメタノール(最大20mL)中に3時間浸漬し、メタノールで表面を洗い流した後、減圧乾燥させた。
(2) Removal of PEO site from thin film of P3HT-acetal-PEO A second sample tube (capacity 10 mL) filled with water was stored in the first sample tube (capacity 50 mL). Therefore, trifluoroacetic acid (maximum 15 mL) was put outside the second sample tube. The board | substrate with which the thin film of P3HT-acetal-PEO was formed there was immersed there, and it left still for 3 hours, and cut | disconnected the acetal bond. After that, the substrate on which the P3HT-acetal-PEO thin film was formed was immersed in methanol (maximum 20 mL) in a third sample tube (capacity 50 mL) for 3 hours, rinsed with methanol, and then dried under reduced pressure. It was.
(実施例3)有機光電変換素子の作製例1
スパッタ法により150nmの厚さでITO膜を形成したガラス基板に対し、オゾンUV処理による表面処理を行い、次に、PEDOT:PSS(Heraeus社製AI4083)をスピンコート法により塗布し、200℃で10分間熱処理を行う。その上にP3HT−acetal−PEOの薄膜を実施例2の方法により作成し、得られた薄膜にC60フラーレンを5×10−4Pa以下の真空度で真空蒸着することにより、光学活性層を形成することができる。次いで金属電極を蒸着し、有機薄膜太陽電池を得ることができる。得られた有機薄膜太陽電池にソーラシミュレーターを用いて一定の光量の光を照射すると、優れた光電変換特性を示す。
(Example 3) Preparation Example 1 of an organic photoelectric conversion element
A glass substrate on which an ITO film having a thickness of 150 nm is formed by sputtering is subjected to surface treatment by ozone UV treatment. Next, PEDOT: PSS (AI 4083 manufactured by Heraeus) is applied by spin coating, and is applied at 200 ° C. Heat treatment is performed for 10 minutes. A P3HT-acetal-PEO thin film was formed thereon by the method of Example 2, and C 60 fullerene was vacuum deposited on the obtained thin film at a vacuum of 5 × 10 −4 Pa or less to form an optically active layer. Can be formed. Subsequently, a metal electrode is vapor-deposited and an organic thin film solar cell can be obtained. When the obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator, excellent photoelectric conversion characteristics are exhibited.
(実施例4)有機光電変換素子の作製例2
スパッタ法により150nmの厚さでITO膜を形成したガラス基板に対し、オゾンUV処理による表面処理を行い、次に、PEDOT:PSS(Heraeus社製AI4083)をスピンコート法により塗布し、200℃で10分間熱処理を行う。その上にP3HT−acetal−PEOの薄膜を実施例2の方法により作成し、得られた薄膜に低エネルギー電子線を照射し、架橋させ、その後、第2の化合物を含む溶液に浸漬することにより光学活性層を形成することができる。続いて5×10−4Pa以下で金属電極を真空蒸着し、有機薄膜太陽電池を得ることができる。得られた有機薄膜太陽電池にソーラシミュレーターを用いて一定の光量の光を照射すると、優れた光電変換特性を示す。
(Example 4) Preparation example 2 of an organic photoelectric conversion element
A glass substrate on which an ITO film having a thickness of 150 nm is formed by sputtering is subjected to surface treatment by ozone UV treatment. Next, PEDOT: PSS (AI 4083 manufactured by Heraeus) is applied by spin coating, and is applied at 200 ° C. Heat treatment is performed for 10 minutes. A thin film of P3HT-acetal-PEO is formed thereon by the method of Example 2, and the resulting thin film is irradiated with a low energy electron beam to crosslink, and then immersed in a solution containing the second compound. An optically active layer can be formed. Then, a metal electrode is vacuum-deposited at 5 * 10 <-4> Pa or less, and an organic thin film solar cell can be obtained. When the obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator, excellent photoelectric conversion characteristics are exhibited.
(合成例4)2−Bromo−5−butyl−thiophene(化合物2)の合成
下記のスキームに従って化合物1から化合物2を合成した。
Synthesis Example 4 Synthesis of 2-Bromo-5-butyl-thiophene (Compound 2) Compound 2 was synthesized from Compound 1 according to the following scheme.
2−Butyl−thiophene(化合物1)(7.09g、50.5mmol)とテトラヒドロフラン(50mL)との混合溶液にN−Bromosuccinimide(NBS)(9.00g、50.6mmol、1eq.)を2回に分けて加えて室温で3時間撹拌した。次いで純水で反応を停止させ、得られた溶液をジエチルエーテルで抽出した。有機層を洗浄し、乾燥させて溶媒を留去して、赤色液体の化合物2(10.7g、49.0mmol、収率97%)を得た。1H NMRの測定結果を以下に示す。 2-Butyl-thiophene (Compound 1) (7.09 g, 50.5 mmol) and tetrahydrofuran (50 mL) were mixed with N-bromosuccinimide (NBS) (9.00 g, 50.6 mmol, 1 eq.) In two portions. Separately added and stirred at room temperature for 3 hours. The reaction was then stopped with pure water, and the resulting solution was extracted with diethyl ether. The organic layer was washed and dried, and the solvent was distilled off to obtain a red liquid compound 2 (10.7 g, 49.0 mmol, yield 97%). The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 6.84 (d, 1H), 6.53 (d, 1H), 2.74 (t, 2H), 1.64-1.57 (sext, 2H), 1.41-1.34 (sext, 2H), 0.92 (t, 3H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 6.84 (d, 1H), 6.53 (d, 1H), 2.74 (t, 2H), 1.64-1.57 ( sext, 2H), 1.41-1.34 (sext, 2H), 0.92 (t, 3H).
(合成例5)2−Butyl−5−[2−(trimethylsilyl)ethynyl]−thiophene(化合物3)の合成
下記のスキームに従って化合物2から化合物3を合成した。
Synthesis Example 5 Synthesis of 2-Butyl-5- [2- (trimethylsilyl) ethyl] -thiophene (Compound 3) Compound 3 was synthesized from Compound 2 according to the following scheme.
PdCl2(PPh3)2(0.936g、1.33mmol、3mol%)とヨウ化銅(0.300g、1.58mmol、3.5mol%)との混合物に、2−Bromo−5−butyl−thiophene(化合物2)(9.78g、44.6mmol)とトリメチルシリルアセチレン(TMSA)(6.86g、69.8mmol、1.6eq.)とトリエチルアミン(50mL)との混合溶液を加え、アルゴンガス雰囲気下、室温で17時間撹拌した。次いで塩酸を用いて反応を停止させ、黒色固体をろ別した。得られた溶液をジエチルエーテルで抽出し、有機層を洗浄し、乾燥させて溶媒を留去して、黒色液体を得た。得られた黒色液体をシリカゲルカラムクロマトグラフィー(展開溶媒:ヘキサン)により精製し、赤褐色液体の化合物3(8.03g、31.8mmol、71%)を得た。1H NMRの測定結果を以下に示す。 To a mixture of PdCl 2 (PPh 3 ) 2 (0.936 g, 1.33 mmol, 3 mol%) and copper iodide (0.300 g, 1.58 mmol, 3.5 mol%), 2-Bromo-5-butyl- A mixed solution of thiophene (compound 2) (9.78 g, 44.6 mmol), trimethylsilylacetylene (TMSA) (6.86 g, 69.8 mmol, 1.6 eq.) and triethylamine (50 mL) was added, and an argon gas atmosphere was added. And stirred at room temperature for 17 hours. The reaction was then stopped using hydrochloric acid and the black solid was filtered off. The resulting solution was extracted with diethyl ether, the organic layer was washed, dried and evaporated to give a black liquid. The resulting black liquid was purified by silica gel column chromatography (developing solvent: hexane) to obtain a reddish brown liquid compound 3 (8.03 g, 31.8 mmol, 71%). The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 7.04 (d, 1H), 6.60 (d, 1H), 2.76 (t, 2H), 1.66-1.60 (quint, 2H), 1.41-1.33 (sext, 2H), 0.91 (t, 3H), 0.23 (s, 9H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.04 (d, 1H), 6.60 (d, 1H), 2.76 (t, 2H), 1.66-1.60 ( quint, 2H), 1.41-1.33 (sext, 2H), 0.91 (t, 3H), 0.23 (s, 9H).
(合成例6)2−Butyl−5−ethynyl−thiophene(化合物4)の合成
下記のスキームに従って化合物3から化合物4を合成した。
Synthesis Example 6 Synthesis of 2-Butyl-5-ethylyl-thiophene (Compound 4) Compound 4 was synthesized from compound 3 according to the following scheme.
ビーカーに入れた炭酸カリウム(6.60g、47.8mmol、1.5eq.)とメタノール(200mL)との混合溶液に2−Butyl−5−[2−(trimethylsilyl)ethynyl]−thiophene(化合物3)(8.03g、31.8mmol)を滴下して室温で20時間撹拌した。次いで溶液をクロロホルムで抽出した。有機層を洗浄し、乾燥させて溶媒を留去して、赤褐色液体の化合物4(4.79g、29.2mmol、収率92%)を得た。1H NMRの測定結果を以下に示す。 2-Butyl-5- [2- (trimethylsilyl) ethyl] -thiophene (compound 3) was added to a mixed solution of potassium carbonate (6.60 g, 47.8 mmol, 1.5 eq.) And methanol (200 mL) in a beaker. (8.03 g, 31.8 mmol) was added dropwise and stirred at room temperature for 20 hours. The solution was then extracted with chloroform. The organic layer was washed and dried, and the solvent was distilled off to obtain reddish brown liquid compound 4 (4.79 g, 29.2 mmol, yield 92%). The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 7.09 (d, 1H), 6.63 (d, 1H), 3.28 (s, 1H), 2.77 (t, 2H), 1.67-1.61 (quint, 2H), 1.42-1.34 (sext, 2H), 0.93 (t, 3H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.09 (d, 1H), 6.63 (d, 1H), 3.28 (s, 1H), 2.77 (t, 2H) , 1.67-1.61 (quint, 2H), 1.42-1.34 (sext, 2H), 0.93 (t, 3H).
(合成例7)2−Thiophenebutanol(化合物6)の合成
下記のスキームに従って化合物5から化合物6を合成した。
Synthesis Example 7 Synthesis of 2-Thiophenebutanol (Compound 6) Compound 6 was synthesized from compound 5 according to the following scheme.
2口ナスフラスコに水素化リチウムアルミニウム(LAH)(2.25g、59.4mmol、1eq.)とジエチルエーテル(50mL)とを入れ、2−Thiophenebutanoic Acid(化合物5)(10.0g、58.7mmol)とジエチルエーテル(10mL)との混合物を氷冷下で滴下して、アルゴンガス雰囲気下、50℃で3時間還流した。その後、純水(2.3mL)を用いて30分間かけて反応を停止させ、水酸化ナトリウム水溶液(15%、2.3mL)、純水(7.0mL)を順に加えた。析出した白色固体をろ別し、得られた有機層を乾燥させて溶媒を留去して、薄黄色液体の化合物6(9.06g、収率99%)を得た。1H NMRの測定結果を以下に示す。 A two-necked eggplant flask was charged with lithium aluminum hydride (LAH) (2.25 g, 59.4 mmol, 1 eq.) And diethyl ether (50 mL), and 2-Thiophenebutanoic Acid (Compound 5) (10.0 g, 58.7 mmol). ) And diethyl ether (10 mL) were added dropwise under ice cooling, and the mixture was refluxed at 50 ° C. for 3 hours under an argon gas atmosphere. Thereafter, the reaction was stopped using pure water (2.3 mL) for 30 minutes, and an aqueous sodium hydroxide solution (15%, 2.3 mL) and pure water (7.0 mL) were sequentially added. The precipitated white solid was filtered off, the obtained organic layer was dried and the solvent was distilled off to obtain a light yellow liquid compound 6 (9.06 g, yield 99%). The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 7.11 (dd, 1H), 6.91 (dd, 1H), 6.79 (dd, 1H), 3.68 (q, 2H), 2.87 (t, 2H), 1.78-1.74 (m, 2H), 1.67-1.61 (m, 2H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.11 (dd, 1H), 6.91 (dd, 1H), 6.79 (dd, 1H), 3.68 (q, 2H) , 2.87 (t, 2H), 1.78-1.74 (m, 2H), 1.67-1.61 (m, 2H).
(合成例8)Tetrahydro−2−[4−(2−thienyl)butoxy]−2H−pyran(化合物7)の合成
下記のスキームに従って化合物6から化合物7を合成した。
Synthesis Example 8 Synthesis of Tetrahydro-2- [4- (2-thienyl) butoxy] -2H-pyran (Compound 7) Compound 7 was synthesized from compound 6 according to the following scheme.
ナスフラスコに2−Thiophenebutanol(化合物6)(2.00g、12.8mmol)と3,4−Dihydro−2H−pyran(DHP)(1.21g、14.3mmol、1.1eq.)を入れ、塩化アルミニウム(III)6水和物(AlCl3・6H2O、33.1mg、0.137mmol、1mol%)を加えた。30℃で30分間撹拌した後、60℃で4時間半撹拌した。その後、シリカゲルショートカラム(展開溶媒:クロロホルム)に通し、減圧留去して、薄黄色液体の化合物7(2.88g、12.0mmol、94%)を得た。1H NMRの測定結果を以下に示す。 2-Thiophenebutanol (compound 6) (2.00 g, 12.8 mmol) and 3,4-Dihydro-2H-pyran (DHP) (1.21 g, 14.3 mmol, 1.1 eq.) Were placed in an eggplant flask and salified. Aluminum (III) hexahydrate (AlCl 3 .6H 2 O, 33.1 mg, 0.137 mmol, 1 mol%) was added. After stirring at 30 ° C. for 30 minutes, the mixture was stirred at 60 ° C. for 4 and a half hours. Thereafter, the solution was passed through a silica gel short column (developing solvent: chloroform) and distilled under reduced pressure to obtain Compound 7 (2.88 g, 12.0 mmol, 94%) as a pale yellow liquid. The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 7.10 (d, 1H), 6.91 (t, 1H), 6.79 (d, 1H), 4.58 (t, 1H), 3.88-3.84 (m, 1H), 3.79-3.75 (m, 1H), 3.52-3.48 (m, 1H), 3.44-3.39 (m, 1H), 2.86 (t, 2H), 1.87-1.50 (m, 10H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.10 (d, 1H), 6.91 (t, 1H), 6.79 (d, 1H), 4.58 (t, 1H) , 3.88-3.84 (m, 1H), 3.79-3.75 (m, 1H), 3.52-3.48 (m, 1H), 3.44-3.39 (m, 1H) 1H), 2.86 (t, 2H), 1.87-1.50 (m, 10H).
(合成例9)Tetrahydro−2−[4−(5−bromo−2−thienyl)butoxy]−2H−pyran(化合物8)の合成
下記のスキームに従って化合物7から化合物8を合成した。
(Synthesis Example 9) Synthesis of Tetrahydro-2- [4- (5-bromo-2-thienyl) butoxy] -2H-pyran (Compound 8) Compound 8 was synthesized from Compound 7 according to the following scheme.
2口ナスフラスコにTetrahydro−2−[4−(2−thienyl)butoxy]−2H−pyran(化合物7)(2.88g、12.0mmol)とトルエン(12mL)とを入れ、N−Bromosuccinimide(NBS)(2.14g、12.0mmol、1eq.)を2回に分けて加え、アルゴンガス雰囲気下、室温で4時間撹拌した。次いで、純水で反応を停止させ、有機層を純水と飽和食塩水とで順に洗浄した後、無水硫酸マグネシウムで乾燥させて溶媒を留去して黒色液体を得た。得られた黒色液体をシリカゲルカラムクロマトグラフィー(展開溶媒:クロロホルム)により精製し、赤褐色液体である粗生成物(4.26g)を得た。1H NMR測定を行ったところ、THP保護基が一部はずれていた(THP保護基がはずれた化合物を含む粗生成物を粗生成物8’という。)。 Tetrahydro-2- [4- (2-thienyl) butoxy] -2H-pyran (compound 7) (2.88 g, 12.0 mmol) and toluene (12 mL) were placed in a two-necked eggplant flask, and N-bromosuccinimide (NBS) was added. ) (2.14 g, 12.0 mmol, 1 eq.) Was added in two portions, and the mixture was stirred at room temperature for 4 hours under an argon gas atmosphere. Next, the reaction was stopped with pure water, and the organic layer was washed with pure water and saturated brine in that order, then dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a black liquid. The resulting black liquid was purified by silica gel column chromatography (developing solvent: chloroform) to obtain a crude product (4.26 g) as a reddish brown liquid. As a result of 1 H NMR measurement, a part of the THP protecting group was removed (a crude product containing a compound from which the THP protecting group was removed is referred to as a crude product 8 ′).
下記のスキームに従って粗生成物8’から化合物8を得た。 Compound 8 was obtained from crude product 8 'according to the following scheme.
ナスフラスコに前記粗生成物8’(4.26g、18.1mmol:全て5−Bromo−2−thiophenebutanolとして計算した量)と3,4−Dihydro−2H−pyran(DHP)(1.69g、20.1mmol、1.1eq.)、塩化アルミニウム(III)6水和物(AlCl3・6H2O、45.6mg、0.189mmol、1mol%)を入れて60℃で3時間撹拌した。その後、シリカゲルカラムクロマトグラフィー(展開溶媒:クロロホルム)により精製し、減圧留去して、赤褐色液体の化合物8(3.33g、10.4mmol、収率87%)を得た。 In an eggplant flask, the crude product 8 ′ (4.26 g, 18.1 mmol: all calculated as 5-Bromo-2-thiophenebutanol) and 3,4-Dihydro-2H-pyran (DHP) (1.69 g, 20 0.1 mmol, 1.1 eq.) And aluminum (III) chloride hexahydrate (AlCl 3 .6H 2 O, 45.6 mg, 0.189 mmol, 1 mol%) were added, and the mixture was stirred at 60 ° C. for 3 hours. Then, it refine | purified by silica gel column chromatography (developing solvent: chloroform), and depressurizingly distilled, Compound 8 (3.33g, 10.4mmol, 87% of yield) of reddish brown liquid was obtained.
1H NMR (500 MHz, CDCl3): δ/ppm = 6.84 (d, 1H), 6.54 (d, 1H), 4.57 (t, 1H), 3.88-3.83 (m, 1H), 3.78-3.74 (m, 1H), 3.52-3.48 (m, 1H), 3.42-3.38 (m, 1H), 2.79 (t, 2H), 1.85-1.51 (m, 10H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 6.84 (d, 1H), 6.54 (d, 1H), 4.57 (t, 1H), 3.88-3.83 ( m, 1H), 3.78-3.74 (m, 1H), 3.52-3.48 (m, 1H), 3.42-3.38 (m, 1H), 2.79 (t, 2H), 1.85-1.51 (m, 10H).
(合成例10)Tetrahydro−2−[4−(5−[2−(trimethylsilyl)ethynyl]−2−thienyl)butoxy]−2H−pyran(化合物9)の合成
下記のスキームに従って化合物8から化合物9を合成した。
Synthesis Example 10 Synthesis of Tetrahydro-2- [4- (5- [2- (trimethylsilyl) ethyl] -2-thionyl) butoxy] -2H-pyran (Compound 9) Synthesized.
2口ナスフラスコにPdCl2(PPh3)2(221mg、0.316mmol、3mol%)、ヨウ化銅(70.7mg、0.371mmol、3.6mol%)を入れた。Tetrahydro−2−[4−(5−bromo−2−thienyl)butoxy]−2H−pyran(化合物8)(3.33g、10.4mmol)、トリメチルシリルアセチレン(TMSA)(1.46g、14.8mmol、1.4eq.)、トリエチルアミン(10mL)の混合溶液を加え、アルゴンガス雰囲気下、室温で22時間撹拌した。次いで溶媒を減圧留去し、シリカゲルカラムクロマトグラフィー(展開溶媒:クロロホルム)にかけた。得られた有機層をクロロホルムで2回抽出し、純水および飽和食塩水でこの順に洗浄した。無水硫酸マグネシウムで乾燥させ、溶媒を留去して、シリカゲルカラムクロマトグラフィー(展開溶媒:クロロホルム)による精製をさらに2回行って、褐色液体の化合物9(3.29g、9.79mmol、収率94%)を得た。1H NMRの測定結果を以下に示す。 PdCl 2 (PPh 3 ) 2 (221 mg, 0.316 mmol, 3 mol%) and copper iodide (70.7 mg, 0.371 mmol, 3.6 mol%) were placed in a two- necked eggplant flask. Tetrahydro-2- [4- (5-bromo-2-thienyl) butoxy] -2H-pyran (compound 8) (3.33 g, 10.4 mmol), trimethylsilylacetylene (TMSA) (1.46 g, 14.8 mmol, 1.4 eq.) And triethylamine (10 mL) were added, and the mixture was stirred at room temperature for 22 hours under an argon gas atmosphere. Subsequently, the solvent was distilled off under reduced pressure and subjected to silica gel column chromatography (developing solvent: chloroform). The obtained organic layer was extracted twice with chloroform and washed with pure water and saturated saline in this order. The extract was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was further purified twice by silica gel column chromatography (developing solvent: chloroform) to obtain brown liquid compound 9 (3.29 g, 9.79 mmol, yield 94). %). The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 7.04 (d, 1H), 6.62 (d, 1H), 4.57 (t, 1H), 3.87-3.83 (m, 1H), 3.78-3.73 (m, 1H), 3.52-3.48 (m, 1H), 3.42-3.37 (m, 1H), 2.80 (t, 2H), 1.85-1.51 (m, 10H) 0.23 (s, 9H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.04 (d, 1H), 6.62 (d, 1H), 4.57 (t, 1H), 3.87-3.83 ( m, 1H), 3.78-3.73 (m, 1H), 3.52-3.48 (m, 1H), 3.42-3.37 (m, 1H), 2.80 (t, 2H), 1.85-1.51 (m, 10H) 0.23 (s, 9H).
(合成例11)Tetrahydro−2−[4−(5−ethynyl−2−thienyl)butoxy]−2H−pyran(化合物10)の合成
下記のスキームに従って化合物9から化合物10を合成した。
Synthesis Example 11 Synthesis of Tetrahydro-2- [4- (5-ethyl-2-thienyl) butoxy] -2H-pyran (Compound 10) Compound 10 was synthesized from compound 9 according to the following scheme.
2口ナスフラスコにTetrahydro−2−[4−(5−[2−(trimethylsilyl)ethynyl]−2−thienyl)butoxy]−2H−pyran(化合物9)(3.29g、9.79mmol)とテトラヒドロフラン(60mL)とを入れた。Tetrabutylammonium Fluoride(TBAF)(11.0mL、11.0mmol、1.1eq.)をアルゴンガス雰囲気下で滴下して加え、室温で1時間撹拌した。次いで減圧ろ過し、得られた有機層をクロロホルムで抽出して純水と飽和食塩水とでこの順に洗浄し、無水硫酸マグネシウムで乾燥させ、溶媒を留去して黒色液体を得た。得られた黒色液体をシリカゲルカラムクロマトグラフィー(展開溶媒:クロロホルム)により精製し、赤褐色液体の化合物10(2.21g、8.34mmol、収率85%)を得た。1H NMRの測定結果を以下に示す。 In a two-necked eggplant flask, tetrahydro-2- [4- (5- [2- (trimethylsilyl) ethyl] -2-thionyl) butoxy] -2H-pyran (compound 9) (3.29 g, 9.79 mmol) and tetrahydrofuran ( 60 mL). Tetrabutylammonium Fluoride (TBAF) (11.0 mL, 11.0 mmol, 1.1 eq.) Was added dropwise under an argon gas atmosphere, and the mixture was stirred at room temperature for 1 hour. Subsequently, the mixture was filtered under reduced pressure, and the resulting organic layer was extracted with chloroform, washed with pure water and saturated brine in this order, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a black liquid. The resulting black liquid was purified by silica gel column chromatography (developing solvent: chloroform) to obtain a reddish brown liquid compound 10 (2.21 g, 8.34 mmol, yield 85%). The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 7.09 (d, 1H), 6.65 (d, 1H), 4.57 (t, 1H), 3.88-3.83 (m, 1H), 3.79-3.74 (m, 1H), 3.52-3.48 (m, 1H), 3.43-3.38 (m, 1H), 3.29 (s, 1H), 2.82 (t, 2H), 1.85-1.51 (m, 10H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.09 (d, 1H), 6.65 (d, 1H), 4.57 (t, 1H), 3.88-3.83 ( m, 1H), 3.79-3.74 (m, 1H), 3.52-3.48 (m, 1H), 3.43-3.38 (m, 1H), 3.29 (s, 1H), 2.82 (t, 2H), 1.85-1.51 (m, 10H).
(合成例12)5−Iodo−2,2’:5’,2”−terthiophene(化合物12)の合成
下記のスキームに従って化合物11から化合物12を合成した。
Synthesis Example 12 Synthesis of 5-Iodo-2,2 ′: 5 ′, 2 ″ -tertiophene (Compound 12) Compound 12 was synthesized from Compound 11 according to the following scheme.
2口ナスフラスコに2,2’:5’,2”−Terthiophene(化合物11)(1.00g、4.03mmol)とN−Iodosuccinimide(NIS)(1.08g、4.81mmol、1.2eq.)とを入れ、脱水クロロホルム(8mL)と酢酸(8mL)とを加えた。アルゴンガス雰囲気下、室温で18時間半撹拌した後、純水で反応を停止させ、クロロホルムを加えた。得られた有機層を純水と飽和食塩水とでこの順に洗浄し、無水硫酸マグネシウムで乾燥させ、溶媒を留去して黄色固体を得た。得られた黄色固体をクロロホルムおよびヘキサンを用いて再結晶することにより精製し、黄色固体の化合物12(1.44g、3.86mmol、収率96%)を得た。1H NMRの測定結果を以下に示す。 In a two-necked eggplant flask, 2,2 ′: 5 ′, 2 ″ -Terthiophene (Compound 11) (1.00 g, 4.03 mmol) and N-Iodosuccinimide (NIS) (1.08 g, 4.81 mmol, 1.2 eq. The mixture was added with dehydrated chloroform (8 mL) and acetic acid (8 mL), and stirred for 18 and a half hours at room temperature in an argon gas atmosphere, and then the reaction was stopped with pure water, and chloroform was added. The organic layer was washed with pure water and saturated brine in this order, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a yellow solid, which was recrystallized using chloroform and hexane. To obtain a yellow solid compound 12 (1.44 g, 3.86 mmol, yield 96%) The measurement results of 1 H NMR are shown below.
1H NMR (500 MHz, CDCl3): δ/ppm= 7.23 (dd, 1H), 7.17 (dd, 1H), 7.16 (d, 1H), 7.06 (d, 1H), 7.03 (d, 1H), 7.02 (d, 1H), 6.84 (d, 1H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.23 (dd, 1H), 7.17 (dd, 1H), 7.16 (d, 1H), 7.06 (d, 1H) , 7.03 (d, 1H), 7.02 (d, 1H), 6.84 (d, 1H).
(合成例13)5−Bromo−5”−iodo−2,2’:5’,2”−terthiophene(化合物13)の合成
下記のスキームに従って化合物12から化合物13を合成した。
Synthesis Example 13 Synthesis of 5-Bromo-5 ″ -iodo-2,2 ′: 5 ′, 2 ″ -tertiophene (Compound 13) Compound 13 was synthesized from compound 12 according to the following scheme.
5−Iodo−2,2’:5’,2”−terthiophene(化合物12)(2.62g、7.00mmol)とN−Bromosuccinimide(NBS)(1.25g、7.02mmol、1eq.)とを2口ナスフラスコに入れた後、脱水クロロホルム(14mL)と酢酸(14mL)とを加え、アルゴンガス雰囲気下、室温で19時間半撹拌した。次に、純水で反応を停止させてクロロホルムで抽出し、得られた有機層を純水と飽和食塩水とでこの順に洗浄した。洗浄した有機層を無水硫酸マグネシウムで乾燥させ、溶媒を留去して黄色固体を得た。その後、クロロホルムおよびヘキサンを用いて再結晶を行うことにより、黄色針状結晶の化合物13(2.41g、5.33mmol、収率76%)を得た。 5-Ido-2,2 ′: 5 ′, 2 ″ -tertiophene (compound 12) (2.62 g, 7.00 mmol) and N-bromosuccinimide (NBS) (1.25 g, 7.02 mmol, 1 eq.). After putting into a two-necked eggplant flask, dehydrated chloroform (14 mL) and acetic acid (14 mL) were added, and the mixture was stirred for 19 and a half hours at room temperature in an argon gas atmosphere, then the reaction was stopped with pure water and extracted with chloroform. The obtained organic layer was washed with pure water and saturated brine in this order, and the washed organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a yellow solid, followed by chloroform and hexane. Was used to obtain Compound 13 (2.41 g, 5.33 mmol, yield 76%) of yellow needle crystals.
1H NMR (500 MHz, CDCl3): δ/ppm = 7.16 (d, 1H), 7.01-6.99 (m, 2H), 6.97 (d, 1H), 6.91 (d, 1H), 6.83 (d, 1H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.16 (d, 1H), 7.01-6.99 (m, 2H), 6.97 (d, 1H), 6.91 ( d, 1H), 6.83 (d, 1H).
(合成例14)Tetrahydro−2−(4−{5−[2−(5”−bromo−2,2’:5’,2”−terthiophene)−5−ethynyl]−2−thienyl}butoxy)−2H−pyran(化合物14)の合成
下記のスキームに従って化合物10と化合物13を用いて化合物14を合成した。
Synthesis Example 14 Tetrahydro-2- (4- {5- [2- (5 ″ -bromo-2,2 ′: 5 ′, 2 ″ -tertiophene) -5-ethylnyl] -2-thienyl} butoxy) − Synthesis of 2H-pyran (Compound 14) Compound 14 was synthesized using Compound 10 and Compound 13 according to the following scheme.
2口ナスフラスコに5−Bromo−5”−iodo−2,2’:5’,2”−terthiophene(化合物13)(1.36g、3.01mmol)、PdCl2(PPh3)2(65.3mg、93.0mol、3.1mol%)、ヨウ化銅(21.6mg、0.113mmol、3.8mol%)、テトラヒドロフラン(60mL)を入れ、Tetrahydro−2−[4−(5−ethynyl−2−thienyl)butoxy]−2H−pyran(化合物10)(0.795g、3.01mmol、1eq.)とトリエチルアミン(120mL)との混合溶液を、アルゴンガス雰囲気下、氷浴中で滴下し、室温まで戻しながら3日間撹拌した。その後、溶媒を減圧留去し、ジクロロメタンを加えた。得られた有機層を純水と飽和食塩水とでこの順に洗浄し、無水硫酸マグネシウムで乾燥させ、溶媒を留去して、黒色固体を得た。シリカゲルカラムクロマトグラフィー(展開溶媒:ジクロロメタン)を2回行うことにより精製して、橙色固体の化合物14(0.929g、1.58mmol、収率52%)を得た。 Two-neck eggplant-shaped flask 5-Bromo-5 "-iodo- 2,2 ': 5', 2" -terthiophene ( Compound 13) (1.36g, 3.01mmol), PdCl 2 (PPh 3) 2 (65. 3 mg, 93.0 mol, 3.1 mol%), copper iodide (21.6 mg, 0.113 mmol, 3.8 mol%), tetrahydrofuran (60 mL) were added, and Tetrahydro-2- [4- (5-ethylny-2 -Thienyl) butoxy] -2H-pyran (compound 10) (0.795 g, 3.01 mmol, 1 eq.) And triethylamine (120 mL) were added dropwise in an ice bath under an argon gas atmosphere to room temperature. The mixture was stirred for 3 days while returning. Thereafter, the solvent was distilled off under reduced pressure, and dichloromethane was added. The obtained organic layer was washed with pure water and saturated saline in this order, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a black solid. Purification was performed by silica gel column chromatography (developing solvent: dichloromethane) twice to obtain orange solid compound 14 (0.929 g, 1.58 mmol, yield 52%).
1H NMR (500 MHz, CDCl3): δ/ppm = 7.14 (d, 1H), 7.10 (d, 1H), 7.07 (d, 1H), 7.05 (d, 1H), 7.01 (d, 1H), 6.98 (d, 1H), 6.92 (d, 1H), 6.70 (d, 1H), 4.58 (t, 1H), 3.88-3.84 (m, 1H), 3.80-3.75 (m, 1H), 3.53-3.49 (m, 1H), 3.44-3.40 (m, 1H), 2.85 (t, 2H), 1.85-1.51 (m, 10H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.14 (d, 1H), 7.10 (d, 1H), 7.07 (d, 1H), 7.05 (d, 1H) , 7.01 (d, 1H), 6.98 (d, 1H), 6.92 (d, 1H), 6.70 (d, 1H), 4.58 (t, 1H), 3.88- 3.84 (m, 1H), 3.80-3.75 (m, 1H), 3.53-3.49 (m, 1H), 3.44-3.40 (m, 1H), 85 (t, 2H), 1.85-1.51 (m, 10H).
(合成例15)Tetrahydro−2−(4−{5−[2−(5−{5”−[2−(5−butyl−2−thienyl)ethynyl]−2,2’:5’,2”−terthiophene}−yl)ethynyl]−2−thienyl}butoxy)−2H−pyran(化合物15)の合成
下記のスキームに従って化合物4と化合物14とを用いて化合物15を合成した。
(Synthesis Example 15) Tetrahydro-2- (4- {5- [2- (5- {5 "-[2- (5-butyl-2-thienyl) ethyl]]-2,2 ': 5', 2" Synthesis of -terthiophene} -yl) ethyl] -2-thienyl} butoxy) -2H-pyran (Compound 15) Compound 15 was synthesized using Compound 4 and Compound 14 according to the following scheme.
2口ナスフラスコにTetrahydro−2−(4−{5−[2−(5”−bromo−2,2’:5’,2”−terthiophene)−5−ethynyl]−2−thienyl}butoxy)−2H−pyran(化合物14)(0.901g、1.53mmol)、PdCl2(PPh3)2(37.4mg、53.3mol、3.5mol%)、ヨウ化銅(11.3mg、59.3μmol、3.9mol%)を入れ、2−Butyl−5−ethynylthiophene(化合物4)(0.374g、2.28mmol、1.5eq.)とトリエチルアミン(90mL)との混合溶液を加えた。アルゴンガス雰囲気下、室温で23時間撹拌した後、溶媒を減圧留去し、ジクロロメタンを加えた。得られた有機層を純水、次いで飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥させ、溶媒を留去して、黒色固体を得た。得られた黒色固体をシリカゲルカラムクロマトグラフィー(展開溶媒:ジクロロメタン)により精製して、橙色固体の化合物15(0.938g、1.39mmol、収率91%)を得た。 Tetrahydro-2- (4- {5- [2- (5 "-bromo-2,2 ': 5', 2" -tertiophene) -5-ethylnyl] -2-thienyl} butoxy)- 2H-pyran (compound 14) (0.901 g, 1.53 mmol), PdCl 2 (PPh 3 ) 2 (37.4 mg, 53.3 mol, 3.5 mol%), copper iodide (11.3 mg, 59.3 μmol) 3.9 mol%) was added, and a mixed solution of 2-Butyl-5-ethylthiophene (Compound 4) (0.374 g, 2.28 mmol, 1.5 eq.) And triethylamine (90 mL) was added. After stirring at room temperature for 23 hours under an argon gas atmosphere, the solvent was distilled off under reduced pressure, and dichloromethane was added. The obtained organic layer was washed with pure water and then saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a black solid. The resulting black solid was purified by silica gel column chromatography (developing solvent: dichloromethane) to obtain orange solid compound 15 (0.938 g, 1.39 mmol, yield 91%).
1H NMR (500 MHz, CDCl3): δ/ppm = 7.14 (dd, 2H), 7.11 (d, 2H), 7.01 (s, 2H), 7.06 (d, 2H), 6.70 (d, 1H), 6.68 (d, 1H), 4.58 (t, 1H), 3.89-3.84 (m, 1H), 3.80-3.75 (m, 1H), 3.53-3.49 (m, 1H), 3.44-3.40 (m, 1H), 2.85 (t, 2H), 2.81 (t, 2H), 1.86-1.50 (m, 12H), 0.94 (t, 3H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.14 (dd, 2H), 7.11 (d, 2H), 7.01 (s, 2H), 7.06 (d, 2H) , 6.70 (d, 1H), 6.68 (d, 1H), 4.58 (t, 1H), 3.89-3.84 (m, 1H), 3.80-3.75 (m 1H), 3.53-3.49 (m, 1H), 3.44-3.40 (m, 1H), 2.85 (t, 2H), 2.81 (t, 2H), 86-1.50 (m, 12H), 0.94 (t, 3H).
(合成例16)5−[2−(5−{5”−[2−(5−Butyl−2−thienyl)ethynyl]−2,2’:5’,2”−terthiophene}−yl)ethynyl]−2−thiophenebutanol(化合物16)の合成
下記のスキームに従って化合物15から化合物16を合成した。
(Synthesis Example 16) 5- [2- (5- {5 "-[2- (5-Butyl-2-thienyl) ethyl] -2,2 ': 5', 2" -tertiophene} -yl) ethyl] Synthesis of 2-thiophenebutanol (Compound 16) Compound 16 was synthesized from compound 15 according to the following scheme.
Tetrahydro−2−(4−{5−[2−(5−{5”−[2−(5−butyl−2−thienyl)ethynyl]−2,2’:5’,2”−terthiophene}−yl)ethynyl]−2−thienyl}butoxy)−2H−pyran(化合物15)(0.211g、0.313mmol)をテトラヒドロフラン(10mL)に溶解させ、エタノール(10mL)を加えた。60℃で加熱撹拌しながらPyridinium p−Toluenesulfonate(PPTS)(21.6g、86.0μmol、30mol%)を加え、3時間撹拌した。その後、得られた溶液を減圧留去し、シリカゲルカラムクロマトグラフィー(展開溶媒:クロロホルム)により精製し、橙色固体の化合物16(180mg、0.306mmol、収率98%)を得た。1H NMRの測定結果を以下に示す。 Tetrahydro-2- (4- {5- [2- (5- {5 "-[2- (5-but-2-ylenyl) ethyl]]-2,2 ': 5', 2" -tertiophene} -yl ) Ethynyl] -2-thienyl} butoxy) -2H-pyran (compound 15) (0.211 g, 0.313 mmol) was dissolved in tetrahydrofuran (10 mL) and ethanol (10 mL) was added. Pyridinium p-Toluenesulfate (PPTS) (21.6 g, 86.0 μmol, 30 mol%) was added with stirring at 60 ° C. with stirring for 3 hours. Then, the obtained solution was distilled off under reduced pressure and purified by silica gel column chromatography (developing solvent: chloroform) to obtain orange solid compound 16 (180 mg, 0.306 mmol, yield 98%). The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 7.14 (dd, 2H), 7.11 (d, 2H), 7.10 (s, 2H), 7.06 (d, 2H), 6.70 (d, 1H), 6.68 (d, 1H), 3.68 (q, 2H), 2.85 (t, 2H), 2.81 (t, 2H), 1.81-1.75 (quint, 2H), 1.69-1.62 (m, 4H), 1.43-1.36 (sext, 2H), 0.94 (t, 3H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.14 (dd, 2H), 7.11 (d, 2H), 7.10 (s, 2H), 7.06 (d, 2H) , 6.70 (d, 1H), 6.68 (d, 1H), 3.68 (q, 2H), 2.85 (t, 2H), 2.81 (t, 2H), 1.81- 1.75 (quint, 2H), 1.69-1.62 (m, 4H), 1.43-1.36 (sext, 2H), 0.94 (t, 3H).
(合成例17)4−{5−[2−(5−{5”−[2−(5−Butyl−2−thienyl)ethynyl]−2,2’:5’,2”−terthiophene}−yl)ethynyl]−2−thienyl}butyl Methacrylate(化合物17)の合成
下記のスキームに従って化合物16から化合物17を合成した。
Synthesis Example 17 4- {5- [2- (5- {5 ″-[2- (5-Butyl-2-thienyl) ethyl]]-2,2 ′: 5 ′, 2 ″ -tertiophene} -yl ) Synthesis of ethyl] -2-thienyl} butyl methacrylate (Compound 17) Compound 17 was synthesized from Compound 16 according to the following scheme.
5−[2−(5−{5”−[2−(5−Butyl−2−thienyl)ethynyl]−2,2’:5’,2”−terthiophene}−yl)ethynyl]−2−thiophenebutanol(化合物16)(0.103g、0.174mmol)、トリエチルアミン(0.480mL、3.45mmol、20eq.)、テトラヒドロフラン(20mL)および重合禁止剤としてヒドロキノンを混合した溶液に塩化メタクリロイル(0.330mL、3.47mmol、20eq.)とテトラヒドロフラン(0.670mL)の混合溶液を氷冷下で滴下した。室温で4時間撹拌した後、反応溶液を飽和炭酸水素ナトリウム水溶液に滴下して反応を停止させた。クロロホルムで3回抽出し、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥させ、溶媒を留去して、橙色固体を得た。得られた橙色固体をシリカゲルカラムクロマトグラフィー(展開溶媒:クロロホルム)により精製し、橙色固体の化合物17(97.2mg、0.148mmol、収率85%)を得た。1H NMRの測定結果を以下に示す。 5- [2- (5- {5 "-[2- (5-Butyl-2-thienyl) ethyl]]-2,2 ': 5', 2" -tertiophene} -yl) ethyl] -2-thiophenebutanol ( Compound 16) (0.103 g, 0.174 mmol), triethylamine (0.480 mL, 3.45 mmol, 20 eq.), Tetrahydrofuran (20 mL), and a solution obtained by mixing hydroquinone as a polymerization inhibitor with methacryloyl chloride (0.330 mL, 3 .47 mmol, 20 eq.) And tetrahydrofuran (0.670 mL) were added dropwise under ice cooling. After stirring at room temperature for 4 hours, the reaction solution was dropped into a saturated aqueous sodium hydrogen carbonate solution to stop the reaction. Extracted with chloroform three times, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain an orange solid. The resulting orange solid was purified by silica gel column chromatography (developing solvent: chloroform) to obtain orange solid compound 17 (97.2 mg, 0.148 mmol, 85% yield). The measurement result of 1 H NMR is shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 7.14 (dd, 2H), 7.11 (dd, 2H), 7.09 (s, 2H), 7.06 (d, 2H), 6.70 (d, 1H), 6.68 (d, 1H), 6.11 (s, 1H), 5.56 (s, 1H), 4.18 (t, 2H), 2.86 (t, 2H), 2.81 (t, 2H), 1.95 (s, 3H), 1.81-1.77 (m, 4H), 1.69-1.63 (quint, 2H), 1.44-1.36 (sext, 2H), 0.94 (t, 3H). 1 H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.14 (dd, 2H), 7.11 (dd, 2H), 7.09 (s, 2H), 7.06 (d, 2H) , 6.70 (d, 1H), 6.68 (d, 1H), 6.11 (s, 1H), 5.56 (s, 1H), 4.18 (t, 2H), 2.86 ( t, 2H), 2.81 (t, 2H), 1.95 (s, 3H), 1.81-1.77 (m, 4H), 1.69-1.63 (quint, 2H), 1 .44-1.36 (sext, 2H), 0.94 (t, 3H).
(実施例5)PEO−b−PTR5MAの合成
下記のスキームに従って化合物17とポリエチレンオキサイドとを用いてPEO−b−PTR5MAを合成することができる。
Example 5 Synthesis of PEO-b-PTR5MA PEO-b-PTR5MA can be synthesized using Compound 17 and polyethylene oxide according to the following scheme.
(実施例6)
実施例5の化合物を第1の化合物として、ITO層をパターニングしたガラス基板上にスピンコート法などにより塗布し、乾燥させ、薄膜を形成する。不活性ガス雰囲気下または真空中で熱処理を行ったのち、親水部を切断して除去する処理を行う。再度乾燥させ、第2の化合物を親水部を除去した後に生じた空隙に含浸させて光学活性層を形成し、光学活性層上に電極を形成することにより光電変換素子を製造する。製造される光電変換素子は優れた光電変換効率を示す。
(Example 6)
The compound of Example 5 is applied as a first compound on a glass substrate on which the ITO layer is patterned by spin coating or the like, and dried to form a thin film. After the heat treatment in an inert gas atmosphere or in a vacuum, the hydrophilic portion is cut and removed. The photoelectric conversion element is manufactured by drying again and impregnating the void formed after removing the hydrophilic portion with the second compound to form an optically active layer, and forming an electrode on the optically active layer. The produced photoelectric conversion element exhibits excellent photoelectric conversion efficiency.
(合成例18)化合物17のホモポリマーの合成
下記のスキームに従って化合物17のホモポリマーを合成した。
Synthesis Example 18 Synthesis of Homopolymer of Compound 17 A homopolymer of Compound 17 was synthesized according to the following scheme.
ナスフラスコに4−{5−[2−(5−{5”−[2−(5−Butyl−2−thienyl)ethynyl]−2,2’:5’,2”−terthiophene}−yl)ethynyl]−2−thienyl}butyl Methacrylate(化合物17)(75.0mg、0.114mmol)を入れ、2,2’−Azobis(isobutyronitrile)(AIBN)(0.75mg、4.6μmol、1wt%)とトルエン(0.75mL)との混合溶液を加えた。次にFreeze−pump−thaw cycleによる真空脱気を3回実施した後、封管して60℃で18時間撹拌した。重合溶液が入ったナスフラスコを氷浴につけて重合反応を停止させ、重合溶媒を除去して橙色固体(96.2mg)を得た。得られた黄色固体をクロロホルムに溶解させてメタノールに滴下し、固体を沈殿させて、固体を減圧ろ過により回収してアセトンで洗浄する操作を2回行った。得られた茶色固体を再びクロロホルムに溶解させてヘキサンに滴下して固体を沈殿させ、固体を減圧ろ過により回収した。得られた固体をデシケーターで乾燥させて紫色固体(18.3mg)を得た。1H NMR、分子量(Mn、Mw)の測定結果を以下に示す。 4- {5- [2- (5- {5 ″-[2- (5-Butyl-2-thienyl) ethyl]]-2,2 ′: 5 ′, 2 ″ -tertiophene} -yl) ethylyl ] -2-thienyl} butyl methacrylate (compound 17) (75.0 mg, 0.114 mmol) was added, and 2,2′-Azobis (isobutyronitrile) (AIBN) (0.75 mg, 4.6 μmol, 1 wt%) and toluene A mixed solution with (0.75 mL) was added. Next, vacuum deaeration with Freeze-pump-thaw cycle was performed three times, and the tube was sealed and stirred at 60 ° C. for 18 hours. The eggplant flask containing the polymerization solution was placed in an ice bath to stop the polymerization reaction, and the polymerization solvent was removed to obtain an orange solid (96.2 mg). The obtained yellow solid was dissolved in chloroform and added dropwise to methanol to precipitate the solid, and the solid was collected by vacuum filtration and washed with acetone twice. The obtained brown solid was dissolved again in chloroform and added dropwise to hexane to precipitate the solid, and the solid was recovered by filtration under reduced pressure. The obtained solid was dried with a desiccator to obtain a purple solid (18.3 mg). The measurement results of 1 H NMR and molecular weight (Mn, Mw) are shown below.
1H NMR (500 MHz, CDCl3): δ/ppm = 7.13-6.82 (br, 8H), 6.67-6.61 (br, 2H), 3.96-3.93 (br, 2H), 2.85-2.67 (br, 4H), 1.68-1.59 (br, 6H), 1.41-1.33 (br, 2H), 1.25 (s), 0.97-0.84 (br, 3H).Mn=1.33×104、Mw=2.05×104、Mw/Mn=1.54 1H NMR (500 MHz, CDCl 3 ): δ / ppm = 7.13-6.82 (br, 8H), 6.67-6.61 (br, 2H), 3.96-3.93 (br, 2H), 2.85-2.67 (br, 4H), 1.68-1.59 (br, 6H), 1.41-1.33 (br, 2H), 1.25 (s), 0 97-0.84 (br, 3H). Mn = 1.33 × 10 4 , Mw = 2.05 × 10 4 , Mw / Mn = 1.54
偏光顕微鏡を用いて化合物17のホモポリマーの液晶性を確認した。室温(25℃)においてネマチック相に特有のシュリーレンテクスチャーが観察でき、化合物17のホモポリマーが液晶状態であることが確認できた。化合物17のホモポリマーは200℃まで昇温しても液晶性を有していた。温度を200℃で維持したところ次第に像全体が暗くなり、10分後からは明るさが変化しなくなったため降温した。温度が下がるにつれて像は明るさを取り戻していき、室温でも液晶性を保ったままであった。結果として、化合物17のホモポリマーは25℃から200℃までの広い温度範囲でネマチック相を示すことがわかった。よって、化合物17のホモポリマーはその液晶性により、外力によりその配向性を制御することによってモルフォロジーを最適化するなどできるため、光電変換素子等の材料として好適に用いることができる。 The liquid crystallinity of the homopolymer of Compound 17 was confirmed using a polarizing microscope. A schlieren texture peculiar to the nematic phase could be observed at room temperature (25 ° C.), and it was confirmed that the homopolymer of Compound 17 was in a liquid crystal state. The homopolymer of Compound 17 had liquid crystallinity even when the temperature was raised to 200 ° C. When the temperature was maintained at 200 ° C., the entire image gradually became darker, and after 10 minutes the brightness did not change, so the temperature dropped. As the temperature decreased, the image regained its brightness and remained liquid crystalline even at room temperature. As a result, it was found that the homopolymer of Compound 17 exhibited a nematic phase over a wide temperature range from 25 ° C to 200 ° C. Therefore, the homopolymer of compound 17 can be suitably used as a material for a photoelectric conversion element and the like because its liquid crystallinity allows the morphology to be optimized by controlling its orientation by external force.
(合成例19)ブロックコポリマー(PEO−b−PTR5MA)の合成
下記のスキームに従って化合物17を用いてブロックコポリマー(PEO−b−PTR5MA)を合成した。
Synthesis Example 19 Synthesis of Block Copolymer (PEO-b-PTR5MA) A block copolymer (PEO-b-PTR5MA) was synthesized using Compound 17 according to the following scheme.
10mLナスフラスコにα−(2−Bromo−2−methyl−1−oxopropyl)−ω−methoxy−poly(oxy−1,2−ethanediyl)(PEOBr、15.2mg、2.50μmol)、4−{5−[2−(5−{5”−[2−(5−Butyl−2−thienyl)ethynyl]−2,2’:5’,2”−terthiophene}−yl)ethynyl]−2−thienyl}butyl Methacrylate(化合物17、131.8mg、0.2mmol、80eq.)、Cu(I)Cl(1.2mg,12.1μmol,4.8eq.)を入れ、アルゴンガス置換した。次にHMTETA(3.4μL、12.5μmol、5eq.)、トルエン(0.5mL)を加えて凍結脱気を行い、60℃で24時間撹拌した。その後、重合を停止させて溶媒を留去し、目的物であるPEO−b−PTR5MAを得た。重合停止後に得た固体のGPC測定を行ったところ、Mn=1.93×104、Mw=2.33×104、Mw/Mn=1.21であった。 In a 10 mL eggplant flask, α- (2-Bromo-2-methyl-1-oxopropyl) -ω-methoxy-poly (oxy-1,2-ethanediyl) (PEOBr, 15.2 mg, 2.50 μmol), 4- {5 -[2- (5- {5 "-[2- (5-Butyl-2-thienyl) ethyl]]-2,2 ': 5', 2" -tertiophene} -yl) ethyl] -2-thienyl} butyl Methacrylate (compound 17, 131.8 mg, 0.2 mmol, 80 eq.) And Cu (I) Cl (1.2 mg, 12.1 μmol, 4.8 eq.) Were added, and the atmosphere was replaced with argon gas. Next, HMTETA (3.4 μL, 12.5 μmol, 5 eq.) And toluene (0.5 mL) were added for freeze degassing, and the mixture was stirred at 60 ° C. for 24 hours. Thereafter, the polymerization was stopped and the solvent was distilled off to obtain PEO-b-PTR5MA as the target product. When GPC measurement of the solid obtained after the termination of polymerization was performed, Mn = 1.93 × 10 4 , Mw = 2.33 × 10 4 , and Mw / Mn = 1.21.
得られた薄膜についてAFM(Atomic Force Microscope)測定を実施した。AFM測定はAgilent Technologies 5500 AFM(探針:Olympus OMCL−AC160TS−C3(共振周波数:300kHz))を用い、大気中ACモード(ダイナミックモード)で測定した。走査範囲は500×500nm(256×256points)、走査速度1.0line/secとした。 The obtained thin film was subjected to AFM (Atomic Force Microscope) measurement. The AFM measurement was performed in an atmospheric AC mode (dynamic mode) using an Agilent Technologies 5500 AFM (probe: Olympus OMCL-AC160TS-C3 (resonance frequency: 300 kHz)). The scanning range was 500 × 500 nm (256 × 256 points), and the scanning speed was 1.0 line / sec.
結果を図2に示す。図2は、AFM像を示す写真図である。図2から明らかな通り、写真図において白っぽく示されている明部(有機半導体部位であるPTR5MA部位)と黒っぽく示されている暗部(絶縁性部位であるポリエチレンオキサイド部位:PEO部位)との相分離により、規則性の高いナノ構造が確認できた。 The results are shown in FIG. FIG. 2 is a photograph showing an AFM image. As is clear from FIG. 2, the phase separation between the bright part (PTR5MA part which is an organic semiconductor part) shown as whitish and the dark part (polyethylene oxide part: PEO part which is an insulating part) shown as blackish in the photographic diagram. As a result, a highly ordered nanostructure was confirmed.
(実施例7)有機光電変換素子の作製例3
スパッタ法により150nmの厚さでITO膜を形成したガラス基板に対して、オゾンUV処理による表面処理を行い、次に、PEDOT:PSS(Heraeus社製AI4083)をスピンコート法により塗布し、200℃で10分間熱処理を行う。その上にPEO−b−PTR5MAの薄膜を実施例2の方法により形成し、得られた薄膜にC60フラーレンを5×10−4Pa以下の真空度で真空蒸着することにより、光学活性層を形成することができる。次いで金属電極を蒸着し、有機薄膜太陽電池を得ることができる。得られた有機薄膜太陽電池にソーラシミュレーターを用いて一定の光量の光を照射すると、優れた光電変換特性を示す。
(Example 7) Production Example 3 of Organic Photoelectric Conversion Element
A glass substrate on which an ITO film having a thickness of 150 nm is formed by sputtering is subjected to surface treatment by ozone UV treatment. Next, PEDOT: PSS (AI 4083 manufactured by Heraeus) is applied by spin coating, and 200 ° C. And heat treatment for 10 minutes. A thin film of PEO-b-PTR5MA was formed thereon by the method of Example 2, and C 60 fullerene was vacuum deposited on the obtained thin film at a vacuum degree of 5 × 10 −4 Pa or less to form an optically active layer. Can be formed. Subsequently, a metal electrode is vapor-deposited and an organic thin film solar cell can be obtained. When the obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator, excellent photoelectric conversion characteristics are exhibited.
(実施例8)有機光電変換素子の作製例4
スパッタ法により150nmの厚さでITO膜を形成したガラス基板に対して、オゾンUV処理による表面処理を行い、次に、PEDOT:PSS(Heraeus社製AI4083)をスピンコート法により塗布し、200℃で10分間熱処理を行う。その上にPEO−b−PTR5MAの薄膜を実施例2の方法により形成し、得られた薄膜に低エネルギー電子線を照射し、架橋させ、その後、第2の化合物を含む溶液に浸漬することにより光学活性層を形成することができる。続いて5×10−4Pa以下の真空度で金属電極を真空蒸着し、有機薄膜太陽電池を得ることができる。得られた有機薄膜太陽電池にソーラシミュレーターを用いて一定の光量の光を照射すると、優れた光電変換特性を示す。
(Example 8) Production Example 4 of Organic Photoelectric Conversion Element
A glass substrate on which an ITO film having a thickness of 150 nm is formed by sputtering is subjected to surface treatment by ozone UV treatment. Next, PEDOT: PSS (AI 4083 manufactured by Heraeus) is applied by spin coating, and 200 ° C. And heat treatment for 10 minutes. A thin film of PEO-b-PTR5MA is formed thereon by the method of Example 2, and the resulting thin film is irradiated with a low energy electron beam to crosslink, and then immersed in a solution containing the second compound. An optically active layer can be formed. Then, a metal electrode is vacuum-deposited with the vacuum degree of 5 * 10 <-4> Pa or less, and an organic thin film solar cell can be obtained. When the obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator, excellent photoelectric conversion characteristics are exhibited.
(実施例9)有機発光素子の作製例1
実施例3記載の手法に準じて素子を作製し、電流を印加すると、優れた発光特性を示す。
Example 9 Production Example 1 of Organic Light-Emitting Element
When an element is manufactured according to the method described in Example 3 and a current is applied, excellent light emission characteristics are exhibited.
(実施例10)有機発光素子の作製例2
実施例4記載の手法に準じて素子を作製し、電流を印加すると、優れた発光特性を示す。
Example 10 Production Example 2 of Organic Light-Emitting Element
When an element is manufactured according to the method described in Example 4 and a current is applied, excellent light emission characteristics are exhibited.
(実施例11)有機発光素子の作製例3
実施例7記載の手法に準じて素子を作製し、電流を印加すると、優れた発光特性を示す。
Example 11 Production Example 3 of Organic Light-Emitting Element
When an element is fabricated according to the method described in Example 7 and a current is applied, excellent light emission characteristics are exhibited.
(実施例12)有機発光素子の作製例4
実施例8記載の手法に準じて素子を作製し、電流を印加すると、優れた発光特性を示す。
Example 12 Production Example 4 of Organic Light-Emitting Element
When an element is manufactured according to the method described in Example 8 and a current is applied, excellent light emission characteristics are exhibited.
Claims (20)
前記有機層が、電子供与性及び電子受容性のうちのいずれか一方の整流特性の有機半導体部位と絶縁性部位とこれらを結合する結合部位とを有しており分子量分散が1.6以下である第1の化合物から絶縁性部位が除去された化合物と、前記有機半導体部位とは異なる整流特性の有機半導体部位を有する第2の化合物とを含む、有機デバイス。 A first electrode; a second electrode; and an organic layer provided between the first electrode and the second electrode;
The organic layer has an organic semiconductor site having one of rectifying properties of electron donating property and electron accepting property, an insulating site, and a binding site for binding them, and the molecular weight dispersion is 1.6 or less. An organic device comprising: a compound obtained by removing an insulating part from a first compound; and a second compound having an organic semiconductor part having a rectifying characteristic different from that of the organic semiconductor part.
電子供与性及び電子受容性のうちのいずれか一方の整流特性を有する有機半導体部位と絶縁性部位とこれらを結合する結合部位を有しており、分子量分散が1.6以下である第1の化合物を含む層を形成した後に、該層中の第1の化合物の結合部位を分解することで第1の化合物から絶縁性部位を除去し、次いで前記有機半導体部位とは異なる整流特性の有機半導体部位を有する第2の化合物を、前記層に接触するように添加し、前記絶縁性部位の除去により生じた前記層中の空隙に充填することで有機層を形成する、有機デバイスの製造方法。 In a method for manufacturing an organic device having a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode,
The organic semiconductor part having an rectifying property of either one of electron donating property and electron accepting property, an insulating part, and a binding part for bonding them, and having a molecular weight dispersion of 1.6 or less After forming the layer containing the compound, the insulating portion is removed from the first compound by decomposing the binding site of the first compound in the layer, and then the organic semiconductor having a rectifying characteristic different from that of the organic semiconductor portion The manufacturing method of the organic device which adds the 2nd compound which has a site | part so that the said layer may be contacted, and forms the organic layer by filling the space | gap in the said layer produced by the removal of the said insulating site | part.
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