JP2012222314A - Organic thin-film solar cell - Google Patents
Organic thin-film solar cell Download PDFInfo
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- JP2012222314A JP2012222314A JP2011089895A JP2011089895A JP2012222314A JP 2012222314 A JP2012222314 A JP 2012222314A JP 2011089895 A JP2011089895 A JP 2011089895A JP 2011089895 A JP2011089895 A JP 2011089895A JP 2012222314 A JP2012222314 A JP 2012222314A
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- solar cell
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- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
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- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- LSQODMMMSXHVCN-UHFFFAOYSA-N ovalene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3C5=C6C(C=C3)=CC=C3C6=C6C(C=C3)=C3)C4=C5C6=C2C3=C1 LSQODMMMSXHVCN-UHFFFAOYSA-N 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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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- Photovoltaic Devices (AREA)
Abstract
Description
本発明は、有機薄膜太陽電池及びその製造方法に関する。 The present invention relates to an organic thin film solar cell and a method for manufacturing the same.
有機薄膜太陽電池は、電子受容材料と電子供与材料の２種類の有機半導体を組み合わせて作る次世代太陽電池の１つであり、印刷によって簡便、低コストで生産できることが期待されている。また、電解液等を用いない固体の太陽電池であるため、柔軟性や寿命向上の上でも有利とされている。 The organic thin film solar cell is one of the next generation solar cells made by combining two types of organic semiconductors, ie, an electron accepting material and an electron donating material, and is expected to be easily produced at low cost by printing. In addition, since it is a solid solar cell that does not use an electrolytic solution or the like, it is advantageous for improving flexibility and life.
有機薄膜太陽電池としては、例えば、透明基板と、該透明基板上に形成された透明電極と、電子供与材料としてのｐ型有機半導体層と電子受容材料としてのｎ型有機半導体層からなる光電変換層と、該光電変換層上に形成された、透明電極と対向する電極である対向電極とを有するものが知られている。 As an organic thin film solar cell, for example, a photoelectric conversion comprising a transparent substrate, a transparent electrode formed on the transparent substrate, a p-type organic semiconductor layer as an electron donating material, and an n-type organic semiconductor layer as an electron accepting material One having a layer and a counter electrode, which is an electrode facing the transparent electrode, formed on the photoelectric conversion layer is known.
しかしながら、光電変換層を形成するために用いる有機半導体材料は、導電性が低いことから、光電変換層の膜厚を入射する光を十分に吸収できる程度にまで厚くすることは困難であり、光を有効に利用することができないと いう問題がある。 However, since the organic semiconductor material used for forming the photoelectric conversion layer has low conductivity, it is difficult to increase the thickness of the photoelectric conversion layer to a level that can sufficiently absorb incident light. There is a problem that cannot be used effectively.
このため、有機薄膜太陽電池は、これまで低いエネルギー変換効率しか得られておらず、実用化のためにはエネルギー変換効率の高効率化が課題とされている。 For this reason, only a low energy conversion efficiency has been obtained so far in the organic thin-film solar cell, and for the purpose of practical use, a high efficiency of the energy conversion efficiency is a problem.
そこで、光電変換層の光の吸収率を向上させるために、透明基板、透明電極または対向電極の表面を凹凸化することにより、この凹凸によって入射光を散乱させ、光電変換層における光路長を長くする、いわゆる光閉じ込め効果を利用した太陽電池が数多く報告されている。例えば特許文献１には、透明基板上に、透明電極として凹凸状の酸化スズ膜を形成することにより、光閉じ込め効果を有する太陽電池用基板が提案されている。 Therefore, in order to improve the light absorption rate of the photoelectric conversion layer, the surface of the transparent substrate, the transparent electrode or the counter electrode is made uneven so that incident light is scattered by the unevenness and the optical path length in the photoelectric conversion layer is increased. Many solar cells utilizing the so-called light confinement effect have been reported. For example, Patent Document 1 proposes a solar cell substrate having a light confinement effect by forming an uneven tin oxide film as a transparent electrode on a transparent substrate.
しかしながら、上記のような凹凸を有する透明電極の上に光電変換層を形成する場合には、この凹凸の高低差が数百ｎｍ程度であり、光電変換層の膜厚が数百ｎｍ程度と薄いことから、この凹凸により透明電極と対向電極との間で短絡が生じ、太陽電池として機能しなくなるという問題がある。 However, when the photoelectric conversion layer is formed on the transparent electrode having the unevenness as described above, the height difference of the unevenness is about several hundred nm, and the film thickness of the photoelectric conversion layer is as thin as several hundred nm. Therefore, there is a problem that a short circuit occurs between the transparent electrode and the counter electrode due to the unevenness, and the solar cell does not function.
本発明は、上記した従来技術の現状に鑑みてなされたものであり、その主な目的は、有機半導体層を光電変換層とする有機薄膜太陽電池において、より向上した光電変換特性を有する有機薄膜太陽電池を提供することである。 The present invention has been made in view of the above-described conventional state of the art, and the main object thereof is an organic thin film having improved photoelectric conversion characteristics in an organic thin film solar cell having an organic semiconductor layer as a photoelectric conversion layer. It is to provide a solar cell.
本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、透明電極を形成した透明基板上に鎖状の共役系導電性高分子化合物の固形物を一定圧で押しつけて、一定方向に塗布することによって、基板面に平行に一定方向に配向したポリマー層を形成することができ、このようにして形成されたポリマー層上に、鎖状又は平面状のπ共役系のｐ型有機半導体化合物又はｎ型有機半導体化合物を真空蒸着することによって、該ポリマー層をテンプレートとして、ｐ型有機半導体化合物又はｎ型有機半導体化合物が基板面に平行に一定方向に配向した有機半導体層を形成できることを見出した。そして、この様な方法で形成された有機半導体層は、ｐ型有機半導体化合物又はｎ型有機半導体化合物が、基板面に平行に一定方向に配向することによってπ−πスタック構造が形成され、これによって該半導体層の基板に対して垂直方向の導電性が向上し、その結果、有機薄膜太陽電池におけるエネルギー変換効率が大きく向上することを見出し、ここに本発明を完成するに至った。 The present inventor has intensively studied to achieve the above-described object. As a result, a solid material of a chain-like conjugated conductive polymer compound was pressed at a constant pressure on a transparent substrate on which a transparent electrode was formed, and applied in a certain direction to be oriented in a certain direction parallel to the substrate surface. A polymer layer can be formed, and the chain-like or planar π-conjugated p-type organic semiconductor compound or n-type organic semiconductor compound is vacuum-deposited on the polymer layer thus formed. It has been found that an organic semiconductor layer in which a p-type organic semiconductor compound or an n-type organic semiconductor compound is oriented in a certain direction parallel to the substrate surface can be formed using a polymer layer as a template. The organic semiconductor layer formed by such a method forms a π-π stack structure by aligning a p-type organic semiconductor compound or an n-type organic semiconductor compound in a certain direction parallel to the substrate surface. As a result, the conductivity in the direction perpendicular to the substrate of the semiconductor layer was improved, and as a result, the energy conversion efficiency in the organic thin film solar cell was greatly improved, and the present invention was completed here.
即ち、本発明は、下記の有機薄膜太陽電池及びその製造方法を提供するものである。
項１． 透明電極が形成された透明基板上に、導電性高分子化合物が一定方向に配向したポリマー層と、該ポリマー層上に形成され、該導電性高分子化合物と同一方向に配向したｐ型有機半導体化合物又はｎ型有機半導体化合物からなる有機半導体層を有する、有機薄膜太陽電池。
項２． 導電性高分子化合物が、鎖状のπ共役系又はσ共役系の導電性高分子化合物である上記項１に記載の有機薄膜太陽電池。
項３． 有機半導体層を形成するｐ型有機半導体化合物及びｎ型有機半導体化合物が、平面状又は鎖状のπ共役系有機半導体化合物である上記項１又は２に記載の有機薄膜太陽電池。
項４． 下記（１）〜（３）のいずれかの構成を有する上記項１〜３のいずれかに記載の有機薄膜太陽電池：
（１） 透明電極が形成された透明基板／（必要に応じて正孔注入材層）／ｐ型半導体の性質を有さない導電性高分子化合物による配向したポリマー層／ｐ型有機半導体化合物の蒸着層／ｎ型有機半導体化合物のスピンコート層／（必要に応じて正孔ブロック材層）／金属電極、
（２） 透明電極が形成された透明基板／（必要に応じて正孔注入材層）／ｐ型導電性高分子化合物による配向したポリマー層／ｎ型有機半導体化合物の蒸着層／（必要に応じて正孔ブロック材層）／金属電極
（３） 透明電極が形成された透明基板／（必要に応じて正孔注入材層）／ｐ型導電性高分子化合物による配向したポリマー層／ｐ型有機半導体化合物の蒸着層／ｎ型有機半導体化合物のスピンコート層／（必要に応じて正孔ブロック材層）／金属電極。
項５． 透明電極が形成された透明基板上に、導電性高分子化合物が基板に平行方向に一定方向に配向したポリマー層を形成し、次いで、該ポリマー層上に、真空蒸着法によって、ｐ型半導体又はｎ型半導体としての性質を有する有機半導体化合物の層を形成する工程を含む、上記項１〜４のいずれかに記載された有機薄膜太陽電池の製造方法。
項６． 導電性高分子化合物が基板に平行に一定方向に配向したポリマー層を形成する方法が、鎖状のπ共役系又はσ共役系の導電性高分子化合物の固形成形体を、透明電極が形成された透明基板に一定圧力で押しつけて一定方向に掃引する方法である、上記項５に記載の有機薄膜太陽電池の製造方法。
項７． ｐ型半導体又はｎ型半導体としての性質を有する有機半導体化合物が、鎖状又は平面状のπ共役系有機化合物である上記項５又は６に記載の方法。
That is, this invention provides the following organic thin film solar cell and its manufacturing method.
Item 1. A polymer layer in which a conductive polymer compound is oriented in a certain direction on a transparent substrate on which a transparent electrode is formed, and a p-type organic semiconductor formed on the polymer layer and oriented in the same direction as the conductive polymer compound An organic thin film solar cell having an organic semiconductor layer made of a compound or an n-type organic semiconductor compound.
Item 2. Item 2. The organic thin-film solar cell according to Item 1, wherein the conductive polymer compound is a chain π-conjugated or σ-conjugated conductive polymer compound.
Item 3. Item 3. The organic thin-film solar cell according to Item 1 or 2, wherein the p-type organic semiconductor compound and the n-type organic semiconductor compound forming the organic semiconductor layer are planar or chain π-conjugated organic semiconductor compounds.
Item 4. The organic thin-film solar cell according to any one of Items 1 to 3, which has any one of the following (1) to (3):
(1) Transparent substrate on which a transparent electrode is formed / (Positive hole injection material layer if necessary) / Organic polymer layer with conductive polymer compound having no p-type semiconductor properties / p-type organic semiconductor compound Deposition layer / spin coat layer of n-type organic semiconductor compound / (hole blocking material layer if necessary) / metal electrode,
(2) Transparent substrate on which a transparent electrode is formed / (Positive hole injection material layer if necessary) / Polymer layer oriented with p-type conductive polymer compound / Vapor deposition layer of n-type organic semiconductor compound / (As necessary Hole blocking material layer) / metal electrode (3) transparent substrate on which transparent electrode is formed / (hole injection material layer if necessary) / polymer layer oriented by p-type conductive polymer compound / p-type organic Vapor deposition layer of semiconductor compound / spin coat layer of n-type organic semiconductor compound / (hole blocking material layer if necessary) / metal electrode.
Item 5. On the transparent substrate on which the transparent electrode is formed, a polymer layer in which a conductive polymer compound is oriented in a certain direction parallel to the substrate is formed, and then a p-type semiconductor or a polymer layer is formed on the polymer layer by vacuum deposition. Item 5. The method for producing an organic thin-film solar cell according to any one of Items 1 to 4, comprising a step of forming a layer of an organic semiconductor compound having properties as an n-type semiconductor.
Item 6. A method of forming a polymer layer in which a conductive polymer compound is oriented in a certain direction parallel to the substrate is formed by forming a solid molded body of a chain-like π-conjugated or σ-conjugated conductive polymer compound into a transparent electrode. Item 6. The method for producing an organic thin-film solar cell according to Item 5, wherein the method is a method in which the transparent substrate is pressed with a constant pressure and swept in a certain direction.
Item 7. Item 7. The method according to Item 5 or 6, wherein the organic semiconductor compound having properties as a p-type semiconductor or an n-type semiconductor is a chain or planar π-conjugated organic compound.
本発明の有機薄膜太陽電池は、透明電極が形成された透明基板上に、導電性高分子化合物からなる配向したポリマー層が形成され、その上に、真空蒸着法によってｐ型有機半導体層又はｎ型有機半導体層が形成された構造を有するものである。 In the organic thin film solar cell of the present invention, an oriented polymer layer made of a conductive polymer compound is formed on a transparent substrate on which a transparent electrode is formed, and a p-type organic semiconductor layer or n is formed thereon by vacuum deposition. A type organic semiconductor layer is formed.
以下、まず、上記した各層の形成方法について具体的に説明する。 Hereinafter, first, a method for forming each layer described above will be specifically described.
（I）配向ポリマー層（テンプレート層）の形成
本発明では、まず、透明電極が形成された透明基板上に、導電性高分子化合物が基板に平行方向に一定方向に配向したポリマー層（以下、「配向ポリマー層」ということがある）を形成する。
(I) Formation of oriented polymer layer (template layer) In the present invention, first, a polymer in which a conductive polymer compound is oriented in a certain direction parallel to the substrate on a transparent substrate on which a transparent electrode is formed. A layer (hereinafter sometimes referred to as an “aligned polymer layer”) is formed.
配向ポリマー層を形成するための導電性高分子化合物としては、鎖状のπ共役系又はσ共役系の導電性高分子化合物を用いることが必好ましく、後述する方法で基板に固体状の導電性化合物を押しつけて一定方向に塗布することによって、塗布方向に沿って、分子軸が基板面に平行に一定方向に配向する。該高分子化合物は、側鎖を有する場合には、例えば、炭素数１２程度以下の炭化水素基など比較的短い側鎖を有する高分子化合物が好ましい。 As the conductive polymer compound for forming the oriented polymer layer, it is essential to use a chain-like π-conjugated or σ-conjugated conductive polymer compound. By pressing and applying the compound in a certain direction, the molecular axis is oriented in a certain direction parallel to the substrate surface along the coating direction. When the polymer compound has a side chain, for example, a polymer compound having a relatively short side chain such as a hydrocarbon group having about 12 or less carbon atoms is preferable.
この様な導電性を有する共役系高分子化合物の内で、例えば、π共役系の鎖状導電性高分子化合物として、ポリアセチレン系ポリマー、ポリフェニレン系ポリマー、複素環系ポリマー、イオン性ポリマー、ラダーポリマーなどを用いることができる。これらのπ共役系鎖状導電性高分子化合物の具体例としては、ポリ（ｐ−フェニレン）（PPP）、ポリ（ｐ−フェニレンビニレン）（PPV）、置換基としてアルコキシ基を有するポリ（ｐ−フェニレンビニレン）誘導体、レジオレギュラーポリ（３−アルキルチオフェン）、ポリアニリン、ポリチオフェン（PT）、ポリフルオレン（PF）、ポリフルオレン誘導体、ポリピロール、これらの単量体成分を適宜組み合わせた共重合体などを挙げることができる。 Among such conjugated polymer compounds having electrical conductivity, for example, π-conjugated chain conductive polymer compounds include polyacetylene polymers, polyphenylene polymers, heterocyclic polymers, ionic polymers, and ladder polymers. Etc. can be used. Specific examples of these π-conjugated chain conductive polymer compounds include poly (p-phenylene) (PPP), poly (p-phenylene vinylene) (PPV), and poly (p-phenylene) having an alkoxy group as a substituent. Phenylene vinylene) derivatives, regioregular poly (3-alkylthiophene), polyaniline, polythiophene (PT), polyfluorene (PF), polyfluorene derivatives, polypyrrole, copolymers obtained by appropriately combining these monomer components, and the like. be able to.
また、σ共役系の鎖状導電性高分子化合物としては、ポリシラン、ポリゲルマン、ポリ（１，４−ジシラニレンフェニレン）等を例示できる。 Examples of the σ-conjugated chain conductive polymer compound include polysilane, polygermane, poly (1,4-disilanylenephenylene), and the like.
上記した導電性を有する共役系高分子化合物の構造の一例を示すと次の通りである。 An example of the structure of the above-described conjugated polymer compound having conductivity is as follows.
上記したπ共役系鎖状高分子化合物及びσ共役系鎖状高分子化合物は、いずれもｐ型半導体としての特性を有するものであるが、本発明では、ｐ型半導体としての特性を有する化合物だけではなく、半導体特性を有さない鎖状の共役系導電性高分子化合物も配向ポリマー層を形成するために用いることができる。 Both the π-conjugated chain polymer compound and the σ-conjugated chain polymer compound have characteristics as a p-type semiconductor, but in the present invention, only compounds having characteristics as a p-type semiconductor are used. Instead, a chain-like conjugated conductive polymer compound having no semiconductor characteristics can also be used to form the oriented polymer layer.
上記した導電性高分子化合物を用いて配向ポリマー層を形成するには、透明電極が形成された透明基板に、固体状の該導電性高分子化合物を押しつけて一定方向に塗布すればよい。通常は、該導電性高分子化合物をペレット状等の塗布が容易な形状に成形し、この固形成形体を透明電極面に押しつけながら一定方向に掃引すればよい。この際、均一なテンプレート層を形成するために、透明電極面に押しつける強さを一定として、一定の速度で導電性高分子化合物の固形成形体を掃引することが好ましい。この際、基板の温度を、使用する導電性高分子化合物のガラス転移点±２０℃程度、好ましくはガラス転移点±１０℃程度に加熱することによって、良好に配向したポリマー層を容易に形成することができる。 In order to form an oriented polymer layer using the above-described conductive polymer compound, the solid conductive polymer compound may be pressed against a transparent substrate on which a transparent electrode is formed and applied in a certain direction. Usually, the conductive polymer compound may be formed into a shape that can be easily applied, such as a pellet, and swept in a certain direction while pressing the solid molded body against the transparent electrode surface. At this time, in order to form a uniform template layer, it is preferable to sweep the solid molded body of the conductive polymer compound at a constant speed with a constant pressing strength against the transparent electrode surface. At this time, a well-oriented polymer layer is easily formed by heating the substrate temperature to a glass transition point of about ± 20 ° C., preferably about a glass transition point of about ± 10 ° C. of the conductive polymer compound to be used. be able to.
具体的な圧力や掃引速度などについては、実際に使用する導電性高分子化合物の種類や基板の加熱温度に応じて、均一な配向ポリマー層が形成されるように決めればよい。圧力が弱すぎる場合や掃引速度が速すぎる場合には、配向ポリマー層の厚さが不足することがあり、また、圧力が強すぎる場合や掃引速度が遅すぎる場合には、配向ポリマー層が不均一となることや、導電性高分子化合物の固体成形物が崩壊することがあるので好ましくない。 The specific pressure, sweep speed, etc. may be determined so that a uniform oriented polymer layer is formed according to the type of conductive polymer compound actually used and the heating temperature of the substrate. If the pressure is too weak or the sweep speed is too fast, the thickness of the oriented polymer layer may be insufficient, and if the pressure is too strong or the sweep speed is too slow, the oriented polymer layer may not be sufficient. It is not preferable because it becomes uniform and the solid molded product of the conductive polymer compound may collapse.
例えば、固体状の該導電性高分子化合物を0.5〜5MPa程度の圧力で基板に押しつけて、0.1〜3m/min程度の速度で掃引すればよい。 For example, the solid conductive polymer compound may be pressed against the substrate at a pressure of about 0.5 to 5 MPa and swept at a speed of about 0.1 to 3 m / min.
この方法によれば、上記した鎖状の共役系導電性高分子化合物の分子軸が、掃引方向に沿って、基板面に平行に一定方向に配向したポリマー層が形成される。 According to this method, a polymer layer is formed in which the molecular axes of the chain-like conjugated conductive polymer compound are aligned in a certain direction parallel to the substrate surface along the sweep direction.
形成される配向ポリマー層の厚さについては特に限定的ではないが、通常、後述する真空蒸着工程において、良好に配向した有機半導体層を形成するためには、２〜６０ｎｍ程度とすることが好ましい。 The thickness of the oriented polymer layer to be formed is not particularly limited, but usually it is preferably about 2 to 60 nm in order to form a well-oriented organic semiconductor layer in the vacuum vapor deposition step described later. .
また、配向ポリマー層を形成する導電性高分子化合物として、ｐ型半導体としての性質を有する化合物を用いた場合には、配向ポリマー層の厚さを１０ｎｍ程度以上とすることによって、配向ポリマー層自体を有機薄膜太陽電池における電子供与体層としても利用できる。 Further, when a compound having properties as a p-type semiconductor is used as the conductive polymer compound for forming the oriented polymer layer, the oriented polymer layer itself can be obtained by setting the thickness of the oriented polymer layer to about 10 nm or more. Can also be used as an electron donor layer in an organic thin film solar cell.
（II）真空蒸着による有機半導体層の形成
次いで、上記した方法で形成された配向ポリマー層上に、真空蒸着法によってｐ型半導体又はｎ型半導体としての性質を有する有機半導体化合物の層を形成する。この際、ｐ型半導体又はｎ型半導体としての性質を有する有機半導体化合物としては、鎖状又は平面状のπ共役系有機化合物を用いることが好ましく、これによって配向ポリマー層における導電性高分子化合物の配向方向に沿って、分子軸又は分子面が基板面に平行に配向したπ共役系有機半導体による層が形成される。この際、有機半導体化合物が、基板に平行に配向することによって、有機半導体化合物間において分子間相互作用（π−πスタッキング）が生じ、これによって、基板に対して垂直方向に正孔や電子が流れやすくなり、有機薄膜太陽電池を形成した際に、光電変換特性が大きく向上する。
(II) Formation of organic semiconductor layer by vacuum deposition Next, a layer of an organic semiconductor compound having properties as a p-type semiconductor or an n-type semiconductor is formed on the oriented polymer layer formed by the above-described method by a vacuum deposition method. . At this time, as the organic semiconductor compound having properties as a p-type semiconductor or an n-type semiconductor, a chain-like or planar π-conjugated organic compound is preferably used, whereby the conductive polymer compound in the oriented polymer layer is used. A layer composed of a π-conjugated organic semiconductor having a molecular axis or molecular plane aligned parallel to the substrate surface is formed along the alignment direction. At this time, the organic semiconductor compound is oriented parallel to the substrate, thereby causing an intermolecular interaction (π-π stacking) between the organic semiconductor compounds, whereby holes and electrons are perpendicular to the substrate. When it becomes easy to flow and an organic thin film solar cell is formed, a photoelectric conversion characteristic improves greatly.
真空蒸着に使用する有機半導体化合物としては、配向ポリマー層を形成するために用いた導電性高分子化合物が、ｐ型半導体としての性質を持たない場合には、ｐ型半導体としての性質を有する有機半導体化合物を用いて、ｐ型有機半導体層を形成することが必要である。 As an organic semiconductor compound used for vacuum deposition, when the conductive polymer compound used for forming the oriented polymer layer does not have a property as a p-type semiconductor, an organic material having a property as a p-type semiconductor is used. It is necessary to form a p-type organic semiconductor layer using a semiconductor compound.
また、ｐ型半導体としての性質を有する導電性高分子化合物を用いて配向ポリマー層を形成した場合であって、配向ポリマー層の厚さが薄く、電子供与体層として十分な性能を発揮できない場合、例えば、配向ポリマー層の厚さが10nm程度未満である場合には、ｐ型半導体としての性質を有する有機半導体化合物を用いて真空蒸着を行うことによって、ｐ型有機半導体層の厚さを増加させればよい。この場合、真空蒸着後のｐ型有機半導体層の厚さは、配向ポリマー層がｐ型半導体としての性質を有する場合には、配向ポリマー層との合計として、10nm程度以上、好ましくは15nm程度以上であることが好ましい。 In addition, when the oriented polymer layer is formed using a conductive polymer compound having properties as a p-type semiconductor, the oriented polymer layer is thin, and sufficient performance as an electron donor layer cannot be exhibited. For example, when the thickness of the oriented polymer layer is less than about 10 nm, the thickness of the p-type organic semiconductor layer is increased by performing vacuum deposition using an organic semiconductor compound having properties as a p-type semiconductor. You can do it. In this case, the thickness of the p-type organic semiconductor layer after vacuum deposition is about 10 nm or more, preferably about 15 nm or more in total when the oriented polymer layer has a property as a p-type semiconductor. It is preferable that
また、ｐ型半導体としての性質を有する導電性高分子化合物を用いて配向ポリマー層を形成した場合であって、形成された配向ポリマー層が太陽電池における電子供与体層として十分な性能を有する場合、例えば、配向ポリマー層の厚さが10nm程度以上、好ましくは15nm程度以上の場合には、真空蒸着に使用する有機半導体化合物として、ｎ型半導体としての性質を有する有機半導体化合物を用いることによって、真空蒸着法によって配向ポリマー層上に電子受容体層を直接形成することができる。 Moreover, when the oriented polymer layer is formed using a conductive polymer compound having properties as a p-type semiconductor, and the formed oriented polymer layer has sufficient performance as an electron donor layer in a solar cell. For example, when the thickness of the oriented polymer layer is about 10 nm or more, preferably about 15 nm or more, by using an organic semiconductor compound having properties as an n-type semiconductor as the organic semiconductor compound used for vacuum deposition, An electron acceptor layer can be formed directly on the oriented polymer layer by vacuum deposition.
真空蒸着に用いる有機半導体化合物としては、ｐ型半導体又はｎ型半導体としての性質を有する鎖状又は平面状のπ共役系有機化合物を用いればよい。該有機半導体化合物としては、真空蒸着における圧力条件下、例えば、５×１０−４Ｐａ程度以下の圧力下において、分解温度以下で気化又は昇華する化合物であることが好ましい。以下、これらの有機半導体化合物の具体例を記載する。 As an organic semiconductor compound used for vacuum deposition, a chain or planar π-conjugated organic compound having properties as a p-type semiconductor or an n-type semiconductor may be used. The organic semiconductor compound is preferably a compound that vaporizes or sublimes at a decomposition temperature or lower under a pressure condition in vacuum deposition, for example, at a pressure of about 5 × 10 −4 Pa or lower. Hereinafter, specific examples of these organic semiconductor compounds will be described.
（１）ｐ型有機半導体化合物
ｐ型半導体としての性質を有する化合物は、電子供与性のπ共役系有機化合物であればよい。
(1) p-type organic semiconductor compound The compound having properties as a p-type semiconductor may be any electron-donating π-conjugated organic compound.
（ｉ）鎖状ｐ型有機半導体化合物
電子供与性のπ共役系有機化合物の内で、鎖状の化合物としては、次の化合物を例示できる。
(I) Chain p-type organic semiconductor compound Among the electron donating π-conjugated organic compounds, examples of the chain compound include the following compounds.
（ａ）ヘテロ元素（N, O, S等）を有することのある鎖状の多環芳香族炭化水素化合物：具体例としては、クリセン、ペンタセン、テトラセン、アントラセン、アクリジン、ピセン、キナクリドン、ベンゾチエノベンゾチオフェン(BTBT)、これらの誘導体等を挙げることができる。 (A) Chain-like polycyclic aromatic hydrocarbon compounds that may have heteroelements (N, O, S, etc.): specific examples include chrysene, pentacene, tetracene, anthracene, acridine, picene, quinacridone, benzothieno Examples thereof include benzothiophene (BTBT) and derivatives thereof.
（ｂ）ヘテロ元素（N, O, S等）を有することのある単環化合物のオリゴマー又はコオリゴマー：具体例としては、フラン、ピロール、イミダゾール、 チオフェン、 ホスホール、 ピラゾール、 オキサゾール、 イソオキサゾール、 チアゾール、ベンゼン（フェニレン）、 ピリジン、 ピラジン、 ピリミジン、ピリダジン、トリアジン、これらの誘導体などの単環化合物の重合度１２程度以下のオリゴマーを挙げることができる。 (B) Monocyclic oligomers or co-oligomers that may have heteroelements (N, O, S, etc.): specific examples include furan, pyrrole, imidazole, thiophene, phosphole, pyrazole, oxazole, isoxazole, thiazole And oligomers having a degree of polymerization of about 12 or less of monocyclic compounds such as benzene (phenylene), pyridine, pyrazine, pyrimidine, pyridazine, triazine, and derivatives thereof.
（ｃ）ヘテロ元素（N, O, S等）を有することのある二環化合物のオリゴマー又はコオリゴマー：具体例としては、ベンゾフラン、イソベンゾフラン、インドール、イソインドール、ベンゾチオフェン、ベンゾホスホール、ベンゾイミダゾール、プリン、インダゾール、ベンゾオキサゾール、ベンゾイソオキサゾール、ベンゾチアゾール、ナフタレン、キノリン、イソキノリン、キノキサリン、キナゾリン、シンノリン、これらの誘導体などの二環化合物の重合度６以下のオリゴマー又はコオリゴマーを挙げることができる。 (C) Oligomers or co-oligomers of bicyclic compounds that may have heteroelements (N, O, S, etc.): specific examples include benzofuran, isobenzofuran, indole, isoindole, benzothiophene, benzophosphole, benzo Mention may be made of oligomers or co-oligomers having a degree of polymerization of 6 or less of bicyclic compounds such as imidazole, purine, indazole, benzoxazole, benzoisoxazole, benzothiazole, naphthalene, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline and derivatives thereof. it can.
（ｄ）アリーレンビニレン（フェニレンビニレン、チエニンビニレンなど）を構成単位とする重合度６程度以下のオリゴマー。 (D) An oligomer having a degree of polymerization of about 6 or less having an arylene vinylene (such as phenylene vinylene or thienin vinylene) as a structural unit.
（ii）平面状ｐ型有機半導体化合物
ｐ型半導体としての性質を有する電子供与性のπ共役系有機化合物の内で、平面状の化合物としては、次の化合物を例示できる。
(Ii) Planar p-type organic semiconductor compound Among the electron-donating π-conjugated organic compounds having properties as a p-type semiconductor, the following compounds can be exemplified as the planar compound.
（ａ）芳香族環を４〜１０個有する平面状の多環芳香族炭化水素：具体例としては、ベンゾピレン、コロネン、コランヌレン、ピレン、ペリレン、トリフェニレン、オバレン、ベンゾペリレン、これらの誘導体等を例示できる。 (A) Planar polycyclic aromatic hydrocarbon having 4 to 10 aromatic rings: Specific examples include benzopyrene, coronene, corannulene, pyrene, perylene, triphenylene, ovalene, benzoperylene, and derivatives thereof. it can.
(ｂ)フタロシアニン化合物：具体例としては、フタロシアニン、フタロシアニン金属錯体等を例示できる。 (b) Phthalocyanine compounds: Specific examples include phthalocyanine and phthalocyanine metal complexes.
（ｃ）ポルフィリン化合物：具体例としては、ポルフィリン、ポリフィリン金属錯体等を例示できる。 (C) Porphyrin compounds: Specific examples include porphyrins and porphyrin metal complexes.
（２）n型半導体有機化合物
ｎ型半導体としての性質を有する化合物は、電子受容性のπ共役系有機化合物であれよい。この様な電子受容性のπ共役系有機化合物としては、置換基としてフッ素原子を有する共役系低分子化合物、置換基としてシアノ基を有する共役系低分子化合物、窒素原子を含む多環芳香族化合物などを例示できる。
(2) n-type semiconductor organic compound The compound having properties as an n-type semiconductor may be an electron-accepting π-conjugated organic compound. Examples of such electron-accepting π-conjugated organic compounds include conjugated low-molecular compounds having a fluorine atom as a substituent, conjugated low-molecular compounds having a cyano group as a substituent, and polycyclic aromatic compounds containing a nitrogen atom. Etc. can be illustrated.
(i) 鎖状ｎ型半導体有機化合物
電子受容性のπ共役系有機化合物の内で、鎖状の化合物の具体例としては、フッ素化オリゴチオフェン等を挙げることができる。
(i) Chain n-type semiconductor organic compound Among electron accepting π-conjugated organic compounds, specific examples of the chain compound include fluorinated oligothiophene.
（ii）平面状n型半導体有機化合物
ｎ型半導体としての性質を有する電子受容性のπ共役系有機化合物の内で、平面状の化合物としては、フッ素化フタロシアニン、ペリレンおよびその誘導体（例えば、N,N’-ビス(2,6-ジメチルフェニル)ペリレン-3,4,9,10-テトラカルボン酸ジイミド(PTCDI)、3,4,9,10-ペリレンテトラカルボン酸二無水物(PTCDA)等）、テトラピリジルポルフィリン、フッ素化ポルフィリン等を例示できる。
(Ii) Planar n-type semiconductor organic compound Among electron-accepting π-conjugated organic compounds having properties as an n-type semiconductor, planar compounds include fluorinated phthalocyanine, perylene and derivatives thereof (for example, N N'-bis (2,6-dimethylphenyl) perylene-3,4,9,10-tetracarboxylic acid diimide (PTCDI), 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), etc. ), Tetrapyridylporphyrin, fluorinated porphyrin, and the like.
（３）真空蒸着条件
真空蒸着の条件については特に限定的ではないが、使用する有機半導体化合物の種類に応じて、蒸着時の圧力、温度などを適宜設定して、０．１〜２ｎｍ／分程度の蒸着速度とすることが好ましい。この範囲の蒸着速度とすることによって、特に、良好に配向した有機半導体層を形成できる。
(3) Vacuum deposition conditions The conditions for vacuum deposition are not particularly limited, but depending on the type of organic semiconductor compound used, the pressure, temperature, etc. during deposition are appropriately set to 0.1 to 2 nm / min. It is preferable to set the deposition rate to a degree. By setting the deposition rate within this range, a particularly well-oriented organic semiconductor layer can be formed.
有機半導体層の厚さについては特に限定的ではないが、通常、１０〜６０ｎｍ程度とすればよい。 The thickness of the organic semiconductor layer is not particularly limited, but is usually about 10 to 60 nm.
(III)ｎ型有機半導体層の形成
上記した（II）工程において、ｐ型半導体としての性質を有する有機半導体化合物を用いて真空蒸着を行った場合には、形成されたｐ型有機半導体層の上に、ｎ型有機半導体層を形成する。この場合、ｎ型有機半導体層は、スピンコート法によって形成することが好ましく、これによって、優れた光電変換性能を有する有機薄膜太陽電池を得ることができる。
(III) Formation of n-type organic semiconductor layer In the above step (II), when vacuum deposition is performed using an organic semiconductor compound having properties as a p-type semiconductor, the formed p-type organic semiconductor layer An n-type organic semiconductor layer is formed thereon. In this case, the n-type organic semiconductor layer is preferably formed by a spin coating method, whereby an organic thin film solar cell having excellent photoelectric conversion performance can be obtained.
ｎ型有機半導体層を形成するために用いる有機半導体化合物としては、スピンコート法に使用する溶媒に対して可溶性のｎ型有機半導体化合物を用いることが好ましい。 As the organic semiconductor compound used for forming the n-type organic semiconductor layer, it is preferable to use an n-type organic semiconductor compound that is soluble in the solvent used in the spin coating method.
スピンコートに用いる溶媒としては、ｐ型有機半導体層およびテンプレート層に対して不溶性の溶媒を用いることが必要であり、使用するｎ型有機半導体化合物の種類に応じて適宜決めればよい。例えば、クロロホルム、クロロベンゼン、ジメチルホルムアミド、メタンスルホン酸等を用いることができる。 As a solvent used for spin coating, it is necessary to use a solvent that is insoluble in the p-type organic semiconductor layer and the template layer, and may be appropriately determined according to the type of the n-type organic semiconductor compound to be used. For example, chloroform, chlorobenzene, dimethylformamide, methanesulfonic acid and the like can be used.
この様なｎ型有機半導体化合物の具体例としては下記の化合物を挙げることができる。
（i） [6.6]-フェニル-C61-酪酸メチル（PCBM）（クロロホルム、クロロベンゼン可溶）等のフラーレンC60,C70誘導体
（ii）N,N’-ビス(2,6-ジメチルフェニル)ペリレン-3,4,9,10-テトラカルボン酸ジイミド（ジメチルホルムアミド(DMF)可溶）、3,4,9,10-ペリレンテトラカルボン酸二無水物等のペリレンおよびその誘導体
（iii）フッ素化ポルフィリン、テトラピリジルポルフィリン
（iv） フッ素化フタロシアニン
（ｖ） フッ素化オリゴチオフェン
（vi) テトラシアノキノジメタン(TCNQ)およびその誘導体
（vii）ナフタレン-1,4,5,8-テトラカルボン酸二無水物等のナフタレンおよびその誘導体
（viii）シアノ基を導入した PPV 誘導体(CN-PPV)（クロロホルム可溶）
（ix） ポリ(ベンゾイミダゾベンゾフェナントロリン) (BBL)（メタンスルホン酸可溶）
（ｘ） ポリ[(2,5-ジデシロキシ-1,4-フェニレン)(2,4,6-トリイソプロピルフェニルボラン)]（クロロホルム、クロロベンゼン可溶）。
Specific examples of such an n-type organic semiconductor compound include the following compounds.
(I) Fullerene C 60 and C 70 derivatives such as [6.6] -phenyl-C 61 -methyl butyrate (PCBM) (soluble in chloroform and chlorobenzene) (ii) N, N'-bis (2,6-dimethylphenyl) Perylene and its derivatives (iii) fluorination such as perylene-3,4,9,10-tetracarboxylic acid diimide (soluble in dimethylformamide (DMF)), 3,4,9,10-perylenetetracarboxylic dianhydride Porphyrin, tetrapyridylporphyrin (iv) Fluorinated phthalocyanine (v) Fluorinated oligothiophene (vi) Tetracyanoquinodimethane (TCNQ) and its derivatives (vii) Naphthalene-1,4,5,8-tetracarboxylic dianhydride Naphthalene and its derivatives (viii) PPV derivative (CN-PPV) with cyano group (chloroform soluble)
(Ix) Poly (benzimidazobenzophenanthroline) (BBL) (soluble in methanesulfonic acid)
(X) Poly [(2,5-didecyloxy-1,4-phenylene) (2,4,6-triisopropylphenylborane)] (soluble in chloroform and chlorobenzene).
スピンコート法によって形成されるｎ型有機半導体層の厚さについては特に限定的ではないが、電子受容体層としての機能を十分に発揮するためには、10〜50nm程度であることが好ましい。 The thickness of the n-type organic semiconductor layer formed by the spin coating method is not particularly limited, but is preferably about 10 to 50 nm in order to sufficiently exhibit the function as the electron acceptor layer.
有機薄膜太陽電池の素子構造
上記した方法で形成されるｐ型有機半導体層とｎ型有機半導体層を有する有機薄膜太陽電池素子の具体的な構造については特に限定はなく、通常の有機薄膜太陽電池素子と同様の構造とすることができる。例えば、透明電極が形成された透明基板上にｐ型有機半導体層とｎ型有機半導体層が順次積層され、更に、この上に金属電極が形成された構造とすることができる。この場合、透明電極が形成された透明基板とｐ型半導体層の間には、正孔注入材層が形成されていてもよく、また、ｎ型有機半導体膜と金属電極との間には、正孔ブロック材料層が形成されていてもよい。この様な有機薄膜太陽電池の各種構成要素の材料、即ち、透明基板、透明電極、正孔注入材、正孔ブロック材、金属電極などの材料としては、公知の有機薄膜太陽電池で使用されている材料を用いることができ、各構成要素の形成方法も常法に従えばよい。
Element structure of organic thin film solar cell There is no particular limitation on the specific structure of the organic thin film solar cell element having the p-type organic semiconductor layer and the n-type organic semiconductor layer formed by the above-described method. A structure similar to that of the element can be employed. For example, a p-type organic semiconductor layer and an n-type organic semiconductor layer are sequentially stacked on a transparent substrate on which a transparent electrode is formed, and a metal electrode is further formed thereon. In this case, a hole injection material layer may be formed between the transparent substrate on which the transparent electrode is formed and the p-type semiconductor layer, and between the n-type organic semiconductor film and the metal electrode, A hole blocking material layer may be formed. Materials for various components of such organic thin film solar cells, that is, materials such as transparent substrates, transparent electrodes, hole injection materials, hole blocking materials, metal electrodes, etc. are used in known organic thin film solar cells. The material which is used can be used, and the formation method of each component should just follow a conventional method.
本発明により得られる有機薄膜太陽電池素子のより具体的な構造としては、例えば、ｐ型半導体としての性質を有さない導電性高分子化合物によって配向ポリマー層を形成した場合には、下記（１）に示す各層が順次積層した構造とすることができる。
（１） 透明電極が形成された透明基板／（必要に応じて正孔注入材層）／ｐ型半導体の性質を有さない導電性高分子化合物による配向ポリマー層／ｐ型有機半導体化合物の蒸着膜／ｎ型有機半導体化合物のスピンコート層／（必要に応じて正孔ブロック材層）／金属電極。
As a more specific structure of the organic thin film solar cell element obtained by the present invention, for example, when an oriented polymer layer is formed of a conductive polymer compound having no properties as a p-type semiconductor, the following (1 The layers shown in FIG.
(1) Transparent substrate on which a transparent electrode is formed / (Positive hole injection material layer if necessary) / Evaporation of oriented polymer layer with conductive polymer compound having no p-type semiconductor properties / p-type organic semiconductor compound deposition Film / spin coat layer of n-type organic semiconductor compound / (hole blocking material layer as required) / metal electrode.
また、配向ポリマー層をｐ型半導体としての性質を有する導電性高分子化合物によって形成した場合には、下記（２）又は（３）に示す各層が順次積層した構造とすることができる。
（２） 透明電極が形成された透明基板／（必要に応じて正孔注入材層）／ｐ型導電性高分子化合物による配向ポリマー層／ｎ型有機半導体化合物の蒸着層／（必要に応じて正孔ブロック材層）／金属電極
（３） 透明電極が形成された透明基板／（必要に応じて正孔注入材層）／ｐ型導電性高分子化合物による配向ポリマー層／ｐ型有機半導体化合物の蒸着層／ｎ型有機半導体化合物のスピンコート層／（必要に応じて正孔ブロック材層）／金属電極
Moreover, when the oriented polymer layer is formed of a conductive polymer compound having a property as a p-type semiconductor, a structure in which the layers shown in the following (2) or (3) are sequentially laminated can be obtained.
(2) Transparent substrate on which a transparent electrode is formed / (Hole injection material layer if necessary) / Oriented polymer layer by p-type conductive polymer compound / Vapor deposition layer of n-type organic semiconductor compound / (If necessary) Hole blocking material layer) / Metal electrode (3) Transparent substrate on which a transparent electrode is formed / (Hole injection material layer if necessary) / Oriented polymer layer by p-type conductive polymer compound / p-type organic semiconductor compound Vapor-deposited layer / spin coat layer of n-type organic semiconductor compound / (hole blocking material layer if necessary) / metal electrode
本発明の有機薄膜太陽電池では、真空蒸着によって形成される鎖状又は平面状のｐ型有機半導体化合物又はｎ型有機半導体化合物が、基板面に平行に一定方向に配向したものとなる。これにより、有機半導体層においてπ−πスタック構造が形成されて該半導体層の基板に対して垂直方向における導電性が向上する。このため、本発明の有機薄膜太陽電池は、高いエネルギー変換効率を有するものとなる。 In the organic thin film solar cell of the present invention, a chain-like or planar p-type organic semiconductor compound or n-type organic semiconductor compound formed by vacuum deposition is oriented in a certain direction parallel to the substrate surface. Thereby, a π-π stack structure is formed in the organic semiconductor layer, and the conductivity in the direction perpendicular to the substrate of the semiconductor layer is improved. For this reason, the organic thin film solar cell of the present invention has high energy conversion efficiency.
以下、実施例を挙げて本発明を具体的に説明する。
参考例１
ポリチオフェン粉末を圧縮成型した断面が1mm×10mmの半円形のペレットを、250℃に加熱した溶融石英ガラス基板（10mm×38mm×0.7mm）に1.96MPaの圧力で押圧して、基板の長辺方向に沿って1m/minの掃引速度で掃引し、基板上に幅10mmのポリチオフェンの配向薄膜を形成した。膜厚は約5nmであった。
Hereinafter, the present invention will be specifically described with reference to examples.
Reference example 1
A semicircular pellet with a cross section of 1 mm x 10 mm, compression-molded from polythiophene powder, is pressed against a fused silica glass substrate (10 mm x 38 mm x 0.7 mm) heated to 250 ° C at a pressure of 1.96 MPa, and the long side direction of the substrate A polythiophene alignment thin film having a width of 10 mm was formed on the substrate. The film thickness was about 5 nm.
次いで、α-セキシチオフェン約30mgを直径10mm、長さ30mmの石英ルツボに入れ、真空チャンバー内において、該ルツボの上方約20cmのところにポリチオフェン配向処理した石英ガラス基板をホルダーに固定した。次いで、真空チャンバーを5×10-4Paの圧力に脱気し、水晶振動子で膜厚をモニターしながら、膜厚が5nm又は25nmになるように1〜3nm/minの蒸着速度で室温に保った基板にα-セキシチオフェンを蒸着した。 Next, about 30 mg of α-sexithiophene was placed in a quartz crucible having a diameter of 10 mm and a length of 30 mm, and a quartz glass substrate subjected to polythiophene orientation treatment was fixed to a holder in a vacuum chamber at a position about 20 cm above the crucible. Next, the vacuum chamber is evacuated to a pressure of 5 × 10 −4 Pa, and while monitoring the film thickness with a crystal oscillator, the film thickness is brought to room temperature at a deposition rate of 1 to 3 nm / min so that the film thickness becomes 5 nm or 25 nm. Α-sexithiophene was deposited on the kept substrate.
このようにして得られた薄膜に、ポリチオフェンペレットの掃引方向にそれぞれ平行と垂直の偏光を照射して吸収スペクトルを測定し、吸収の2色比を計算した。ここで、２色比は、（掃引方向に平行方向の吸収強度）／（掃引方向に垂直方向の吸収強度）として定義する。5nmのα-セキシチオフェン蒸着膜と25nmのα-セキシチオフェン蒸着膜の２色比はそれぞれ4.2と5.5であった。これは、α-セキシチオフェンの分子が、一軸配向したポリチオフェン配向薄膜におけるポリチオフェン分子鎖の方向に沿って一軸配向していることを示すものである。 The thin film thus obtained was irradiated with polarized light parallel to and perpendicular to the sweep direction of the polythiophene pellet, the absorption spectrum was measured, and the two-color ratio of absorption was calculated. Here, the dichroic ratio is defined as (absorption intensity in a direction parallel to the sweep direction) / (absorption intensity in a direction perpendicular to the sweep direction). The dichroic ratio of the 5 nm α-sexithiophene deposited film and the 25 nm α-sexithiophene deposited film was 4.2 and 5.5, respectively. This indicates that the α-sexithiophene molecules are uniaxially oriented along the direction of the polythiophene molecular chain in the uniaxially oriented polythiophene alignment thin film.
一方、ポリチオフェン粉末のペレットを用いてポリチオフェンの配向薄膜を形成する操作を行うことなく、それ以外は上記した方法と同様にして、溶融石英ガラス基板上に、α-セキシチオフェンを厚さが8nmとなるように真空蒸着させた。このα-セキシチオフェン膜について、上記した方法と同様にして吸収の2色比を計算したところ、２色比は１となり、一軸配向していないことが判った。 On the other hand, without performing an operation of forming an alignment thin film of polythiophene using pellets of polythiophene powder, the thickness of α-sexithiophene was 8 nm on a fused silica glass substrate in the same manner as described above. It was made to vacuum-deposit so that it might become. With respect to this α-sexithiophene film, the absorption two-color ratio was calculated in the same manner as described above, and it was found that the two-color ratio was 1, indicating that the film was not uniaxially oriented.
参考例２
n型シリコン(100)ウェハー（15mm×20mm×0.65mm）上に、ポリ(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルフォネート)（PEDOT:PSS, Baytron P AI 4083）を滴下し、3000回転/分で90秒の条件でスピンコートして、厚さ約45nmのPEDOT:PSS膜を形成した。このPEDOT:PSS膜上に参考例１と同様の方法で幅10mmのポリチオフェンの配向薄膜を形成し、次いで、参考例１と同様の方法で、真空蒸着法によってα-セキシチオフェンを50nm堆積させた。
Reference example 2
Poly (3,4-ethylenedioxythiophene) -poly (styrene sulfonate) (PEDOT: PSS, Baytron P AI 4083) is dropped onto an n-type silicon (100) wafer (15mm x 20mm x 0.65mm) A PEDOT: PSS film having a thickness of about 45 nm was formed by spin coating at 3000 rpm for 90 seconds. On this PEDOT: PSS film, a polythiophene alignment thin film having a width of 10 mm is formed in the same manner as in Reference Example 1, and then α-sexithiophene is deposited to a thickness of 50 nm by vacuum evaporation in the same manner as in Reference Example 1. It was.
このようにして得られた薄膜の微小角入射X線回折(GIXD)測定を行ったところ、α-セキシチオフェンは下地のポリチオフェン配向薄膜におけるポリチオフェン分子鎖の方向に沿って一軸配向していることが明らかになった。 The thin-angle X-ray diffraction (GIXD) measurement of the thin film thus obtained showed that α-sexithiophene was uniaxially oriented along the direction of the polythiophene molecular chain in the underlying polythiophene-oriented thin film. Became clear.
一方、ポリチオフェンの配向薄膜を形成する操作を行うことなく、それ以外は上記した方法と同様にして、真空蒸着法によってPEDOT:PSS膜上にα-セキシチオフェンを厚さが50nmとなるように堆積させた。 On the other hand, without performing an operation of forming an oriented thin film of polythiophene, the thickness of α-sexithiophene is 50 nm on the PEDOT: PSS film by vacuum deposition in the same manner as described above. Deposited.
このようにして得られた薄膜の微小角入射X線回折(GIXD)測定を行ったところ、α-セキシチオフェンは基板に対してほぼ垂直方向に配列していることが明らかになった。 The thin-film thus obtained was subjected to fine-angle incidence X-ray diffraction (GIXD) measurement, and it was found that α-sexithiophene was arranged almost perpendicularly to the substrate.
実施例１
ガラス上に幅2mm、長さ38mmの透明導電膜を2本形成した基板（13mm×38mm×0.7mm）の上に、正孔注入剤であるポリ(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルフォネート)（PEDOT:PSS, Baytron P AI 4083）を滴下し、3000回転/分で90秒の条件でスピンコートすることで、厚さ約45nmのPEDOT:PSS膜を形成した。
Example 1
Poly (3,4-ethylenedioxythiophene) -poly as a hole injecting agent on a substrate (13mm x 38mm x 0.7mm) with two transparent conductive films 2mm wide and 38mm long on glass (Styrene sulfonate) (PEDOT: PSS, Baytron P AI 4083) was added dropwise, and spin coating was performed at 3000 rpm for 90 seconds to form a PEDOT: PSS film having a thickness of about 45 nm.
一方、p型半導体であるポリチオフェン粉末を圧縮成形して断面が1mm×10mmの半円形のペレット状とし、これを250℃に加熱した上記基板のPEDOT:PSS膜上に1.96MPaの圧力で押圧して、基板長辺方向に沿って1m/minの掃引速度で掃引し、基板上に膜厚約5nm、幅10mmのポリチオフェンの配向薄膜を形成した。 On the other hand, a polythiophene powder, which is a p-type semiconductor, is compression-molded into a semicircular pellet with a cross section of 1 mm x 10 mm, and this is pressed onto the PEDOT: PSS film on the substrate heated to 250 ° C at a pressure of 1.96 MPa. Thus, an oriented polythiophene thin film having a thickness of about 5 nm and a width of 10 mm was formed on the substrate by sweeping along the long side direction of the substrate at a sweep speed of 1 m / min.
次いで、p型半導体であるα-セキシチオフェン約30mgを直径10mm、長さ30mmの石英ルツボに入れ、真空チャンバー内において、該ルツボの上方約20cmのところに上記基板をホルダーに固定した。次いで、真空チャンバーを5×10-4Paの圧力に脱気し、水晶振動子で膜厚をモニターしながら、膜厚が15nmになるように1〜3nm/minの蒸着速度で室温に保った基板にα-セキシチオフェンを蒸着した。 Next, about 30 mg of α-sexithiophene, which is a p-type semiconductor, was put in a quartz crucible having a diameter of 10 mm and a length of 30 mm, and the substrate was fixed to a holder at a position about 20 cm above the crucible in a vacuum chamber. Next, the vacuum chamber was evacuated to a pressure of 5 × 10 −4 Pa and kept at room temperature at a deposition rate of 1 to 3 nm / min so that the film thickness was 15 nm while monitoring the film thickness with a crystal resonator. Α-sexithiophene was deposited on the substrate.
上記した方法でα-セキシチオフェン膜を形成した基板を一度真空チャンバーから取り出し、α-セキシチオフェン上に、n型半導体である[6.6]-フェニル-C61-酪酸メチル(PCBM)の1.2wt%クロロベンゼン溶液を滴下し、3000回転/分で90秒の条件でスピンコートすることで、厚さ約40nmのPCBM膜を形成した。 The substrate on which the α-sexithiophene film was formed by the above-mentioned method was once taken out of the vacuum chamber, and 1.2 [1.6] -phenyl-C 61 -methyl butyrate (PCBM), which is an n-type semiconductor, was placed on α-sexithiophene. A PCBM film having a thickness of about 40 nm was formed by dropping a wt% chlorobenzene solution and performing spin coating at 3000 rpm for 90 seconds.
次いで、正孔ブロック材料であるバトクプロイン(BCP)約30mgを直径10mm、長さ30mmの石英ルツボに入れ、真空チャンバー内で、該ルツボの上方約20cmのところに上記基板をホルダーに固定した。基板ホルダーは真空チャンバー内で搬送することができ、フッ化リチウム約30mgを入れた蓋付タングステンボートと、アルミニウム約0.5gを入れたタングステン製フィラメントバスケットを共に、基板ホルダーの下方20cmの位置となるよう、真空チャンバー内に設置した。 Next, about 30 mg of Batocuproine (BCP), which is a hole blocking material, was placed in a quartz crucible having a diameter of 10 mm and a length of 30 mm, and the substrate was fixed to a holder at a position about 20 cm above the crucible in a vacuum chamber. The substrate holder can be transported in a vacuum chamber. A tungsten boat with a lid containing about 30 mg of lithium fluoride and a tungsten filament basket containing about 0.5 g of aluminum are both positioned 20 cm below the substrate holder. It was installed in a vacuum chamber.
次いで、真空チャンバーを5×10-4Paの圧力に脱気し、水晶振動子で膜厚をモニターしながら、膜厚が12nmになるように、BCPを1〜5nm/minの蒸着速度で室温に保った基板に蒸着した。次いで、幅2mm、長さ25mmのスリットが3本入ったマスクの直上に基板ホルダーを搬送し、スリットを介してフッ化リチウムを0.6nm/min以下の蒸着速度で基板に0.5nm堆積し、最後にAlを5〜15nm/minの蒸着速度で基板に50nm堆積し、金属電極とした。なお、マスクのスリットは、基板の透明電極と直交するように設置した。 Next, the vacuum chamber was evacuated to a pressure of 5 × 10 −4 Pa, and while monitoring the film thickness with a crystal resonator, BCP was deposited at room temperature at a deposition rate of 1 to 5 nm / min so that the film thickness became 12 nm. It vapor-deposited on the board | substrate kept at. Next, the substrate holder is transported directly above the mask with 3 slits with a width of 2 mm and a length of 25 mm, and lithium fluoride is deposited to 0.5 nm on the substrate through the slits at a deposition rate of 0.6 nm / min or less. Then, 50 nm of Al was deposited on the substrate at a deposition rate of 5 to 15 nm / min to form a metal electrode. In addition, the slit of the mask was installed so as to be orthogonal to the transparent electrode of the substrate.
こうして得た有機薄膜太陽電池素子を真空チャンバーより取り出した。透明電極と金属電極は直交しており、直交部分の面積は2×2mm2だった。窒素置換したグローブBOX中で、エポキシ系接着剤を塗布したガラス板（26mm×9mm×0.8mm）を有機薄膜太陽電池素子上に設置し、封止した。 The organic thin film solar cell element thus obtained was taken out from the vacuum chamber. The transparent electrode and the metal electrode were orthogonal to each other, and the area of the orthogonal part was 2 × 2 mm 2 . A glass plate (26 mm x 9 mm x 0.8 mm) coated with an epoxy adhesive was placed on the organic thin-film solar cell element and sealed in a nitrogen-substituted globe BOX.
こうして封止した有機薄膜太陽電池を、気温25度、湿度25%に制御された暗室に移動させ、正極側が透明電極、負極側が金属電極となるようにサブフェムトアンペアリモートソースメータ（KEITHLEY、6430）を接続し、-1Vから1Vの電圧印加下での暗電流値を測定した。 The organic thin-film solar cell thus sealed is moved to a dark room controlled at a temperature of 25 degrees and humidity of 25%, and the sub-femtoampere remote source meter (KEITHLEY, 6430) so that the positive electrode side is a transparent electrode and the negative electrode side is a metal electrode The dark current value was measured under the application of a voltage of -1V to 1V.
次いで、100mW/cm2の擬似太陽光（AM-1.5、関西科学機械株式会社、XES-502S）を照射し、-1Vから1Vの電圧印加下での光電流値を測定した。 Next, 100 mW / cm 2 of artificial sunlight (AM-1.5, Kansai Scientific Machinery Co., Ltd., XES-502S) was irradiated, and the photocurrent value was measured under the application of a voltage from -1V to 1V.
0Vから1Vに電圧を引加したときに、電流Iと電圧Vの積の絶対値、|IV|が最大になる点で最大電力Pmaxを得ることができる。入射光エネルギーをPinとすると、光を電気に変換する効率（光電変換効率; η）は、
η＝（Pmax/Pin）×100 [%] (1)
で表される。こうして光電変換効率を算出したところ、0.90%となった。
When a voltage is applied from 0 V to 1 V, the maximum power P max can be obtained at the point where the absolute value of the product of the current I and the voltage V, | IV | When the incident light energy and P in, the efficiency of converting light into electricity (photoelectric conversion efficiency; eta) is
η = (P max / P in ) × 100 [%] (1)
It is represented by Thus, the photoelectric conversion efficiency was calculated to be 0.90%.
比較例１
p型半導体であるポリチオフェン粉末のペレットを用いてポリチオフェンの配向薄膜を形成する操作を行うことなく、それ以外は、実施例１と同様にして、エポキシ系接着剤を塗布したガラス板による封止までの処理を行って有機薄膜太陽電池を得た。得られた有機薄膜太陽電池について、実施例１と同様にして光電変換効率を測定したところ、0.20%となった。
Comparative Example 1
Without performing the operation of forming an alignment thin film of polythiophene using pellets of polythiophene powder, which is a p-type semiconductor, other than that, up to sealing with a glass plate coated with an epoxy-based adhesive in the same manner as in Example 1 Thus, an organic thin film solar cell was obtained. The obtained organic thin film solar cell was measured for photoelectric conversion efficiency in the same manner as in Example 1. As a result, it was 0.20%.
以上の参考例１、参考例２、実施例１及び比較例１の結果から明らかなように、ポリチオフェン配向膜上に真空蒸着法で堆積させたα-セキシチオフェンは基板に平行に配向し、この薄膜を用いて有機薄膜太陽電池を形成した場合には（実施例１）、基板に垂直に配向したα-セキシチオフェン膜を用いた比較例１の有機薄膜太陽電池よりも光電変換効率が向上した。これは、実施例１の有機薄膜太陽電池では、基板に平行に配向したα-セキシチオフェンは、π-πスタッキングにより基板に垂直方向に正孔が移動しやすくなり、これにより有機薄膜太陽電池の光電変換効率が向上したと考えられる。 As is clear from the results of Reference Example 1, Reference Example 2, Example 1 and Comparative Example 1 above, α-sexithiophene deposited on the polythiophene alignment film by vacuum evaporation is aligned in parallel with the substrate, When an organic thin film solar cell was formed using this thin film (Example 1), the photoelectric conversion efficiency was higher than that of the organic thin film solar cell of Comparative Example 1 using an α-sexithiophene film oriented perpendicular to the substrate. Improved. This is because, in the organic thin film solar cell of Example 1, α-sexithiophene oriented parallel to the substrate facilitates movement of holes in the direction perpendicular to the substrate by π-π stacking. The photoelectric conversion efficiency is considered to have improved.
参考例３
ポリ(p-パラフェニレン)粉末を圧縮成形して得た断面が1mm×10mmの半円形のペレットを、220℃に加熱した溶融石英ガラス基板（10mm×38mm×0.7mm）に4MPaの圧力で押圧して、基板長辺方向に沿って0.34m/minの掃引速度で掃引し、基板上に膜厚約10nm、幅10mmのポリ(p-パラフェニレン)の配向薄膜を形成した。
Reference example 3
Pressing a semi-circular pellet with a cross section of 1 mm x 10 mm obtained by compression molding poly (p-paraphenylene) powder onto a fused silica glass substrate (10 mm x 38 mm x 0.7 mm) heated to 220 ° C at a pressure of 4 MPa Then, sweeping was performed along the long side direction of the substrate at a sweep speed of 0.34 m / min, and an oriented thin film of poly (p-paraphenylene) having a film thickness of about 10 nm and a width of 10 mm was formed on the substrate.
次いで、ペリレンテトラカルボン酸ジイミド(PTCDI)約30mgを直径10mm、長さ30mmの石英ルツボに入れ、真空チャンバー内において、該ルツボの上方約20cmのところに上記基板をホルダーに固定した。次いで、真空チャンバーを5×10-4Paの圧力に脱気し、水晶振動子で膜厚をモニターしながら、膜厚が27nmになるように0.5〜2.5nm/minの蒸着速度で室温に保った基板にPTCDIを蒸着した。 Next, about 30 mg of perylenetetracarboxylic acid diimide (PTCDI) was put in a quartz crucible having a diameter of 10 mm and a length of 30 mm, and the substrate was fixed to a holder at a position about 20 cm above the crucible in a vacuum chamber. Next, the vacuum chamber is evacuated to a pressure of 5 × 10 −4 Pa, and while maintaining the film thickness with a crystal resonator, the film is kept at room temperature at a deposition rate of 0.5 to 2.5 nm / min so that the film thickness becomes 27 nm. PTCDI was deposited on the substrate.
このようにして得られた薄膜にポリ(p-パラフェニレン)の掃引方向にそれぞれ平行と垂直の偏光を照射して吸収スペクトルを測定し、吸収の2色比を計算した。27nmのPTCDIを蒸着した膜の２色比は11であった。これは、下地のポリ(p-パラフェニレン)の一軸配向薄膜上に、基板に平行方向にPTCDIのペリレン骨格平面が配列することから生み出されると考えられる。 The thin film thus obtained was irradiated with polarized light parallel and perpendicular to the sweep direction of poly (p-paraphenylene), and the absorption spectrum was measured, and the two-color ratio of absorption was calculated. The 2 color ratio of the film deposited with 27 nm PTCDI was 11. This is thought to be caused by the arrangement of the PTCDI perylene skeleton planes in parallel to the substrate on the underlying poly (p-paraphenylene) uniaxially oriented thin film.
また、この薄膜のX線回折測定を行ったところ、PTCDIのペリレン骨格平面が基板に平行方向に配列していることが明らかになった。 In addition, X-ray diffraction measurement of this thin film revealed that the PTCDI perylene skeleton planes were aligned in parallel to the substrate.
一方、ポリ(p-パラフェニレン)配向薄膜を形成する操作を行うことなく、それ以外は上記した方法と同様にして、溶融石英ガラス基板上に、PTCDIを厚さが27nmとなるように真空蒸着させた。このα-セキシチオフェン膜について、上記した方法と同様にして吸収の2色比を計算したところ、２色比は１となり、基板面内でPTCDIは配向していないことが判った。 On the other hand, without performing the operation of forming a poly (p-paraphenylene) oriented thin film, PTCDI was vacuum-deposited on the fused silica glass substrate to a thickness of 27 nm in the same manner as described above, otherwise I let you. With respect to this α-sexithiophene film, the two-color ratio of absorption was calculated in the same manner as described above. The two-color ratio was 1, and it was found that PTCDI was not oriented in the substrate plane.
実施例２
ガラス上に幅2mm、長さ38mmの透明導電膜を2本形成した基板（13mm×38mm×0.7mm）の上に、正孔注入剤であるポリ(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルフォネート)（PEDOT:PSS, Baytron P AI 4083）を滴下し、3000回転/分で90秒の条件でスピンコートすることで、厚さ約45nmのPEDOT:PSS膜を形成した。
Example 2
Poly (3,4-ethylenedioxythiophene) -poly as a hole injecting agent on a substrate (13mm x 38mm x 0.7mm) with two transparent conductive films 2mm wide and 38mm long on glass (Styrene sulfonate) (PEDOT: PSS, Baytron P AI 4083) was added dropwise, and spin coating was performed at 3000 rpm for 90 seconds to form a PEDOT: PSS film having a thickness of about 45 nm.
一方、p型半導体であるポリ(p-パラフェニレン)粉末を圧縮成形して断面が1mm×10mmの半円形のペレット状とし、これを220℃に加熱した上記基板のPEDOT:PSS膜上に4MPaの圧力で押圧して、基板長辺方向に沿って0.34m/minの掃引速度で掃引し、基板上に膜厚約10nm、幅10mmのポリ(p-パラフェニレン)の配向薄膜を形成した。 On the other hand, a poly (p-paraphenylene) powder, which is a p-type semiconductor, is compression-molded into a semicircular pellet shape with a cross section of 1 mm × 10 mm, and this is 4 MPa on the PEDOT: PSS film of the substrate heated to 220 ° C. And a poly (p-paraphenylene) oriented thin film having a film thickness of about 10 nm and a width of 10 mm was formed on the substrate along the long side direction of the substrate at a sweep speed of 0.34 m / min.
次いで、n型半導体であるペリレンテトラカルボン酸ジイミド(PTCDI)約30mgを直径10mm、長さ30mmの石英ルツボに入れ、正孔ブロック材料であるバトクプロイン(BCP)約30mgを直径10mm、長さ30mmの別の石英ルツボに入れ、真空チャンバー内で、これらのルツボの上方約20cmのところに上記基板をホルダーに固定した。基板ホルダーは真空チャンバー内で搬送することができ、フッ化リチウム約30mgを入れた蓋付タングステンボートと、アルミニウム約0.5gを入れたタングステン製フィラメントバスケットを共に、基板ホルダーの下方20cmの位置となるよう、真空チャンバー内に設置した。 Next, about 30 mg of perylenetetracarboxylic acid diimide (PTCDI), which is an n-type semiconductor, is placed in a quartz crucible having a diameter of 10 mm and a length of 30 mm, and about 30 mg of batocuproine (BCP), which is a hole blocking material, is 10 mm in diameter and 30 mm in length. The substrate was placed in another quartz crucible, and the substrate was fixed to a holder at about 20 cm above these crucibles in a vacuum chamber. The substrate holder can be transported in a vacuum chamber. A tungsten boat with a lid containing about 30 mg of lithium fluoride and a tungsten filament basket containing about 0.5 g of aluminum are both positioned 20 cm below the substrate holder. It was installed in a vacuum chamber.
次いで、真空チャンバーを5×10-4Paの圧力に脱気し、水晶振動子で膜厚をモニターしながら、膜厚が25nmになるように0.5〜2.5nm/minの蒸着速度で室温に保った基板にPTCDIを蒸着した。次に、水晶振動子で膜厚をモニターしながら、膜厚が12nmになるように、BCPを1〜5nm/minの蒸着速度で室温に保った基板に蒸着した。次いで、幅2mm、長さ25mmのスリットが3本入ったマスクの直上に基板ホルダーを搬送し、スリットを介してフッ化リチウムを0.6nm/min以下の蒸着速度で基板に0.5nm堆積し、最後にAlを5〜15nm/minの蒸着速度で基板に50nm堆積して、金属電極とした。なお、マスクのスリットは、基板の透明電極と直交するように設置した。 Next, the vacuum chamber is evacuated to a pressure of 5 × 10 −4 Pa, and while maintaining the film thickness with a crystal resonator, the film is kept at room temperature at a deposition rate of 0.5 to 2.5 nm / min so that the film thickness becomes 25 nm. PTCDI was deposited on the substrate. Next, while monitoring the film thickness with a crystal resonator, BCP was deposited on a substrate kept at room temperature at a deposition rate of 1 to 5 nm / min so that the film thickness was 12 nm. Next, the substrate holder is transported directly above the mask with 3 slits with a width of 2 mm and a length of 25 mm, and lithium fluoride is deposited to 0.5 nm on the substrate through the slits at a deposition rate of 0.6 nm / min or less. A metal electrode was formed by depositing 50 nm of Al on the substrate at a deposition rate of 5 to 15 nm / min. In addition, the slit of the mask was installed so as to be orthogonal to the transparent electrode of the substrate.
こうして得た有機薄膜太陽電池素子を真空チャンバーより取り出した。透明電極と金属電極は直交しており、直交部分の面積は2×2mm2だった。窒素置換したグローブBOX中で、エポキシ系接着剤を塗布したガラス板（26mm×9mm×0.8mm）を有機薄膜太陽電池素子上に設置し、封止した。 The organic thin film solar cell element thus obtained was taken out from the vacuum chamber. The transparent electrode and the metal electrode were orthogonal to each other, and the area of the orthogonal part was 2 × 2 mm 2 . A glass plate (26 mm x 9 mm x 0.8 mm) coated with an epoxy adhesive was placed on the organic thin-film solar cell element and sealed in a nitrogen-substituted globe BOX.
こうして得た有機薄膜太陽電池について、実施例１と同様にして光電変換効率を算出したところ、1.9×10-3%となった。 With respect to the organic thin film solar cell thus obtained, the photoelectric conversion efficiency was calculated in the same manner as in Example 1. As a result, it was 1.9 × 10 −3 %.
比較例２
ガラス上に幅2mm、長さ38mmの透明導電膜を2本形成した基板（13mm×38mm×0.7mm）の上に、正孔注入剤であるポリ(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルフォネート)（PEDOT:PSS, Baytron P AI 4083）を滴下し、3000回転/分で90秒の条件でスピンコートすることで、厚さ約45nmのPEDOT:PSS膜を形成した。
Comparative Example 2
Poly (3,4-ethylenedioxythiophene) -poly as a hole injecting agent on a substrate (13mm x 38mm x 0.7mm) with two transparent conductive films 2mm wide and 38mm long on glass (Styrene sulfonate) (PEDOT: PSS, Baytron P AI 4083) was added dropwise, and spin coating was performed at 3000 rpm for 90 seconds to form a PEDOT: PSS film having a thickness of about 45 nm.
次いで、p型半導体であるポリ(p-パラフェニレン)の0.50wt%クロロベンゼン溶液を上記基板のPEDOT:PSS膜上に滴下し、500回転/分で90秒の条件でスピンコートし、真空中で130℃、一時間加熱することで、厚さ約10nmのポリ(p-パラフェニレン)薄膜を形成した。 Next, a 0.50 wt% chlorobenzene solution of poly (p-paraphenylene), which is a p-type semiconductor, is dropped on the PEDOT: PSS film of the substrate, spin-coated at 500 rpm for 90 seconds, and in vacuum A poly (p-paraphenylene) thin film having a thickness of about 10 nm was formed by heating at 130 ° C. for 1 hour.
この様にして基板上にポリ(p-パラフェニレン)薄膜を形成した後、n型半導体であるペリレンテトラカルボン酸ジイミドを蒸着する操作以降を実施例２と同様にして行い、エポキシ系接着剤を塗布したガラス板で封止した有機薄膜太陽電池を得た。得られた有機薄膜太陽電池について、実施例１と同様にして光電変換効率を測定したところ、7.5×10-6%となった。 After forming a poly (p-paraphenylene) thin film on the substrate in this manner, the operation of depositing perylenetetracarboxylic acid diimide, which is an n-type semiconductor, is performed in the same manner as in Example 2, and an epoxy adhesive is applied. The organic thin-film solar cell sealed with the apply | coated glass plate was obtained. When the photoelectric conversion efficiency of the obtained organic thin film solar cell was measured in the same manner as in Example 1, it was 7.5 × 10 −6 %.
以上の参考例３、実施例２及び比較例２の結果から、ポリ(p-パラフェニレン)配向膜上に真空蒸着法で堆積させたPTCDIは、ペリレン骨格が基板に平行に配向しており、この薄膜を用いて有機薄膜太陽電池を形成した場合には（実施例２）、スピンコート法で形成したポリ(p-パラフェニレン)上にランダムに配向したPTCDIを用いた比較例２の有機薄膜太陽電池よりも光電変換効率が向上した。 From the results of Reference Example 3, Example 2 and Comparative Example 2 described above, PTCDI deposited on a poly (p-paraphenylene) alignment film by a vacuum deposition method has a perylene skeleton aligned parallel to the substrate. When an organic thin film solar cell is formed using this thin film (Example 2), the organic thin film of Comparative Example 2 using PTCDI randomly oriented on poly (p-paraphenylene) formed by spin coating. Photoelectric conversion efficiency was improved compared to solar cells.
これは、実施例２の有機薄膜太陽電池では、基板に平行に配向したPTCDIは、π-πスタッキングにより基板に垂直方向に電子が移動しやすくなり、これにより有機薄膜太陽電池の光電変換効率が向上したと考えられる。 This is because, in the organic thin film solar cell of Example 2, the PTCDI oriented parallel to the substrate facilitates the movement of electrons in the direction perpendicular to the substrate due to the π-π stacking, which increases the photoelectric conversion efficiency of the organic thin film solar cell. It is thought that it improved.
実施例３
ガラス上に幅2mm、長さ38mmの透明導電膜を2本形成した基板（13mm×38mm×0.7mm）を用い、これを180℃に加熱し、導電性ポリマーであるポリアニリン粉末を圧縮成形して得た断面が1mm×10mmの半円形のペレットを2.1MPaの圧力で該基板に押圧して、基板長辺方向に沿って1m/minの掃引速度で掃引し、基板上に膜厚約2nm、幅10mmのポリアニリンの配向薄膜を形成した。
Example 3
Using a substrate (13mm x 38mm x 0.7mm) with two transparent conductive films 2mm wide and 38mm long on glass, this was heated to 180 ° C and the polyaniline powder, a conductive polymer, was compression molded. The obtained cross-section is 1 mm × 10 mm semi-circular pellets pressed against the substrate at a pressure of 2.1 MPa, and swept at a sweep speed of 1 m / min along the long side direction of the substrate. An oriented thin film of polyaniline having a width of 10 mm was formed.
次いで、p型半導体である銅フタロシアニン約50mgを直径10mm、長さ30mmの石英ルツボに入れ、真空チャンバー内で、ルツボの上方約30cmのところに上記基板をホルダーに固定した。次いで、真空チャンバーを2×10-4Paの圧力に脱気し、水晶振動子で膜厚をモニターしながら、膜厚が50nmになるように1〜3nm/minの蒸着速度で室温に保った基板に銅フタロシアニンを蒸着した。 Next, about 50 mg of copper phthalocyanine, which is a p-type semiconductor, was placed in a quartz crucible having a diameter of 10 mm and a length of 30 mm, and the substrate was fixed to a holder at a position about 30 cm above the crucible in a vacuum chamber. Next, the vacuum chamber was degassed to a pressure of 2 × 10 −4 Pa, and while maintaining the film thickness with a crystal resonator, the film thickness was kept at room temperature at a deposition rate of 1 to 3 nm / min so that the film thickness became 50 nm. Copper phthalocyanine was deposited on the substrate.
銅フタロシアニンを蒸着した基板を一度真空チャンバーから取り出し、銅フタロシアニン薄膜上に、n型半導体であるN,N’-ビス(2,6-ジメチルフェニル)ペリレン-3,4,9,10-テトラカルボン酸ジイミドの1.0wt%クロロベンゼン溶液を滴下し、2000回転/分で90秒の条件でスピンコートすることで、厚さ約30nmのN,N’-ビス(2,6-ジメチルフェニル)ペリレン-3,4,9,10-テトラカルボン酸ジイミド膜を形成した。 The substrate on which copper phthalocyanine is deposited is once taken out of the vacuum chamber, and N, N'-bis (2,6-dimethylphenyl) perylene-3,4,9,10-tetracarboxylic is an n-type semiconductor on the copper phthalocyanine thin film. A 1.0 wt% chlorobenzene solution of acid diimide was added dropwise and spin-coated at 2000 rpm for 90 seconds, resulting in N, N'-bis (2,6-dimethylphenyl) perylene-3 having a thickness of about 30 nm. A 4,9,10-tetracarboxylic acid diimide film was formed.
真空チャンバー内において、基板ホルダーを幅2mm、長さ25mmのスリットが3本入ったマスクの直上に設置し、マグネシウム約100mgを入れたタンタル製ボートと、銀約50mgを入れたタングステン製ボートを共に基板ホルダーの下方30cmの位置となるよう、真空チャンバー内に設置した。 Inside the vacuum chamber, a substrate holder is placed directly above the mask with 3 slits with a width of 2 mm and a length of 25 mm, and both a tantalum boat containing about 100 mg of magnesium and a tungsten boat containing about 50 mg of silver are both used. It set in the vacuum chamber so that it might be 30 cm below the substrate holder.
真空チャンバーを2×10-4Paの圧力に脱気し、N,N’-ビス(2,6-ジメチルフェニル)ペリレン-3,4,9,10-テトラカルボン酸ジイミド膜を形成した基板に対して、スリットを介してマグネシウムを9〜15nm/minの蒸着速度で、銀を0.9〜1.5nm/minの蒸着速度で共蒸着して50nm堆積させて金属電極を形成した。なお、マスクのスリットは、基板の透明電極と直交するように設置した。 The vacuum chamber was evacuated to a pressure of 2 × 10 −4 Pa and applied to the substrate on which the N, N′-bis (2,6-dimethylphenyl) perylene-3,4,9,10-tetracarboxylic acid diimide film was formed. In contrast, magnesium was co-evaporated at a deposition rate of 9 to 15 nm / min and silver was deposited at a deposition rate of 0.9 to 1.5 nm / min through a slit to deposit 50 nm to form a metal electrode. In addition, the slit of the mask was installed so as to be orthogonal to the transparent electrode of the substrate.
こうして得た有機薄膜太陽電池素子を真空チャンバーより取り出した。透明電極と金属電極は直交しており、直交部分の面積は2×2mm2だった。窒素置換したグローブBOX中で、エポキシ系接着剤を塗布したガラス板（26mm×9mm×0.8mm）を有機薄膜太陽電池素子上に設置し、封止した。 The organic thin film solar cell element thus obtained was taken out from the vacuum chamber. The transparent electrode and the metal electrode were orthogonal to each other, and the area of the orthogonal part was 2 × 2 mm 2 . A glass plate (26 mm x 9 mm x 0.8 mm) coated with an epoxy adhesive was placed on the organic thin-film solar cell element and sealed in a nitrogen-substituted globe BOX.
こうして封止した有機薄膜太陽電池について、実施例１と同様にして光電変換効率を算出したところ、3.0×10-1%となった。 With respect to the organic thin film solar cell thus sealed, the photoelectric conversion efficiency was calculated in the same manner as in Example 1. As a result, it was 3.0 × 10 −1 %.
比較例３
ガラス上に幅2mm、長さ38mmの透明導電膜を2本形成した基板（13mm×38mm×0.7mm）の上に、導電性ポリマーであるポリアニリンの0.30wt%N-メチルピロリドン溶液を滴下し、2500回転/分で60秒の条件でスピンコートすることで、厚さ約2nmのポリアニリン膜を形成した。
Comparative Example 3
A 0.30 wt% N-methylpyrrolidone solution of polyaniline, a conductive polymer, is dropped on a substrate (13 mm x 38 mm x 0.7 mm) on which two transparent conductive films with a width of 2 mm and a length of 38 mm are formed on glass. A polyaniline film having a thickness of about 2 nm was formed by spin coating at 2500 rpm for 60 seconds.
この様にしてポリアニリン膜を形成した後、銅フタロシアニン薄膜を蒸着する操作以降を実施例３と同様にして行い、エポキシ系接着剤を塗布したガラス板で封止した有機薄膜太陽電池を得た。得られた有機薄膜太陽電池について、実施例１と同様にして光電変換効率を測定したところ、2.0×10-2%となった。 After forming the polyaniline film in this way, the operation after vapor deposition of the copper phthalocyanine thin film was performed in the same manner as in Example 3 to obtain an organic thin film solar cell sealed with a glass plate coated with an epoxy adhesive. About the obtained organic thin film solar cell, when the photoelectric conversion efficiency was measured like Example 1, it was set to 2.0 * 10 <-2> %.
以上の実施例３及び比較例３の結果から明らかなように、ポリアニリン配向膜上に、銅フタロシアニンを蒸着させて得た薄膜を用いて有機薄膜太陽電池を形成した場合には（実施例３）、スピンコート法で形成した無配向のポリアニリン薄膜上に銅フタロシアニンを蒸着させて得た薄膜を用いた比較例３の有機薄膜太陽電池よりも光電変換効率が向上した。 As is clear from the results of Example 3 and Comparative Example 3 above, when an organic thin film solar cell is formed on a polyaniline alignment film using a thin film obtained by vapor deposition of copper phthalocyanine (Example 3). The photoelectric conversion efficiency was improved as compared with the organic thin film solar cell of Comparative Example 3 using a thin film obtained by depositing copper phthalocyanine on a non-oriented polyaniline thin film formed by spin coating.
これは、実施例３の有機薄膜太陽電池では、銅フタロシアニンが基板に平行に配向し、π-πスタッキングにより基板に垂直方向に正孔が移動しやすくなり、これにより光電変換効率が向上したと考えられる。 This is because, in the organic thin film solar cell of Example 3, copper phthalocyanine is oriented parallel to the substrate, and holes are easily moved in the direction perpendicular to the substrate by π-π stacking, thereby improving the photoelectric conversion efficiency. Conceivable.
実施例４
ガラス上に幅2mm、長さ38mmの透明導電膜を2本形成した基板（13mm×38mm×0.7mm）を用い、これを100℃に加熱し、p型半導体であるpoly(2,5-dioctyloxy-1,4-
phenylenevinylene) (DOPPV)粉末を圧縮成形して得た断面が1mm×10mmの半円形のペレットを2.94MPaの圧力で該基板に押圧して、基板長辺方向に沿って1m/minの掃引速度で掃引し、基板上に膜厚約30nm、幅10mmのDOPPVの配向薄膜を形成した。
Example 4
Using a substrate (13mm x 38mm x 0.7mm) with two transparent conductive films 2mm wide and 38mm long on glass, this is heated to 100 ° C and poly (2,5-dioctyloxy), a p-type semiconductor -1,4-
A semicircular pellet with a cross section of 1 mm x 10 mm obtained by compression molding (phenylenevinylene) (DOPPV) powder was pressed against the substrate at a pressure of 2.94 MPa, and a sweep speed of 1 m / min along the long side direction of the substrate. By sweeping, an oriented thin film of DOPPV having a thickness of about 30 nm and a width of 10 mm was formed on the substrate.
次いで、n型半導体であるテトラピリジルポルフィリン約60mgを直径10mm、長さ30mmの石英ルツボに入れ、真空チャンバー内で、該ルツボの上方約30cmのところに上記基板をホルダーに固定した。次いで、真空チャンバーを3×10-4Paの圧力に脱気し、水晶振動子で膜厚をモニターしながら、膜厚が35nmになるように1〜4nm/minの蒸着速度で室温に保った基板にテトラピリジルポルフィリンを蒸着した。 Next, about 60 mg of tetrapyridylporphyrin, which is an n-type semiconductor, was put into a quartz crucible having a diameter of 10 mm and a length of 30 mm, and the substrate was fixed to a holder at a position about 30 cm above the crucible in a vacuum chamber. Next, the vacuum chamber was evacuated to a pressure of 3 × 10 −4 Pa, and while maintaining the film thickness with a crystal resonator, it was kept at room temperature at a deposition rate of 1 to 4 nm / min so that the film thickness became 35 nm. Tetrapyridyl porphyrin was deposited on the substrate.
真空チャンバー内において、基板ホルダーを幅2mm、長さ25mmのスリットが3本入ったマスクの直上に設置し、マグネシウム約100mgを入れたタンタル製ボートと、銀約50mgを入れたタングステン製ボートを共に基板ホルダーの下方30cmの位置となるよう、真空チャンバー内に設置した。真空チャンバーを2×10-4Paの圧力に脱気し、テトラピリジルポルフィリン膜を形成した基板に対して、スリットを介してマグネシウムを9〜15nm/minの蒸着速度で、銀を0.9〜1.5nm/minの蒸着速度で共蒸着して50nm堆積させて金属電極とした。なお、マスクのスリットは、基板の透明電極と直交するように設置した。 Inside the vacuum chamber, a substrate holder is placed directly above the mask with 3 slits with a width of 2 mm and a length of 25 mm, and both a tantalum boat containing about 100 mg of magnesium and a tungsten boat containing about 50 mg of silver are both used. It set in the vacuum chamber so that it might be 30 cm below the substrate holder. The vacuum chamber was degassed to a pressure of 2 × 10 −4 Pa, and a substrate on which a tetrapyridylporphyrin film was formed, magnesium was deposited at a deposition rate of 9 to 15 nm / min through a slit, and silver was 0.9 to 1.5 nm. A metal electrode was formed by co-evaporation at an evaporation rate of / min and depositing 50 nm. In addition, the slit of the mask was installed so as to be orthogonal to the transparent electrode of the substrate.
こうして得た有機薄膜太陽電池素子を真空チャンバーより取り出した。透明電極と金属電極は直交しており、直交部分の面積は2×2mm2だった。窒素置換したグローブBOX中で、エポキシ系接着剤を塗布したガラス板（26mm×9mm×0.8mm）を有機薄膜太陽電池素子上に設置し、封止した。 The organic thin film solar cell element thus obtained was taken out from the vacuum chamber. The transparent electrode and the metal electrode were orthogonal to each other, and the area of the orthogonal part was 2 × 2 mm 2 . A glass plate (26 mm x 9 mm x 0.8 mm) coated with an epoxy adhesive was placed on the organic thin-film solar cell element and sealed in a nitrogen-substituted globe BOX.
こうして封止をした有機薄膜太陽電池について、実施例１と同様にして光電変換効率を算出したところ、0.10%となった。 With respect to the organic thin film solar cell thus sealed, the photoelectric conversion efficiency was calculated in the same manner as in Example 1, and the result was 0.10%.
比較例４
ガラス上に幅2mm、長さ38mmの透明導電膜を2本形成した基板（13mm×38mm×0.7mm）の上に、p型半導体であるpoly(2,5-dioctyloxy-1,4-phenylenevinylene) (DOPPV)の1.5wt%水溶液を滴下し、1000回転/分で30秒の条件でスピンコートすることで、厚さ約30nmのDOPPV膜を形成した。
Comparative Example 4
Poly (2,5-dioctyloxy-1,4-phenylenevinylene), a p-type semiconductor, on a substrate (13mm × 38mm × 0.7mm) with two transparent conductive films 2mm wide and 38mm long on glass A DOPPV film having a thickness of about 30 nm was formed by dropping a 1.5 wt% aqueous solution of (DOPPV) and spin-coating it at 1000 rpm for 30 seconds.
この様にしてDOPPV膜を形成した後、テトラピリジルポルフィリンを蒸着する操作以降を実施例４と同様にして行い、エポキシ系接着剤を塗布したガラス板で封止した有機薄膜太陽電池を得た。得られた有機薄膜太陽電池について、実施例１と同様にして光電変換効率を測定したところ、0.073%となった。 After forming the DOPPV film in this manner, the operation after vapor deposition of tetrapyridylporphyrin was performed in the same manner as in Example 4 to obtain an organic thin film solar cell sealed with a glass plate coated with an epoxy-based adhesive. The obtained organic thin film solar cell was measured for photoelectric conversion efficiency in the same manner as in Example 1. As a result, it was 0.073%.
以上の実施例４及び比較例４の結果から明らかなように、DOPPV配向膜上にテトラピリジルポルフィリンを蒸着させて得た薄膜を用いて有機薄膜太陽電池を形成した場合には（実施例４）、スピンコート法で形成した無配向のDOPPV膜上にテトラピリジルポルフィリンを蒸着させて得た薄膜を用いた比較例４の有機薄膜太陽電池よりも光電変換効率が向上した。 As is clear from the results of Example 4 and Comparative Example 4 above, when an organic thin film solar cell is formed using a thin film obtained by vapor-depositing tetrapyridylporphyrin on a DOPPV alignment film (Example 4) The photoelectric conversion efficiency was improved as compared with the organic thin film solar cell of Comparative Example 4 using a thin film obtained by vapor-depositing tetrapyridylporphyrin on a non-oriented DOPPV film formed by spin coating.
これは、実施例４の有機薄膜太陽電池では、テトラピリジルポルフィリンが基板に平行に配向し、π-πスタッキングにより基板に垂直方向に電子が移動しやすくなり、これにより有機薄膜太陽電池の光電変換効率が向上したと考えられる。 This is because in the organic thin film solar cell of Example 4, tetrapyridylporphyrin is oriented parallel to the substrate, and π-π stacking facilitates movement of electrons in the direction perpendicular to the substrate. The efficiency is thought to have improved.
実施例５
ガラス上に幅2mm、長さ38mmの透明導電膜を2本形成した基板（13mm×38mm×0.7mm）の上に、正孔注入剤であるポリ(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルフォネート)（PEDOT:PSS, Baytron P AI 4083）を滴下し、3000回転/分で90秒の条件でスピンコートすることで、厚さ約45nmのPEDOT:PSS膜を形成した。
Example 5
Poly (3,4-ethylenedioxythiophene) -poly as a hole injecting agent on a substrate (13mm x 38mm x 0.7mm) with two transparent conductive films 2mm wide and 38mm long on glass (Styrene sulfonate) (PEDOT: PSS, Baytron P AI 4083) was added dropwise, and spin coating was performed at 3000 rpm for 90 seconds to form a PEDOT: PSS film having a thickness of about 45 nm.
一方、p型半導体であるコポリマー、poly(4-(3,4'-dihexyl-2,2'-bithiophen-5-yl)-7-(5'-(9,9-dioctyl-9H-fluoren-2-yl)-3,4'-dihexyl-2,2'-bithiophen-5-yl)benzo[c][1,2,5]-thiadiazole) (F8TTBTT)粉末を圧縮成形して断面が1mm×10mmの半円形のペレット状とし、これを100℃に加熱した上記基板のPEDOT:PSS膜上に1.96MPaの圧力で押圧して、基板長辺方向に沿って1m/minの掃引速度で掃引し、基板上に膜厚約40nm、幅10mmのF8TTBTTの配向薄膜を形成した。 On the other hand, a copolymer that is a p-type semiconductor, poly (4- (3,4'-dihexyl-2,2'-bithiophen-5-yl) -7- (5 '-(9,9-dioctyl-9H-fluoren- 2-yl) -3,4'-dihexyl-2,2'-bithiophen-5-yl) benzo [c] [1,2,5] -thiadiazole) (F8TTBTT) Press the PEDOT: PSS film of the above substrate heated to 100 ° C with a pressure of 1.96 MPa and sweep it at a sweep speed of 1 m / min along the long side direction of the substrate. An oriented thin film of F8TTBTT having a thickness of about 40 nm and a width of 10 mm was formed on the substrate.
次いで、n型半導体であるフッ素化フタロシアニン(F16CuPc)約30mgを直径10mm、長さ30mmの石英ルツボにいれ、正孔ブロック材料であるバトクプロイン(BCP)約30mgを直径10mm、長さ30mmの別の石英ルツボに入れ、真空チャンバー内で、これらのルツボの上方約20cmのところに上記基板をホルダーに固定した。基板ホルダーは真空チャンバー内で搬送することができ、フッ化リチウム約30mgを入れた蓋付タングステンボートと、アルミニウム約0.5gを入れたタングステン製フィラメントバスケットを共に、基板ホルダーの下方20cmの位置となるよう、真空チャンバー内に設置した。 Next, about 30 mg of fluorinated phthalocyanine (F 16 CuPc), which is an n-type semiconductor, is put in a quartz crucible having a diameter of 10 mm and a length of 30 mm, and about 30 mg of hole blocking material, batocuproine (BCP), is 10 mm in diameter and 30 mm in length. The substrate was placed in another quartz crucible, and the substrate was fixed to a holder at about 20 cm above these crucibles in a vacuum chamber. The substrate holder can be transported in a vacuum chamber. A tungsten boat with a lid containing about 30 mg of lithium fluoride and a tungsten filament basket containing about 0.5 g of aluminum are both positioned 20 cm below the substrate holder. It was installed in a vacuum chamber.
真空チャンバーを8×10-5Paの圧力に脱気し、水晶振動子で膜厚をモニターしながら、膜厚が30nmになるように0.5〜2.0nm/minの蒸着速度で室温に保った基板にF16CuPcを蒸着した。次に、水晶振動子で膜厚をモニターしながら、膜厚が10nmになるように、BCPを1〜5nm/minの蒸着速度で室温に保った基板に蒸着した。次いで、幅2mm、長さ25mmのスリットが3本入ったマスクの直上に基板ホルダーを搬送し、スリットを介してフッ化リチウムを0.6nm/min以下の蒸着速度で基板に0.5nm堆積させ、最後にAlを5〜15nm/minの蒸着速度で基板に100nm堆積させ、金属電極を形成した。なお、マスクのスリットは、基板の透明電極と直交するように設置した。 The substrate was kept at room temperature at a deposition rate of 0.5 to 2.0 nm / min so that the film thickness would be 30 nm while the vacuum chamber was degassed to a pressure of 8 × 10 −5 Pa and the film thickness was monitored with a crystal resonator. F 16 CuPc was deposited on the film. Next, while monitoring the film thickness with a quartz resonator, BCP was deposited on a substrate kept at room temperature at a deposition rate of 1 to 5 nm / min so that the film thickness was 10 nm. Next, transport the substrate holder directly above the mask with 3 slits with a width of 2 mm and a length of 25 mm, and deposit lithium fluoride on the substrate at a deposition rate of 0.6 nm / min or less through the slits, Then, Al was deposited to a thickness of 100 nm on the substrate at a deposition rate of 5 to 15 nm / min to form a metal electrode. In addition, the slit of the mask was installed so as to be orthogonal to the transparent electrode of the substrate.
こうして得た有機薄膜太陽電池素子を真空チャンバーより取り出した。透明電極と金属電極は直交しており、直交部分の面積は2×2mm2だった。窒素置換したグローブBOX中で、エポキシ系接着剤を塗布したガラス板（26mm×9mm×0.8mm）を有機薄膜太陽電池素子上に設置し、封止した。 The organic thin film solar cell element thus obtained was taken out from the vacuum chamber. The transparent electrode and the metal electrode were orthogonal to each other, and the area of the orthogonal part was 2 × 2 mm 2 . A glass plate (26 mm x 9 mm x 0.8 mm) coated with an epoxy adhesive was placed on the organic thin-film solar cell element and sealed in a nitrogen-substituted globe BOX.
こうして封止をした有機薄膜太陽電池について、実施例１と同様にして光電変換効率を算出したところ、0.21%となった。 With respect to the organic thin film solar cell thus sealed, the photoelectric conversion efficiency was calculated in the same manner as in Example 1. As a result, it was 0.21%.
比較例５
ガラス上に幅2mm、長さ38mmの透明導電膜を2本形成した基板（13mm×38mm×0.7mm）の上に、正孔注入剤であるポリ(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルフォネート)（PEDOT:PSS, Baytron P AI 4083）を滴下し、3000回転/分で90秒の条件でスピンコートすることで、厚さ約45nmのPEDOT:PSS膜を形成した。次いで、p型半導体であるコポリマー（F8TTBTT）の1.2wt%クロロベンゼン溶液を滴下し、2000回転/分で60秒の条件でスピンコートし、次いで真空中で130℃、一時間加熱することで、厚さ約40nmのF8TTBTT薄膜を形成した。
Comparative Example 5
Poly (3,4-ethylenedioxythiophene) -poly as a hole injecting agent on a substrate (13mm x 38mm x 0.7mm) with two transparent conductive films 2mm wide and 38mm long on glass (Styrene sulfonate) (PEDOT: PSS, Baytron P AI 4083) was added dropwise, and spin coating was performed at 3000 rpm for 90 seconds to form a PEDOT: PSS film having a thickness of about 45 nm. Next, a 1.2 wt% chlorobenzene solution of a copolymer (F8TTBTT), which is a p-type semiconductor, is added dropwise, spin-coated at 2000 rpm for 60 seconds, and then heated in a vacuum at 130 ° C. for 1 hour, An F8TTBTT thin film with a thickness of about 40 nm was formed.
この様にして基板上にF8TTBTT薄膜を形成した後、n型半導体であるフッ素化フタロシアニン(F16CuPc)を蒸着する操作以降を実施例５と同様にして行い、エポキシ系接着剤を塗布したガラス板で封止した有機薄膜太陽電池を得た。得られた有機薄膜太陽電池について、実施例１と同様にして光電変換効率を測定したところ、0.068%となった。 After the F8TTBTT thin film was formed on the substrate in this way, the operation of depositing fluorinated phthalocyanine (F 16 CuPc), which is an n-type semiconductor, was performed in the same manner as in Example 5 and the glass coated with an epoxy adhesive was applied. An organic thin film solar cell sealed with a plate was obtained. When the photoelectric conversion efficiency of the obtained organic thin film solar cell was measured in the same manner as in Example 1, it was 0.068%.
以上の実施例５及び比較例５の結果から、p型半導体であるF8TTBTT配向膜上に真空蒸着法で堆積させたn型半導体である(F16CuPc)は、フタロシアニン骨格が基板に平行に配向しており、この薄膜を用いて有機薄膜太陽電池を形成した場合には（実施例５）、スピンコート法で形成したF8TTBTT膜上に、ランダムに配向したF16CuPc を用いた比較例５の有機薄膜太陽電池よりも光電変換効率が向上した。 From the results of Example 5 and Comparative Example 5 above, the n-type semiconductor (F 16 CuPc) deposited by vacuum deposition on the F8TTBTT alignment film, which is a p-type semiconductor, has a phthalocyanine skeleton aligned parallel to the substrate. When an organic thin-film solar cell is formed using this thin film (Example 5), the comparative example 5 using F 16 CuPc randomly oriented on the F8TTBTT film formed by spin coating is used. Photoelectric conversion efficiency was improved compared to organic thin film solar cells.
これは、実施例５の有機薄膜太陽電池では、F16CuPcが基板に平行に配向し、π-πスタッキングにより基板に垂直方向に電子が移動しやすくなり、これにより有機薄膜太陽電池の光電変換効率が向上したと考えられる。 This is because in the organic thin film solar cell of Example 5, F 16 CuPc is oriented parallel to the substrate, and π-π stacking makes it easy for electrons to move in the direction perpendicular to the substrate. The efficiency is thought to have improved.
Claims (7)
（１） 透明電極が形成された透明基板／（必要に応じて正孔注入材層）／ｐ型半導体の性質を有さない導電性高分子化合物による配向したポリマー層／ｐ型有機半導体化合物の蒸着層／ｎ型有機半導体化合物のスピンコート層／（必要に応じて正孔ブロック材層）／金属電極、
（２） 透明電極が形成された透明基板／（必要に応じて正孔注入材層）／ｐ型導電性高分子化合物による配向したポリマー層／ｎ型有機半導体化合物の蒸着層／（必要に応じて正孔ブロック材層）／金属電極
（３） 透明電極が形成された透明基板／（必要に応じて正孔注入材層）／ｐ型導電性高分子化合物による配向したポリマー層／ｐ型有機半導体化合物の蒸着層／ｎ型有機半導体化合物のスピンコート層／（必要に応じて正孔ブロック材層）／金属電極。 The organic thin-film solar cell according to any one of claims 1 to 3, which has any one of the following (1) to (3):
(1) Transparent substrate on which a transparent electrode is formed / (Positive hole injection material layer if necessary) / Organic polymer layer with conductive polymer compound having no p-type semiconductor properties / p-type organic semiconductor compound Deposition layer / spin coat layer of n-type organic semiconductor compound / (hole blocking material layer if necessary) / metal electrode,
(2) Transparent substrate on which a transparent electrode is formed / (Positive hole injection material layer if necessary) / Polymer layer oriented with p-type conductive polymer compound / Vapor deposition layer of n-type organic semiconductor compound / (As necessary Hole blocking material layer) / metal electrode (3) transparent substrate on which transparent electrode is formed / (hole injection material layer if necessary) / polymer layer oriented by p-type conductive polymer compound / p-type organic Vapor deposition layer of semiconductor compound / spin coat layer of n-type organic semiconductor compound / (hole blocking material layer if necessary) / metal electrode.
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| JP2018170369A (en) * | 2017-03-29 | 2018-11-01 | 新日鉄住金化学株式会社 | Material for organic electroluminescent element and organic electroluminescent element using the same |
| JP2018170383A (en) * | 2017-03-29 | 2018-11-01 | 新日鉄住金化学株式会社 | Material for organic electroluminescent element and organic electroluminescent element using the same |
| JP2019140316A (en) * | 2018-02-14 | 2019-08-22 | 国立大学法人京都工芸繊維大学 | Laminate having organic semiconductor crystal layer and conductive polymer alignment film, device including the same, and method for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018170369A (en) * | 2017-03-29 | 2018-11-01 | 新日鉄住金化学株式会社 | Material for organic electroluminescent element and organic electroluminescent element using the same |
| JP2018170383A (en) * | 2017-03-29 | 2018-11-01 | 新日鉄住金化学株式会社 | Material for organic electroluminescent element and organic electroluminescent element using the same |
| JP2019140316A (en) * | 2018-02-14 | 2019-08-22 | 国立大学法人京都工芸繊維大学 | Laminate having organic semiconductor crystal layer and conductive polymer alignment film, device including the same, and method for manufacturing the same |
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