JP6613037B2 - Organic photoelectric conversion device and manufacturing method thereof - Google Patents
Organic photoelectric conversion device and manufacturing method thereof Download PDFInfo
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- JP6613037B2 JP6613037B2 JP2015057355A JP2015057355A JP6613037B2 JP 6613037 B2 JP6613037 B2 JP 6613037B2 JP 2015057355 A JP2015057355 A JP 2015057355A JP 2015057355 A JP2015057355 A JP 2015057355A JP 6613037 B2 JP6613037 B2 JP 6613037B2
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- photoelectric conversion
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- metal nanoparticles
- organic photoelectric
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- DCZNSJVFOQPSRV-UHFFFAOYSA-N n,n-diphenyl-4-[4-(n-phenylanilino)phenyl]aniline Chemical class C1=CC=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 DCZNSJVFOQPSRV-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002848 poly(3-alkoxythiophenes) Polymers 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Photovoltaic Devices (AREA)
Description
本発明の実施形態は、有機光電変換素子及びその製造方法に関する。 Embodiments described herein relate generally to an organic photoelectric conversion element and a method for manufacturing the same.
有機光電変換素子として、例えば、有機薄膜太陽電池が知られている。有機薄膜太陽電池は、導電性ポリマーやフラーレン等を組み合わせた有機薄膜半導体を用いた太陽電池である。有機薄膜太陽電池は、シリコンやＣＩＧＳ（Copper Indium Gallium DiSelenide）、ＣｄＴｅなどの無機系材料をベースとした太陽電池に比べて光電変換膜を塗布や印刷という簡便な方法で生産でき、低コスト化できる可能性がある。その反面、有機薄膜太陽電池の変換効率は、従来の無機系太陽電池と比較して低いという問題を有する。 As an organic photoelectric conversion element, for example, an organic thin film solar cell is known. An organic thin film solar cell is a solar cell using an organic thin film semiconductor in which a conductive polymer, fullerene, or the like is combined. Organic thin-film solar cells can be produced by a simple method of applying or printing a photoelectric conversion film compared to solar cells based on inorganic materials such as silicon, CIGS (Copper Indium Gallium DiSelenide), and CdTe, which can reduce costs. there is a possibility. On the other hand, the conversion efficiency of the organic thin film solar cell has a problem that it is lower than that of a conventional inorganic solar cell.
そこで、従来から、金属ナノ粒子を有機薄膜太陽電池に組み込むことで変換効率を向上させる試みがなされてきた。例えば、金属ナノ粒子に光を照射すると、金属ナノ粒子中の電子が光と相互作用し、局在表面プラズモン共鳴が起こり、金属ナノ粒子表面近傍の電場が増強される現象が生じる。光電変換層にこの強い電場生じるとキャリア数の生成が増加し、その結果変換効率も向上する。 Therefore, conventionally, attempts have been made to improve conversion efficiency by incorporating metal nanoparticles into an organic thin film solar cell. For example, when a metal nanoparticle is irradiated with light, electrons in the metal nanoparticle interact with light, local surface plasmon resonance occurs, and the electric field near the surface of the metal nanoparticle is enhanced. When this strong electric field is generated in the photoelectric conversion layer, the generation of the number of carriers increases, and as a result, the conversion efficiency is also improved.
例えば、光リソグラフィーとエッチング技術を用いて導電性基板上に金属ナノ構造を形成した第１の有機薄膜太陽電池が知られている。この第１の有機薄膜太陽電池においては、金属ナノ構造による電場増強光効果によって有機薄膜太陽電池の短絡電流密度向上が確認されている。 For example, a first organic thin film solar cell in which metal nanostructures are formed on a conductive substrate using photolithography and etching techniques is known. In the first organic thin-film solar cell, it has been confirmed that the short-circuit current density of the organic thin-film solar cell is improved by the electric field-enhanced light effect due to the metal nanostructure.
また、導電性基板上に金属ナノ粒子を内包した正孔輸送層を形成した第２の有機薄膜太陽電池が知られている。この第２の有機薄膜太陽電池では、金属ナノ粒子を内包していない場合と比較して有機薄膜太陽電池の特性は向上しているが、必ずしも局在表面プラズモン効果によって変換効率が改善したわけではないと考えられる。 In addition, a second organic thin-film solar cell is known in which a hole transport layer including metal nanoparticles is formed on a conductive substrate. In the second organic thin film solar cell, the characteristics of the organic thin film solar cell are improved as compared with the case where the metal nanoparticles are not included, but the conversion efficiency is not necessarily improved by the localized surface plasmon effect. It is not considered.
このように、有機薄膜太陽電池の導電性基板上に金属ナノ粒子を内包した正孔輸送層を形成することで、変換効率の向上が可能である。 Thus, the conversion efficiency can be improved by forming the hole transport layer including the metal nanoparticles on the conductive substrate of the organic thin film solar cell.
ところが、導電性基板上に金属ナノ粒子を内包した正孔輸送層を低コストかつ簡便に形成することは容易ではない。上記第１の有機薄膜太陽電池は、光リソグラフィーとエッチング技術を用いて製造するため、設備コストが大きく、プロセス数も多い。 However, it is not easy to form a hole transport layer containing metal nanoparticles on a conductive substrate at low cost and in a simple manner. Since the first organic thin-film solar cell is manufactured using photolithography and etching technology, the equipment cost is high and the number of processes is also large.
また、上記第２の有薄膜太陽電池は、金属ナノ粒子溶液を導電性高分子溶液に添加して製造するため、材料コストは低い。しかし、金属ナノ粒子溶液を添加した導電性高分子溶液を透明電極上に滴下し、一般的に用いられているスピンコート塗布法で正孔輸送層の成膜を試みると、スピンコート回転による遠心力で金属ナノ粒子の大部分が飛散される。このため、所望の金属ナノ粒子濃度を有する正孔輸送層の形成は容易では無く、結局材料コストも増えてしまう。 In addition, since the second thin film solar cell is manufactured by adding the metal nanoparticle solution to the conductive polymer solution, the material cost is low. However, when a conductive polymer solution with a metal nanoparticle solution added is dropped onto a transparent electrode and a hole transport layer is formed by a generally used spin coat coating method, a spin coating by centrifugal rotation is performed. Most of the metal nanoparticles are scattered by the force. For this reason, it is not easy to form a hole transport layer having a desired metal nanoparticle concentration, resulting in an increase in material cost.
本実施形態は、変換効率が高く、低コスト、かつ既存のプロセスラインの大幅な変更を必要としない有機光電変換素子およびその製造方法を提供する。 The present embodiment provides an organic photoelectric conversion element that has high conversion efficiency, low cost, and does not require significant changes to existing process lines, and a method for manufacturing the same.
本実施形態による有機光電変換素子は、第１電極と、前記第１電極上に設けられた正孔輸送層と、前記正孔輸送層上に設けられ、有機ｐ型半導体および有機ｎ型半導体を有する有機光電変換層と、前記有機光電変換層上に設けられた電子輸送層と、前記電子輸送層上に設けられた第２電極と、を備え、前記正孔輸送層は、金属ナノ粒子とポリエチレンジオキシチオフェン／ポリスチレンスルホン酸（ＰＥＤＯＴ／ＰＳＳ）を含み、前記金属ナノ粒子の平均粒径ｄと前記正孔輸送層の膜厚ｔとの間にｄ＜ｔの関係が成立し、かつ、前記金属ナノ粒子が前記第１電極側に偏在し、前記第１電極側に配置されている前記金属ナノ粒子の密度が１〜５５粒子／μｍ２の範囲内にある。 The organic photoelectric conversion device according to the present embodiment includes a first electrode, a hole transport layer provided on the first electrode, an organic p-type semiconductor and an organic n-type semiconductor provided on the hole transport layer. An organic photoelectric conversion layer, an electron transport layer provided on the organic photoelectric conversion layer, and a second electrode provided on the electron transport layer, wherein the hole transport layer includes metal nanoparticles and Including polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT / PSS), a relationship of d <t is established between the average particle diameter d of the metal nanoparticles and the film thickness t of the hole transport layer, and The metal nanoparticles are unevenly distributed on the first electrode side, and the density of the metal nanoparticles arranged on the first electrode side is in the range of 1 to 55 particles / μm 2 .
以下、図面を参照して本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
（一実施形態）
一実施形態による有機光電変換素子を図１に示す。この実施形態の有機光電変換素子１は、基板１１と、透明電極１２と、金属ナノ粒子１３が内包された正孔輸送層１４と、光電変換層１５と、電子輸送層１６と、対向電極１７と、を備えている。透明電極１２は基板１１上に設けられ、正孔輸送層１４は透明電極１２上に設けられる。光電変換層１５は正孔輸送層１４上に設けられ、ｐ型半導体とｎ型半導体とがバルクヘテロジャンクションした構造の薄膜である。電子輸送層１６は光電変換層１５上に設けられ、対向電極１７は電子輸送層１６上に設けられる。
(One embodiment)
The organic photoelectric conversion element by one Embodiment is shown in FIG. The organic photoelectric conversion element 1 according to this embodiment includes a substrate 11, a transparent electrode 12, a hole transport layer 14 including metal nanoparticles 13, a photoelectric conversion layer 15, an electron transport layer 16, and a counter electrode 17. And. The transparent electrode 12 is provided on the substrate 11, and the hole transport layer 14 is provided on the transparent electrode 12. The photoelectric conversion layer 15 is provided on the hole transport layer 14, and is a thin film having a structure in which a p-type semiconductor and an n-type semiconductor are bulk heterojunctioned. The electron transport layer 16 is provided on the photoelectric conversion layer 15, and the counter electrode 17 is provided on the electron transport layer 16.
以下、本実施形態の有機光電変換素子を構成する各部材について詳細に説明する。 Hereinafter, each member which comprises the organic photoelectric conversion element of this embodiment is demonstrated in detail.
（基板）
基板１１は、他の構成部材を支持するためのものである。この基板１１は、電極を形成でき、熱や有機溶剤によって変質しないものが好ましい。基板１１の材料としては、例えば、無アルカリガラス、石英ガラス等の無機材料、ポリエチレン、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリイミド、ポリアミド、ポリアミドイミド、液晶ポリマー、シクロオレフィンポリマー等のプラスチック、高分子フィルム、ステンレス鋼（ＳＵＳ）、シリコン等の金属基板等が挙げられる。
(substrate)
The substrate 11 is for supporting other constituent members. The substrate 11 is preferably one that can form electrodes and is not altered by heat or an organic solvent. Examples of the material of the substrate 11 include inorganic materials such as alkali-free glass and quartz glass, polyethylene, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide, polyamide, polyamideimide, liquid crystal polymer, cycloolefin polymer, and the like. Examples thereof include metal substrates such as plastic, polymer film, stainless steel (SUS), and silicon.
基板１１は、光が入射する側に配置される場合、透明な材料が使用される。対向電極１７が透明または半透明である場合、基板１１として不透明な基板を使用してもよい。基板１１の厚さは、その他の構成部材を支持するために十分な強度があれば、特に限定されない。 The substrate 11 is made of a transparent material when arranged on the light incident side. When the counter electrode 17 is transparent or translucent, an opaque substrate may be used as the substrate 11. The thickness of the substrate 11 is not particularly limited as long as it has sufficient strength to support other components.
光が入射される側に基板１１が配置された場合、例えば、図２に示す一変形例のように、基板１１の光入射面には、例えばモスアイ構造の反射防止膜１８を設けることで光を効率的に取り込み、セルのエネルギー変換効率を向上させることが可能である。モスアイ構造は表面に１００ｎｍ程度の規則的な突起配列を有する構造をしており、この突起構造により厚み方向の屈折率が連続的に変化する。このため、無反射フィルムを媒介させることで屈折率の不連続的な変化面が無くなり、光の反射が減少し、セル効率が向上する。 When the substrate 11 is disposed on the light incident side, for example, as in a modification shown in FIG. 2, the light incident surface of the substrate 11 is provided with an antireflection film 18 having a moth-eye structure, for example. It is possible to improve the energy conversion efficiency of the cell. The moth-eye structure has a structure having a regular protrusion arrangement of about 100 nm on the surface, and the refractive index in the thickness direction is continuously changed by this protrusion structure. For this reason, by disposing the non-reflective film, there is no discontinuous change surface of the refractive index, light reflection is reduced, and the cell efficiency is improved.
（透明電極）
透明電極１２の材料としては、導電性を有するものであれば特に限定されない。通常は、透明または半透明の導電性を有する材料を、真空蒸着法、スパッタリング法、イオンプレーティング法、メッキ法、塗布法等で成膜する。透明または半透明の電極材料としては、導電性の金属酸化物膜、半透明の金属薄膜等が挙げられる。具体的には、酸化インジウム、酸化亜鉛、酸化スズ、およびそれらの複合体であるＩＴＯ（Indium Tin Oxide)、フッ素ドープ酸化スズ（ＦＴＯ（Fluorine-doped Tin Oxide））、またはインジウム、亜鉛、およびオキサイド等からなる導電性ガラスを用いて作製された酸化スズ膜等が用いられる。特に、ＩＴＯまたはＦＴＯが好ましい。また、金、白金、銀、銅等の金属を用いてもよい。
(Transparent electrode)
The material of the transparent electrode 12 is not particularly limited as long as it has conductivity. Usually, a transparent or translucent conductive material is formed by vacuum deposition, sputtering, ion plating, plating, coating, or the like. Examples of the transparent or translucent electrode material include a conductive metal oxide film and a translucent metal thin film. Specifically, indium oxide, zinc oxide, tin oxide, and composites thereof, ITO (Indium Tin Oxide), fluorine-doped tin oxide (FTO), or indium, zinc, and oxide A tin oxide film or the like produced using conductive glass made of or the like is used. In particular, ITO or FTO is preferable. Moreover, you may use metals, such as gold | metal | money, platinum, silver, copper.
また、透明電極１２の材料として、有機系の導電性ポリマーである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を用いてもよい。透明電極１２の膜厚は、ＩＴＯを用いた場合、３０ｎｍ〜３００ｎｍであることが好ましい。３０ｎｍより薄くすると、導電性が低下して抵抗が高くなり、光電変換効率の低下の原因となる。３００ｎｍよりも厚くすると、ＩＴＯに可撓性がなくなり、応力が透明電極１２に作用するとひび割れてしまう。 Further, as the material of the transparent electrode 12, polyaniline and its derivative, polythiophene and its derivative, etc., which are organic conductive polymers, may be used. The film thickness of the transparent electrode 12 is preferably 30 nm to 300 nm when ITO is used. If it is thinner than 30 nm, the conductivity is lowered, the resistance is increased, and the photoelectric conversion efficiency is lowered. If the thickness is greater than 300 nm, the ITO becomes inflexible and cracks when stress acts on the transparent electrode 12.
また、透明電極１２のシート抵抗は可能な限り低いことが好ましく、１０Ω／□以下であることが好ましい。透明電極１２は、単層であってもよく、異なる仕事関数の材料で構成される層を積層したものであってもよい。 Further, the sheet resistance of the transparent electrode 12 is preferably as low as possible, and is preferably 10Ω / □ or less. The transparent electrode 12 may be a single layer or may be a laminate of layers made of materials having different work functions.
（金属ナノ粒子が内包された正孔輸送層）
正孔輸送層１４は、透明電極１２上に金属ナノ粒子溶液を塗布して金属ナノ粒子１３を透明電極１２上に配置してから、ポリエチレンジオキシチオフェン−ポリスチレンスルホン酸(以下、ＰＥＤＯＴ−ＰＳＳ（poly(3,4-ethylenedioxythiopherene)-polystyrene acid)とも云う））溶液を透明電極１２上に塗布することで形成される。金属ナノ粒子溶液は、金属イオンを含む液体に還元剤を添加して金属ナノ粒子１３を析出した後、液体に分散させてもよい。
(Hole transport layer containing metal nanoparticles)
The hole transport layer 14 is formed by applying a metal nanoparticle solution on the transparent electrode 12 and disposing the metal nanoparticles 13 on the transparent electrode 12, and then polyethylene dioxythiophene-polystyrenesulfonic acid (hereinafter, PEDOT-PSS ( Poly (3,4-ethylenedioxythiopherene) -polystyrene acid)))) solution is applied on the transparent electrode 12. The metal nanoparticle solution may be dispersed in a liquid after adding a reducing agent to the liquid containing metal ions to precipitate the metal nanoparticles 13.
金属ナノ粒子１３を透明電極１２に配置する方法は、配置できる方法であれば特に限定されないが、例えばスピンコート法で塗布することが可能である。金属ナノ粒子１３を透明電極１２に配置した後、自然乾燥させる。塗布する金属ナノ粒子溶液は、フィルタで予め濾過したものを使用することが望ましい。 Although the method of arrange | positioning the metal nanoparticle 13 to the transparent electrode 12 will not be specifically limited if it is a method which can be arrange | positioned, For example, it can apply | coat by a spin coat method. After the metal nanoparticles 13 are disposed on the transparent electrode 12, they are naturally dried. It is desirable to use a metal nanoparticle solution to be applied that has been filtered in advance with a filter.
また、後述するように、透明電極１２上に配置する金属ナノ粒子１３の密度は１〜５５粒子／μｍ２の範囲内であることが好ましい。金属ナノ粒子１３の密度を５５粒子／μｍ２以下にすることで、金属ナノ粒子１３同士の凝集が抑制される。金属ナノ粒子１３同士が凝集すると、金属ナノ粒子１３の２次粒子径が増加し、光電変換層１５に露出してしまう。この場合、光電変換層１５で光照射によって発生したキャリアが金属ナノ粒子１３の２次粒子で再結合してしまうため変換効率が低下してしまう。 As will be described later, the density of the metal nanoparticles 13 disposed on the transparent electrode 12 is preferably in the range of 1 to 55 particles / μm 2 . By setting the density of the metal nanoparticles 13 to 55 particles / μm 2 or less, aggregation of the metal nanoparticles 13 is suppressed. When the metal nanoparticles 13 are aggregated, the secondary particle diameter of the metal nanoparticles 13 increases and is exposed to the photoelectric conversion layer 15. In this case, since the carriers generated by light irradiation in the photoelectric conversion layer 15 are recombined with the secondary particles of the metal nanoparticles 13, the conversion efficiency is lowered.
ＰＥＤＯＴ−ＰＳＳ層の成膜方法は、薄膜を形成できる方法であれば特に限定されないが、例えばスピンコート法で塗布することが可能である。ＰＥＤＯＴ−ＰＳＳを所望の膜厚に塗布した後、ホットプレート等で加熱乾燥する。１４０℃〜２００℃で数分〜１０分間程度加熱乾燥することが好ましい。塗布する溶液は、フィルタで予め濾過したものを使用することが望ましい。 The method for forming the PEDOT-PSS layer is not particularly limited as long as it is a method capable of forming a thin film, but it can be applied by, for example, a spin coating method. After applying PEDOT-PSS to a desired film thickness, it is heated and dried with a hot plate or the like. Heat drying is preferably performed at 140 to 200 ° C. for several minutes to 10 minutes. As the solution to be applied, it is desirable to use a solution preliminarily filtered with a filter.
また、金属ナノ粒子１３の平均粒径ｄ（ｎｍ）と正孔輸送層１４の膜厚ｔ（ｎｍ）との間にｄ＜ｔ≦１００ｎｍの関係が成立することが好ましい。正孔輸送層１４の膜厚ｔが平均粒径ｄよりも小さいと、金属ナノ粒子１３が光電変換層１５に露出してしまう。この場合、光電変換層１５において入射光によって発生したキャリアが金属ナノ粒子１３で再結合してしまうため変換効率が低下してしまう。さらに、膜厚ｔが薄いと透明電極１２と光電変換層１５間と間の並列抵抗が小さくなり、光電変換層１５で発生した光電流がリークしてしまう。 Further, it is preferable that a relationship of d <t ≦ 100 nm is established between the average particle diameter d (nm) of the metal nanoparticles 13 and the film thickness t (nm) of the hole transport layer 14. When the film thickness t of the hole transport layer 14 is smaller than the average particle diameter d, the metal nanoparticles 13 are exposed to the photoelectric conversion layer 15. In this case, since the carriers generated by the incident light in the photoelectric conversion layer 15 are recombined with the metal nanoparticles 13, the conversion efficiency is lowered. Furthermore, when the film thickness t is thin, the parallel resistance between the transparent electrode 12 and the photoelectric conversion layer 15 is reduced, and the photocurrent generated in the photoelectric conversion layer 15 is leaked.
なお、金属ナノ粒子１３の平均粒径は１０ｎｍ〜５０ｎｍであることが好ましい。金属ナノ粒子１３の平均粒径が１０ｎｍよりも小さくなると、ファンデルワールス引力による凝集が生じる。そして、凝集の効果が大きくなると、透明電極１２と光電変換層１５との間もしくは透明電極１２と対向電極１７との間に、凝集した多数の金属ナノ粒子１３を介してリーク電流が生じる原因となり、有機薄膜太陽電池の特性が低下してしまうためである。また、正孔輸送層１４の厚みは一般的には数１０ｎｍ〜１００ｎｍである。１００ｎｍ以上の厚さを有すると、正孔輸送層１４による入射光の光吸収割合が大きくなるので有機薄膜太陽電池の短絡電流密度（Ｊｓｃ）が減少すること、および直列抵抗成分が大きくなるので有機薄膜太陽電池の形状因子（ＦＦ）が小さくなることにより、変換効率が低下してしまう。また、金属ナノ粒子１３の平均粒径が大きくなると少ない数の金属ナノ粒子１３が凝集しても、透明電極１２と光電変換層１５間をリークする確率が増える。例えば、透明電極１２に対して垂直方向に粒径が５０ｎｍの金属ナノ粒子１３が２個凝集した場合、１００ｎｍ厚の正孔輸送層１４に対して透明電極１２と光電変換層１５間が短絡してしまう。以上の理由から、上限を５０ｎｍとした。 In addition, it is preferable that the average particle diameter of the metal nanoparticle 13 is 10 nm-50 nm. When the average particle diameter of the metal nanoparticles 13 is smaller than 10 nm, aggregation due to van der Waals attraction occurs. When the effect of aggregation is increased, a leakage current is generated between the transparent electrode 12 and the photoelectric conversion layer 15 or between the transparent electrode 12 and the counter electrode 17 through a large number of aggregated metal nanoparticles 13. This is because the characteristics of the organic thin film solar cell are deteriorated. The thickness of the hole transport layer 14 is generally several tens of nm to 100 nm. When the thickness is 100 nm or more, the light absorption ratio of incident light by the hole transport layer 14 is increased, so that the short-circuit current density (Jsc) of the organic thin film solar cell is reduced and the series resistance component is increased. Conversion efficiency will fall by the small form factor (FF) of a thin film solar cell. Further, when the average particle diameter of the metal nanoparticles 13 is increased, the probability of leakage between the transparent electrode 12 and the photoelectric conversion layer 15 is increased even if a small number of metal nanoparticles 13 are aggregated. For example, when two metal nanoparticles 13 having a particle diameter of 50 nm are aggregated in a direction perpendicular to the transparent electrode 12, the transparent electrode 12 and the photoelectric conversion layer 15 are short-circuited with respect to the hole transport layer 14 having a thickness of 100 nm. End up. For the above reasons, the upper limit is set to 50 nm.
本実施形態においては、金属ナノ粒子１３を透明電極１２に配置した後、ＰＥＤＯＴ−ＰＳＳ層を成膜することで正孔輸送層１４を形成する。このため、一般的に用いられているスピンコート塗布法で正孔輸送層１４を形成したものよりも材料コストを低減することができる。その理由は、金属ナノ粒子溶液を導電性高分子溶液に添加したものをスピンコートすると、スピンコート回転による遠心力で金属ナノ粒子１３の大部分が飛散されるため、材料消費が大きいからである。 In this embodiment, after arrange | positioning the metal nanoparticle 13 to the transparent electrode 12, the positive hole transport layer 14 is formed by forming a PEDOT-PSS layer into a film. For this reason, material cost can be reduced rather than what formed the positive hole transport layer 14 with the spin coat application method generally used. The reason is that when a metal nanoparticle solution added to a conductive polymer solution is spin-coated, the material consumption is large because most of the metal nanoparticles 13 are scattered by the centrifugal force generated by spin coating rotation. .
金属ナノ粒子１３が作る局在表面プラズモンによる増強電場の発生範囲は金属ナノ粒子１３の表面からその粒径程度と言われている。従って、局在表面プラズモンを利用して変換効率を向上させるためには、金属ナノ粒子１３の表面から光電変換層１４までの距離を数１０ｎｍ以内に制御する必要がある。 It is said that the generation range of the enhanced electric field by the localized surface plasmon produced by the metal nanoparticles 13 is about the particle size from the surface of the metal nanoparticles 13. Therefore, in order to improve the conversion efficiency using the localized surface plasmon, it is necessary to control the distance from the surface of the metal nanoparticle 13 to the photoelectric conversion layer 14 within several tens of nm.
一方、本発明者らの実験結果によると、金属ナノ粒子１３の表面から光電変換層１４までの距離が金属ナノ粒子１３の粒径よりも十分大きいにも関わらず、変換効率の向上が確認された。この実験結果は、金属ナノ粒子が作る局在表面プラズモンでは、変換効率が向上するという現象を説明できないことを示している。なお、本発明者らは、上記現象は金属ナノ粒子１３による光散乱強度が何らかの形で寄与していると推察している。 On the other hand, according to the experiment results of the present inventors, although the distance from the surface of the metal nanoparticle 13 to the photoelectric conversion layer 14 is sufficiently larger than the particle size of the metal nanoparticle 13, the conversion efficiency is improved. It was. This experimental result shows that localized surface plasmons produced by metal nanoparticles cannot explain the phenomenon that the conversion efficiency is improved. The present inventors presume that the above phenomenon contributes in some way to the light scattering intensity by the metal nanoparticles 13.
なお、ＰＥＤＯＴ−ＰＳＳ以外の正孔輸送層１４の材料として、酸化ニッケル、酸化モリブデン、酸化バナジウムの群から選択された少なくとも１つを含んでいることが好ましい。ＰＥＤＯＴ−ＰＳＳの仕事関数は〜−５ｅＶである。酸化ニッケルは価電子帯エネルギー準位Ｅｖが−５．５ｅＶ、酸化モリブデンは伝導帯エネルギー準位Ｅｃが−５．１ｅＶ、酸化バナジウムは伝導帯エネルギー準位Ｅｃが−５．１ｅＶである。これらの準位は、ＰＥＤＯＴ−ＰＳＳの仕事関数と近い値なので、正孔が輸送されるエネルギー準位として機能する。また、正孔輸送層１４は、浅い伝導帯エネルギー準位Ｅｃを有することで電子ブロッキング機能を持つ。酸化ニッケルは、浅い伝導帯エネルギー準位Ｅｃ（−１．７ｅＶ）を有するので優れた電子ブロッキング機能を持つ。一方、酸化モリブデンと酸化バナジウムは伝導帯エネルギー準位Ｅｃが深い（−５．１ｅＶ）ので、電子ブロッキング機能が劣ると考えられるが、実際の有機薄膜太陽電池素子では高い性能を示すことが知られている。 In addition, it is preferable that the material of the hole transport layer 14 other than PEDOT-PSS includes at least one selected from the group consisting of nickel oxide, molybdenum oxide, and vanadium oxide. The work function of PEDOT-PSS is -5 eV. Nickel oxide has a valence band energy level Ev of −5.5 eV, molybdenum oxide has a conduction band energy level Ec of −5.1 eV, and vanadium oxide has a conduction band energy level Ec of −5.1 eV. Since these levels are close to the work function of PEDOT-PSS, they function as energy levels for transporting holes. The hole transport layer 14 has an electron blocking function by having a shallow conduction band energy level Ec. Since nickel oxide has a shallow conduction band energy level Ec (-1.7 eV), it has an excellent electron blocking function. On the other hand, molybdenum oxide and vanadium oxide have a deep conduction band energy level Ec (−5.1 eV), so it is considered that the electron blocking function is inferior, but it is known that an actual organic thin film solar cell element exhibits high performance. ing.
（光電変換層）
光電変換層１５は、透明電極１２と対向電極１７との間に配置される。本実施形態による有機光電変換素子は、バルクへテロ接合型の光電変換素子である。バルクヘテロ接合型の光電変換素子は、ｐ型半導体とｎ型半導体が光電変換層中で混合してミクロ層分離構造を取ることが特徴である。バルクへテロ接合型は、混合されたｐ型半導体とｎ型半導体が光電変換層内でナノオーダーのサイズのｐｎ接合を形成し、接合面において生じる光電荷分離を利用して電流を得る。
(Photoelectric conversion layer)
The photoelectric conversion layer 15 is disposed between the transparent electrode 12 and the counter electrode 17. The organic photoelectric conversion element according to the present embodiment is a bulk heterojunction photoelectric conversion element. A bulk heterojunction photoelectric conversion element is characterized in that a p-type semiconductor and an n-type semiconductor are mixed in a photoelectric conversion layer to form a micro layer separation structure. In the bulk heterojunction type, a mixed p-type semiconductor and n-type semiconductor form a pn junction having a nano-order size in the photoelectric conversion layer, and a current is obtained by utilizing photocharge separation generated at the junction surface.
ｐ型半導体は、電子供与性の性質を有する材料で構成される。これに対して、ｎ型半導体は、電子受容性の性質を有する材料で構成される。本実施形態においては、ｐ型半導体およびｎ型半導体の少なくとも一方が有機半導体であってもよい。 A p-type semiconductor is composed of a material having an electron donating property. On the other hand, the n-type semiconductor is composed of a material having an electron accepting property. In the present embodiment, at least one of the p-type semiconductor and the n-type semiconductor may be an organic semiconductor.
ｐ型有機半導体としては、例えば、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、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、フタロシアニン誘導体、ポルフィリンおよびその誘導体、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を使用することができ、これらを併用してもよい。また、これらの共重合体を使用してもよく、例えば、チオフェン−フルオレン共重合体、フェニレンエチニレン−フェニレンビニレン共重合体等が挙げられる。 Examples of p-type organic semiconductors include polythiophene and derivatives thereof, polypyrrole and derivatives thereof, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof. , Polysiloxane derivatives having an aromatic amine in the side chain or main chain, polyaniline and derivatives thereof, phthalocyanine derivatives, porphyrin and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, and the like, These may be used in combination. These copolymers may be used, and examples thereof include a thiophene-fluorene copolymer, a phenylene ethynylene-phenylene vinylene copolymer, and the like.
好ましいｐ型有機半導体は、π共役を有する導電性高分子であるポリチオフェンおよびその誘導体である。ポリチオフェンおよびその誘導体は、優れた立体規則性を確保することができ、溶媒への溶解性が比較的高い。ポリチオフェンおよびその誘導体は、チオフェン骨格を有する化合物であれば特に限定されない。ポリチオフェンおよびその誘導体の具体例としては、ポリ３−メチルチオフェン、ポリ３−ブチルチオフェン、ポリ３−ヘキシルチオフェン、ポリ３−オクチルチオフェン、ポリ３−デシルチオフェン、ポリ３−ドデシルチオフェン等のポリアルキルチオフェン；ポリ３−フェニルチオフェン、ポリ３−（ｐ−アルキルフェニルチオフェン）等のポリアリールチオフェン；ポリ３−ブチルイソチオナフテン、ポリ３−ヘキシルイソチオナフテン、ポリ３−オクチルイソチオナフテン、ポリ３−デシルイソチオナフテン等のポリアルキルイソチオナフテン；ポリエチレンジオキシチオフェン等が挙げられる。 A preferred p-type organic semiconductor is polythiophene which is a conductive polymer having π conjugation and derivatives thereof. Polythiophene and its derivatives can ensure excellent stereoregularity and have relatively high solubility in a solvent. Polythiophene and derivatives thereof are not particularly limited as long as they are compounds having a thiophene skeleton. Specific examples of polythiophene and derivatives thereof include polyalkylthiophenes such as poly-3-methylthiophene, poly-3-butylthiophene, poly-3-hexylthiophene, poly-3-octylthiophene, poly-3-decylthiophene, poly-3-dodecylthiophene, etc. Polyarylthiophene such as poly-3-phenylthiophene and poly-3- (p-alkylphenylthiophene); poly-3-butylisothionaphthene, poly-3-hexylisothionaphthene, poly-3-octylisothionaphthene, poly-3- And polyalkylisothionaphthene such as decylisothionaphthene; polyethylenedioxythiophene and the like.
また近年では、カルバゾール、ベンゾチアジアゾールおよびチオフェンからなる共重合体であるＰＣＤＴＢＴ（ポリ［Ｎ−９”−ヘプタ−デカニル−２，７−カルバゾール−アルト−５，５−（４’，７’−ジ−２−チエニル−２’，１’，３’−ベンゾチアジアゾール）］）などの誘導体やチエノチオフェンとベンゾジチオフェンからなる共重合体であるＰＴＢ７（ポリ［［４，８−ビス［（２−エチルヘキシル）オキシ］ベンゾ［１，２−ｂ：４−５−ｂ’］ジチオフェン−２，６−ジル］［３−フルオロ−２−［（２−エチルヘキシル）カルボニル］チエノ［３，４−６］チオフェンジル］）などの誘導体が、優れた光電変換効率を得られる化合物として知られている。 In recent years, PCDTBT (poly [N-9 "-hepta-decanyl-2,7-carbazole-alt-5,5- (4 ', 7'-di ()), which is a copolymer of carbazole, benzothiadiazole and thiophene. -2-thienyl-2 ′, 1 ′, 3′-benzothiadiazole)]) and the like, and PTB7 (poly [[4,8-bis [(2- Ethylhexyl) oxy] benzo [1,2-b: 4-5-b ′] dithiophene-2,6-diyl] [3-fluoro-2-[(2-ethylhexyl) carbonyl] thieno [3,4-4] Derivatives such as thiophenzyl]) are known as compounds capable of obtaining excellent photoelectric conversion efficiency.
これらの導電性高分子は、溶媒に溶解させた溶液を塗布することにより成膜可能である。従って、大面積の有機薄膜太陽電池を、印刷法等により、安価な設備にて低コストで製造できるという利点がある。 These conductive polymers can be formed by applying a solution dissolved in a solvent. Therefore, there is an advantage that a large-area organic thin film solar cell can be manufactured at low cost with inexpensive equipment by a printing method or the like.
ｎ型有機半導体としては、フラーレンおよびその誘導体が好適に使用される。ここで使用されるフラーレン誘導体は、フラーレン骨格を有する誘導体であれば特に限定されない。具体的には、Ｃ６０、Ｃ７０、Ｃ７６、Ｃ７８、Ｃ８４等を基本骨格として構成される誘導体が挙げられる。フラーレン誘導体は、フラーレン骨格における炭素原子が任意の官能基で修飾されていてもよく、この官能基同士が互いに結合して環を形成していてもよい。フラーレン誘導体には、フラーレン結合ポリマーも含まれる。溶剤に親和性の高い官能基を有し、溶媒への可溶性が高いフラーレン誘導体が好ましい。 As the n-type organic semiconductor, fullerene and derivatives thereof are preferably used. The fullerene derivative used here is not particularly limited as long as it is a derivative having a fullerene skeleton. Specific examples include derivatives composed of C 60 , C 70 , C 76 , C 78 , C 84 and the like as a basic skeleton. In the fullerene derivative, carbon atoms in the fullerene skeleton may be modified with an arbitrary functional group, and these functional groups may be bonded to each other to form a ring. Fullerene derivatives also include fullerene bonded polymers. A fullerene derivative having a functional group with high affinity for the solvent and high solubility in the solvent is preferred.
フラーレン誘導体における官能基としては、例えば、水素原子；水酸基；フッ素原子、塩素原子等のハロゲン原子；メチル基、エチル基等のアルキル基；ビニル基等のアルケニル基；シアノ基；メトキシ基、エトキシ基等のアルコキシ基；フェニル基、ナフチル基等の芳香族炭化水素基、チエニル基、ピリジル基等の芳香族複素環基等が挙げられる。具体的には、Ｃ６０Ｈ３６、Ｃ７０Ｈ３６等の水素化フラーレン、Ｃ６０、Ｃ７０等のオキサイドフラーレン、フラーレン金属錯体等が挙げられる。 Examples of the functional group in the fullerene derivative include hydrogen atom; hydroxyl group; halogen atom such as fluorine atom and chlorine atom; alkyl group such as methyl group and ethyl group; alkenyl group such as vinyl group; cyano group; methoxy group and ethoxy group. Alkoxy groups such as phenyl groups, aromatic hydrocarbon groups such as naphthyl groups, and aromatic heterocyclic groups such as thienyl groups and pyridyl groups. Specific examples include hydrogenated fullerenes such as C 60 H 36 and C 70 H 36 , oxide fullerenes such as C 60 and C 70 , fullerene metal complexes, and the like.
上述した中でも、フラーレン誘導体として、６０ＰＣＢＭ（［６，６］−フェニルＣ６１酪酸メチルエステル）または７０ＰＣＢＭ（［６，６］−フェニルＣ７１酪酸メチルエステル）を使用することが特に好ましい。 Among the above, a fullerene derivative, 60PCBM ([6,6] - phenyl C 61 butyric acid methyl ester), or 70PCBM - it is particularly preferred to use ([6,6] phenyl C 71 butyric acid methyl ester).
未修飾のフラーレンを使用する場合、Ｃ７０を使用することが好ましい。フラーレンＣ７０は、光キャリアの発生効率が高く、有機薄膜太陽電池に使用するのに適している。 When using the unmodified fullerene, it is preferred to use a C 70. Fullerene C 70 is the generation efficiency of photocarriers high, are suitable for use in organic thin film solar cell.
光電変換層１５におけるｎ型有機半導体とｐ型有機半導体の混合比率は、ｎ型有機半導体の含有率をｐ型半導体がＰ３ＡＴ系の場合、およそｎ：ｐ＝１：１とすることが好ましく、ｐ型半導体がＰＣＤＴＢＴ系の場合、およそｎ：ｐ＝４：１とすることが好ましい。また、ｐ型半導体がＰＴＢ７系の場合、およそｎ：ｐ＝１：１．５とすることが好ましい。 The mixing ratio of the n-type organic semiconductor and the p-type organic semiconductor in the photoelectric conversion layer 15 is preferably about n: p = 1: 1 when the p-type semiconductor is a P3AT system, When the p-type semiconductor is a PCDTBT system, it is preferable that n: p = 4: 1. When the p-type semiconductor is PTB7, it is preferable that n: p = 1: 1.5.
有機半導体を塗布するためには、溶媒に溶解する必要があるが、それに用いる溶媒としては、例えば、トルエン、キシレン、テトラリン、デカリン、メシチレン、ｎ−ブチルベンゼン、ｓｅｃ−ブチルベンゼン、ｔｅｒｔ−ブチルベンゼン等の不飽和炭化水素系溶媒、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン等のハロゲン化芳香族炭化水素系溶媒、四塩化炭素、クロロホルム、ジクロロメタン、ジクロロエタン、クロロブタン、ブロモブタン、クロロペンタン、クロロヘキサン、ブロモヘキサン、クロロシクロヘキサン等のハロゲン化飽和炭化水素系溶媒、テトラヒドロフラン、テトラヒドロピラン等のエーテル類が挙げられる。特に、ハロゲン系の芳香族溶剤が好ましい。これらの溶剤を単独、もしくは混合して使用することが可能である。 In order to apply an organic semiconductor, it is necessary to dissolve in a solvent. Examples of the solvent used for the organic semiconductor include toluene, xylene, tetralin, decalin, mesitylene, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene. Unsaturated hydrocarbon solvents such as, halogenated aromatic hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, chlorohexane, bromohexane, Halogenated saturated hydrocarbon solvents such as chlorocyclohexane and ethers such as tetrahydrofuran and tetrahydropyran. In particular, a halogen-based aromatic solvent is preferable. These solvents can be used alone or in combination.
溶液を塗布し成膜する方法としては、スピンコート法、ディップコート法、キャスティング法、バーコート法、ロールコート法、ワイアーバーコート法、スプレー法、スクリーン印刷、グラビア印刷法、フレキソ印刷法、オフセット印刷法、グラビア・オフセット印刷、ディスペンサー塗布、ノズルコート法、キャピラリーコート法、インクジェット法等が挙げられ、これらの塗布法を単独で、もしくは組み合わせて用いることができる。 As a method of applying a solution to form a film, spin coating, dip coating, casting, bar coating, roll coating, wire bar coating, spraying, screen printing, gravure printing, flexographic printing, offset Examples thereof include a printing method, gravure / offset printing, dispenser coating, nozzle coating method, capillary coating method, and ink jet method, and these coating methods can be used alone or in combination.
（電子輸送層）
電子輸送層１６は、対向電極１７と光電変換層１５との間に配置される。電子輸送層１６は、正孔をブロックして電子のみを効率的に輸送する機能、および光電変換層１５と電子輸送層１６との界面で生じたエキシトンの消滅を防ぐ機能を有する。
(Electron transport layer)
The electron transport layer 16 is disposed between the counter electrode 17 and the photoelectric conversion layer 15. The electron transport layer 16 has a function of blocking holes and efficiently transporting only electrons, and a function of preventing the disappearance of excitons generated at the interface between the photoelectric conversion layer 15 and the electron transport layer 16.
電子輸送層１６の材料としては、金属酸化物、たとえばゾルゲル法にてチタンアルコキシドを加水分解して得たアモルファス性の酸化チタンなどが挙げられる。成膜方法は、薄膜を形成できる方法であれば特に限定されないが、例えば、スピンコート法が挙げられる。電子輸送層の材料として酸化チタンを使用する場合、膜厚は５ｎｍ〜２０ｎｍの厚さに成膜することが望ましい。膜厚が上記範囲より薄い場合は、正孔ブロック効果が減少してしまうため、発生したエキシトンが電子とホールに解離する前に失活してしまい、効率的に電流を取り出すことができない。膜厚が厚すぎる場合は、膜抵抗が大きくなり、発生した電流を制限してしまうため光変換効率が低下する。 Examples of the material for the electron transport layer 16 include metal oxides such as amorphous titanium oxide obtained by hydrolyzing titanium alkoxide by a sol-gel method. The film forming method is not particularly limited as long as it is a method capable of forming a thin film, and examples thereof include a spin coating method. When titanium oxide is used as the material for the electron transport layer, the film thickness is desirably 5 nm to 20 nm. When the film thickness is thinner than the above range, the hole blocking effect is reduced, so that the generated exciton is deactivated before dissociating into electrons and holes, and current cannot be efficiently extracted. When the film thickness is too thick, the film resistance increases and the generated current is limited, so that the light conversion efficiency is lowered.
塗布溶液は、フィルタで予め濾過したものを使用することが望ましい。規定の膜厚に塗布した後、ホットプレートなどを用いて加熱乾燥する。５０℃〜１００℃で数分〜１０分間程度、空気中にて加水分解を促進しながら加熱乾燥する。無機物ではフッ化リチウムや金属カルシウムなどが好適な材料である。 It is desirable to use a coating solution that has been filtered in advance with a filter. After applying to a specified film thickness, it is heated and dried using a hot plate or the like. Heat drying at 50 to 100 ° C. for several minutes to 10 minutes while promoting hydrolysis in the air. Among inorganic materials, lithium fluoride, metallic calcium, and the like are suitable materials.
（対向電極）
対向電極１７は、導電性を有する材料を真空蒸着法、スパッタリング法、イオンプレーティング法、メッキ法、塗布法等で成膜する。電極材料としては、導電性の金属薄膜、金属酸化物膜等が挙げられる。対向電極１７を電子輸送層１６と接して形成する場合は、対向電極１７には仕事関数の低い材料を用いることが好ましい。仕事関数の低い材料としては、例えば、アルカリ金属、アルカリ土類金属等が挙げられる。具体的には、Ｌｉ、Ｉｎ、Ａｌ、Ｃａ、Ｍｇ、Ｓｍ、Ｔｂ、Ｙｂ、Ｚｒ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、およびＢａからなる群から選択された１つの元素からなる単体、および選択された元素を少なくとも１つ含む合金を挙げることができる。
(Counter electrode)
The counter electrode 17 is formed by depositing a conductive material by vacuum deposition, sputtering, ion plating, plating, coating, or the like. Examples of the electrode material include a conductive metal thin film and a metal oxide film. When the counter electrode 17 is formed in contact with the electron transport layer 16, it is preferable to use a material having a low work function for the counter electrode 17. Examples of the material having a low work function include alkali metals and alkaline earth metals. Specifically, a single element selected from the group consisting of Li, In, Al, Ca, Mg, Sm, Tb, Yb, Zr, Na, K, Rb, Cs, and Ba, and selected And alloys containing at least one element.
対向電極１７は、単層であってもよく、異なる仕事関数の材料で構成される層を積層したものであってもよい。また、仕事関数の低い材料のうちの１つ以上と、金、銀、白金、銅、マンガン、チタン、コバルト、ニッケル、タングステン、錫などとの合金であってもよい。合金の例としては、リチウム−アルミニウム合金、リチウム−マグネシウム合金、リチウム−インジウム合金、マグネシウム−銀合金、マグネシウム−インジウム合金、マグネシウム−アルミニウム合金、インジウム−銀合金、カルシウム−アルミニウム合金等が挙げられる。 The counter electrode 17 may be a single layer or may be a laminate of layers made of materials having different work functions. Alternatively, an alloy of one or more of materials having a low work function and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, or the like may be used. Examples of the alloy include a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy, a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, and a calcium-aluminum alloy.
対向電極１７の膜厚は、１ｎｍ〜５００ｎｍであり、好ましくは１０ｎｍ〜３００ｎｍである。膜厚が上記範囲より薄い場合は、抵抗が大きくなりすぎ、発生した電荷を十分に外部回路へ伝達できない。膜厚が厚い場合には、対向電極１７の成膜に長時間を要するため材料温度が上昇し、有機層にダメージを与えて性能が劣化してしまう。さらに、材料を大量に使用するため、成膜装置の占有時間が長くなり、コストアップに繋がる。 The thickness of the counter electrode 17 is 1 nm to 500 nm, preferably 10 nm to 300 nm. When the film thickness is smaller than the above range, the resistance becomes too large and the generated charge cannot be sufficiently transmitted to the external circuit. When the film thickness is thick, it takes a long time to form the counter electrode 17, so that the material temperature rises and the organic layer is damaged to deteriorate the performance. Further, since a large amount of material is used, the occupation time of the film forming apparatus becomes longer, leading to an increase in cost.
（実施例１）
本実施形態の有機光電変換素子の変換効率を評価するために、図３（ａ）乃至３（ｈ）に示す製造方法を用いてサンプルを作製し、疑似太陽光を照射したときの電流−電圧（Ｉ−Ｖ）特性を評価した。
Example 1
In order to evaluate the conversion efficiency of the organic photoelectric conversion element of this embodiment, a sample was produced using the manufacturing method shown in FIGS. 3 (a) to 3 (h), and current-voltage when irradiated with pseudo-sunlight. (IV) characteristics were evaluated.
ガラス板の表面上に透明電極としてＩＴＯが形成されたＩＴＯ基板１２ａを用意し、このＩＴＯ基板１２ａの表面に紫外線オゾン（ＵＶ−Ｏ３）を照射し、ＩＴＯ基板１２ａの有機物汚染を除去した（図３（ａ）、３（ｂ））。 An ITO substrate 12a having ITO formed as a transparent electrode on the surface of a glass plate was prepared, and the surface of the ITO substrate 12a was irradiated with ultraviolet ozone (UV-O 3 ) to remove organic contamination of the ITO substrate 12a ( FIG. 3 (a), 3 (b)).
続いて、ＩＴＯ基板１２ａ上に、Ａｇの濃度が１０ｗ％であるＡｇナノ粒子溶液を１００倍希釈したものを、直径が０．２μｍのフィルタを通して滴下し、スピンコート法で塗布し、Ａｇナノ粒子１３をＩＴＯ基板１２ａ上に配置した（図３（ｃ））。このときのＡｇナノ粒子１３の密度は、ＩＴＯ基板１２ａ上に１１粒／μｍ２であった。 Subsequently, a 100-fold diluted Ag nanoparticle solution having an Ag concentration of 10 w% is dropped on the ITO substrate 12a through a filter having a diameter of 0.2 μm, and is applied by a spin coating method. 13 was placed on the ITO substrate 12a (FIG. 3C). The density of the Ag nanoparticles 13 at this time was 11 grains / μm 2 on the ITO substrate 12a.
ここで、Ａｇ粒子溶液は、Ａｇナノ粒子の平均直径がほぼ２０ｎｍ、溶媒はエタノールを用いた。スピンコートの条件は、スピンコータの回転数が１０００ｒｐｍで３０秒間行った。この時のＩＴＯ基板１２ａ上に配置されたＡｇナノ粒子１３のＳＥＭ（Scanning Electron Microscope）像を示す。Ａｇナノ粒子１３の密度は１１粒子／μｍ２であることを確認した。ＩＴＯ基板１２ａ上に配置したＡｇナノ粒子１３は、Ａｇ原子のｄ軌道とＩＴＯの酸素２ｐ軌道とで共有結合を作る。共有結合は原子間の結合で最も強い結合であり、結合の強さを順に並べると、共有結合＞イオン結合＞金属結合＞ファンデルワールス結合である。従って、ＩＴＯ基板１２ａ上に配置されたＡｇナノ粒子１３はＩＴＯ基板１２ａ上に強く結合している。 Here, the Ag particle solution had an average diameter of Ag nanoparticles of approximately 20 nm, and ethanol was used as the solvent. The spin coating was performed at a spin coater rotation speed of 1000 rpm for 30 seconds. An SEM (Scanning Electron Microscope) image of the Ag nanoparticles 13 arranged on the ITO substrate 12a at this time is shown. It was confirmed that the density of the Ag nanoparticles 13 was 11 particles / μm 2 . The Ag nanoparticles 13 arranged on the ITO substrate 12a form a covalent bond between the d orbital of Ag atoms and the oxygen 2p orbital of ITO. A covalent bond is the strongest bond between atoms, and when the bond strengths are arranged in order, it is covalent bond> ionic bond> metal bond> van der Waals bond. Therefore, the Ag nanoparticles 13 arranged on the ITO substrate 12a are strongly bonded to the ITO substrate 12a.
なお、本発明におけるＡｇナノ粒子１３の密度の測定方法は以下のように行われる。 In addition, the measuring method of the density of Ag nanoparticle 13 in this invention is performed as follows.
図４に示す走査型電子顕微鏡の像（以下、ＳＥＭ像とも云う）倍率５万倍条件下でＡｇナノ粒子密度を算出する。まず、ＳＥＭ像に写っているＡｇナノ粒子数を数える。ＳＥＭ像のスケールバーから、ＳＥＭ像の表示面積が分かる。これにより、Ａｇナノ粒子密度を算出することができる。 The Ag nanoparticle density is calculated under the conditions of an image of a scanning electron microscope shown in FIG. First, the number of Ag nanoparticles in the SEM image is counted. The display area of the SEM image is known from the scale bar of the SEM image. Thereby, Ag nanoparticle density is computable.
なお、倍率5万倍の条件は以下の理由により設定した。Ａｇナノ粒子の密度値の精度を向上するためには、ＳＥＭ像の表示範囲を広げ、すなわち、ＳＥＭ像の倍率を下げ、観察するＡｇナノ粒子数が多いことが望ましい。ところが、ＳＥＭ像の倍率を下げすぎると、Ａｇ粒子の見え方が小さくなるので、Ａｇ粒子数を数えにくくなる。一方、ＳＥＭ像の倍率を上げ過ぎると、観察するＡｇナノ粒子数が少なくなり、Ａｇナノ粒子密度の精度が低下する。そこで、両者が両立するＳＥＭの倍率が５万倍条件下で、Ａｇナノ粒子密度を評価した。 The condition of 50,000 times magnification was set for the following reason. In order to improve the accuracy of the density value of Ag nanoparticles, it is desirable that the display range of the SEM image is expanded, that is, the magnification of the SEM image is lowered and the number of Ag nanoparticles to be observed is large. However, if the magnification of the SEM image is lowered too much, the appearance of Ag particles becomes small, so it is difficult to count the number of Ag particles. On the other hand, if the magnification of the SEM image is increased too much, the number of Ag nanoparticles to be observed decreases, and the accuracy of the Ag nanoparticle density decreases. Therefore, the Ag nanoparticle density was evaluated under the condition that the SEM magnification at which both were compatible was 50,000 times.
次に、ＰＥＤＯＴ−ＰＳＳ溶液を、Ａｇナノ粒子１３が配置されたＩＴＯ基板１２ａ上に直径が０．４５μｍのフィルタを通して滴下し、ＰＥＤＯＴ−ＰＳＳ層１４をスピンコート法で成膜した。このときのスピンコートの条件は、スピンコータの回転数が４０００ｒｐｍで、３０秒間行った。成膜後、ＩＴＯ基板１２ａを大気下で１４５℃、１０分加熱を行い、余分な溶媒を飛ばした。Ａｇナノ粒子１３を内包したＰＥＤＯＴ−ＰＳＳ層１４の膜厚は段差計を用いて測定した。得られた膜厚は６０ｎｍ程度である。このとき、Ａｇナノ粒子１３はＩＴＯ基板１２ａ側に偏在していた（図３（ｄ））。ここで偏在とは、Ａｇナノ粒子１３の中心からＩＴＯ基板１２ａの表面までの距離（ＸＡｇ−ＩＴＯ）とＡｇナノ粒子の中心から後述する光電変換層１５までの距離（ＸＡｇ−ｐａｌ）において、ＸＡｇ−ＩＴＯ＜ＸＡｇ−ｐａｌの関係を満たすことである。 Next, the PEDOT-PSS solution was dropped through a filter having a diameter of 0.45 μm on the ITO substrate 12a on which the Ag nanoparticles 13 were arranged, and the PEDOT-PSS layer 14 was formed by a spin coating method. The spin coating conditions at this time were 30 seconds with a spin coater rotating at 4000 rpm. After the film formation, the ITO substrate 12a was heated in the atmosphere at 145 ° C. for 10 minutes to remove excess solvent. The film thickness of the PEDOT-PSS layer 14 including the Ag nanoparticles 13 was measured using a step gauge. The film thickness obtained is about 60 nm. At this time, Ag nanoparticles 13 were unevenly distributed on the ITO substrate 12a side (FIG. 3D). Here, uneven distribution refers to the distance from the center of the Ag nanoparticles 13 to the surface of the ITO substrate 12a (X Ag-ITO ) and the distance from the center of the Ag nanoparticles to the photoelectric conversion layer 15 described later (X Ag-pal ). , X Ag-ITO <X Ag-pal .
また、一般的にはＰＥＤＯＴ−ＰＳＳのＰＳＳ成分１４ａは後述する対向電極１７側に偏析することが知られている。ＰＳＳ成分１４ａは強酸性のため、Ａｇナノ粒子１３を酸化させ、有機光電変換素子の特性に悪影響を与えてしまう。本実施例では、Ａｇナノ粒子１３をＩＴＯ基板１２ａ側に偏在させることで上記問題を回避することができる。 In general, it is known that the PSS component 14a of PEDOT-PSS is segregated on the counter electrode 17 side described later. Since the PSS component 14a is strongly acidic, it oxidizes the Ag nanoparticles 13 and adversely affects the characteristics of the organic photoelectric conversion element. In the present embodiment, the above problem can be avoided by making the Ag nanoparticles 13 unevenly distributed on the ITO substrate 12a side.
次に、その上にＰＴＢ７および７０ＰＣＢＭをクロロベンゼンと１，８−ジヨードオクタンに溶解した混合溶液をスピンコート法で塗布して光電変換層１５を形成した（図３（ｅ））。上記混合溶液は、ＰＴＢ７と７０ＰＣＢＭとの比が１：１．５であり、ＰＴＢ７および７０ＰＣＢＭはクロロベンゼンおよび１，８−ジヨードオクタンの混合溶液（クロロベンゼン：１，８−ジヨードオクタン＝９７Ｖｏｌ％：３Ｖｏｌ％）１ｍｌ中に２０ｍｇ溶解されている。スピンコートの条件は、スピンコータの回転数が７００ｒｐｍで６０秒間行った。 Next, a mixed solution in which PTB7 and 70PCBM were dissolved in chlorobenzene and 1,8-diiodooctane was applied thereon by a spin coating method to form the photoelectric conversion layer 15 (FIG. 3E). In the mixed solution, the ratio of PTB7 to 70PCBM is 1: 1.5, and PTB7 and 70PCBM are mixed solutions of chlorobenzene and 1,8-diiodooctane (chlorobenzene: 1,8-diiodooctane = 97 Vol%: 3 vol%) 20 mg is dissolved in 1 ml. The spin coating was performed at a spin coater rotation speed of 700 rpm for 60 seconds.
続いて、光電変換層１５の表面に、電子輸送層としてフッ化リチウム層１６を蒸着により形成する（図３（ｆ））。その後、電子輸送層１６上にＡｇ−Ｍｇ合金をマスクを用いて蒸着し、対向電極１７を形成する。このようにして形成された有機光電変換素子に光を照射し、ＩＴＯ基板１２ａと対向電極１７との間にＩ−Ｖ特性を測定した（図３（ｇ）、３（ｈ））。 Subsequently, a lithium fluoride layer 16 is formed as an electron transport layer on the surface of the photoelectric conversion layer 15 by vapor deposition (FIG. 3F). Thereafter, an Ag—Mg alloy is deposited on the electron transport layer 16 using a mask to form the counter electrode 17. The organic photoelectric conversion element thus formed was irradiated with light, and IV characteristics were measured between the ITO substrate 12a and the counter electrode 17 (FIGS. 3 (g) and 3 (h)).
（実施例２）
上記の実施例１において、Ａｇナノ粒子１００倍希釈したものに代えて２００倍希釈したものを用いた以外は、実施例１と同様にして有機光電変換素子を作製した。この実施例２においては、Ａｇナノ粒子１３の密度は、ＩＴＯ基板１２ａ上に６粒／μｍ２であった。
(Example 2)
An organic photoelectric conversion device was produced in the same manner as in Example 1 except that in Example 1 above, a 200-fold diluted solution was used instead of the Ag nanoparticle diluted 100-fold. In Example 2, the density of the Ag nanoparticles 13 was 6 particles / μm 2 on the ITO substrate 12a.
（実施例３）
上記の実施例１において、Ａｇナノ粒子１００倍希釈したものに代えて４０倍希釈したものを用いた以外は、実施例１と同様にして有機光電変換素子を作製した。この実施例３においては、Ａｇナノ粒子１３の密度は、ＩＴＯ基板１２ａ上に２８粒／μｍ２であった。
(Example 3)
An organic photoelectric conversion element was produced in the same manner as in Example 1 except that in Example 1 above, a 40-fold diluted one was used instead of the Ag nanoparticle diluted 100-fold. In Example 3, the density of the Ag nanoparticles 13 was 28 grains / μm 2 on the ITO substrate 12a.
（実施例４）
上記の実施例１において、Ａｇナノ粒子１００倍希釈したものに代えて２０倍希釈したものを用いた以外は、実施例１と同様にして有機光電変換素子を作製した。この実施例４においては、Ａｇナノ粒子１３の密度は、ＩＴＯ基板１２ａ上に５５粒／μｍ２であった。
Example 4
An organic photoelectric conversion device was produced in the same manner as in Example 1 except that in Example 1 above, a 20-fold diluted one was used instead of the Ag nanoparticle diluted 100-fold. In Example 4, the density of the Ag nanoparticles 13 was 55 grains / μm 2 on the ITO substrate 12a.
（比較例１）
上記の実施例１において、ＰＥＤＯＴ−ＰＳＳ層にＡｇナノ粒子を内包しない以外は、実施例１と同様にして有機光電変換素子を作製した。
(Comparative Example 1)
In said Example 1, the organic photoelectric conversion element was produced like Example 1 except not including Ag nanoparticle in a PEDOT-PSS layer.
（比較例２）
上記の実施例１において、ＰＥＤＯＴ−ＰＳＳ溶液にＡｇナノ粒子溶液を１００倍希釈したものを添加し、その溶液をＩＴＯ上に滴下、スピンコート法で成膜した以外は、実施例１と同様にして有機光電変換素子を作製した。スピンコートの条件は、スピンコータの回転数が４０００ｒｐｍで３０秒間行った。この比較例２においては、スピンコート回転による遠心力でＡｇナノ粒子の大部分が飛散された。
(Comparative Example 2)
In Example 1 described above, except that a 100-fold diluted Ag nanoparticle solution was added to the PEDOT-PSS solution, and the solution was dropped on ITO and formed into a film by a spin coating method. Thus, an organic photoelectric conversion element was produced. The spin coating was performed at a spin coater rotation speed of 4000 rpm for 30 seconds. In Comparative Example 2, most of the Ag nanoparticles were scattered by centrifugal force due to spin coating rotation.
（比較例３）
上記の実施例１において、Ａｇナノ粒子１００倍希釈したものに代えて５倍希釈したものを用いた以外は、実施例１と同様にして有機光電変換素子を作製した。この比較例３においては、Ａｇナノ粒子１３の密度は、ＩＴＯ基板１２ａ上に２２０粒／μｍ２であった。
(Comparative Example 3)
An organic photoelectric conversion device was produced in the same manner as in Example 1 except that in Example 1 above, a solution diluted 5 times instead of 100 times diluted with Ag nanoparticles was used. In Comparative Example 3 , the density of the Ag nanoparticles 13 was 220 grains / μm 2 on the ITO substrate 12a.
（有機光電変換素子の短絡電流密度（Ｊｓｃ）、開放電圧（Ｖｏｃ）、形状因子（ＦＦ）、変換効率評価）
上記の実施例１乃至４および比較例１乃至３の有機光電変換素子において、１ｃｍ角のマスクを被せて照射光１００ｍｗ／ｃｍ２の条件で電流−電圧特性を評価した。図５は、実施例１乃至４および比較例１乃至３の有機光電変換素子の電流−電圧特性から得られた短絡電流密度（Ｊｓｃ）、開放電圧（Ｖｏｃ）、形状因子（ＦＦ）、変換効率を示す。
(Short-circuit current density (Jsc), open-circuit voltage (Voc), form factor (FF), conversion efficiency evaluation of organic photoelectric conversion element)
In the organic photoelectric conversion elements of Examples 1 to 4 and Comparative Examples 1 to 3, the current-voltage characteristics were evaluated under the condition of irradiation light of 100 mw / cm 2 with a 1 cm square mask. FIG. 5 shows the short-circuit current density (Jsc), open-circuit voltage (Voc), form factor (FF), and conversion efficiency obtained from the current-voltage characteristics of the organic photoelectric conversion elements of Examples 1 to 4 and Comparative Examples 1 to 3. Indicates.
図６にＡｇナノ粒子希釈条件と変換効率の関係を表す。２０〜１００倍の希釈では、Ａｇナノ粒子を内包しない場合よりも変換効率が高い結果が得られた。これは、Ａｇナノ粒子の密度が６〜５５個／μｍ２およびＡｇナノ粒子の被覆率が０．０３３％〜０．３３％に対応する。従って、ＩＴＯ上にＡｇナノ粒子を配置してからＰＥＤＯＴ−ＰＳＳ層を形成した実施例１乃至４は、ＰＥＤＯＴ−ＰＳＳ層中にＡｇナノ粒子を内包しない比較例１よりも高い変換効率が得られた。 FIG. 6 shows the relationship between Ag nanoparticle dilution conditions and conversion efficiency. When the dilution was 20 to 100 times, the conversion efficiency was higher than when no Ag nanoparticles were encapsulated. This corresponds to a density of Ag nanoparticles of 6 to 55 particles / μm 2 and a coverage of Ag nanoparticles of 0.033% to 0.33%. Therefore, Examples 1 to 4 in which the PEDOT-PSS layer was formed after the Ag nanoparticles were placed on the ITO obtained higher conversion efficiency than Comparative Example 1 in which the Ag nanoparticles were not included in the PEDOT-PSS layer. It was.
なお、比較例３は、ＩＴＯ基板上のＡｇナノ粒子の密度が２２０粒／μｍ２であるにも関わらず、比較例１よりも変換効率が低い。これは、比較例３は比較例１に比べて、Ａｇナノ粒子が高濃度（５倍希釈）であり、製造時は２０ｎｍ程度のＡｇナノ粒子は凝集して２次粒子を形成する。２次粒子を形成したＡｇナノ粒子がＩＴＯと光電変換層との間のリークもしくはＩＴＯと対向電極を構成するＡｇ−Ｍｇ合金との間のリークを促進したために変換効率が低下したと推察される。 In Comparative Example 3, although the density of Ag nanoparticles on the ITO substrate is 220 particles / μm 2 , the conversion efficiency is lower than that of Comparative Example 1. This is because Comparative Example 3 has a higher concentration (5 times dilution) of Ag nanoparticles than Comparative Example 1, and Ag nanoparticles of about 20 nm aggregate to form secondary particles during production. It is inferred that the conversion efficiency was lowered because the Ag nanoparticles forming the secondary particles promoted the leakage between the ITO and the photoelectric conversion layer or the leakage between the ITO and the Ag-Mg alloy constituting the counter electrode. .
以上のことから、Ａｇナノ粒子の密度が１〜５５個／μｍ２であれば高い変換効率を得ることができる。 From the above, high conversion efficiency can be obtained when the density of Ag nanoparticles is 1 to 55 particles / μm 2 .
また、図５からわかるように、ＰＥＤＯＴ−ＰＳＳ溶液にＡｇナノ粒子溶液を添加して、その溶液をＩＴＯ上に滴下し、スピンコート法で成膜した比較例２の有機薄膜太陽電池は、Ａｇナノ粒子を内包していない比較例１の有機光電変換素子と同程度の変換効率が得られた。これは、ＰＥＤＯＴ−ＰＳＳ溶液にＡｇナノ粒子溶液を添加し、その溶液をＩＴＯ上に滴下、スピンコート法で成膜すると、スピンコート回転による遠心力でＡｇナノ粒子の大部分が飛散されたと考えられる。そのため、比較例２は実質的に比較例１と同様にＰＥＤＯＴ−ＰＳＳ層にＡｇナノ粒子を内包しないものと近い状態になったために、比較例２の変換効率は比較例１よりも改善しなかったと考えられる。 In addition, as can be seen from FIG. 5, the organic thin-film solar cell of Comparative Example 2 in which an Ag nanoparticle solution was added to a PEDOT-PSS solution, the solution was dropped on ITO, and formed by spin coating, A conversion efficiency comparable to that of the organic photoelectric conversion element of Comparative Example 1 not including nanoparticles was obtained. This is because when Ag nanoparticle solution was added to PEDOT-PSS solution, and the solution was dropped on ITO and deposited by spin coating, most of Ag nanoparticles were scattered by centrifugal force due to spin coating rotation. It is done. For this reason, Comparative Example 2 is substantially similar to Comparative Example 1 in which the PEDOT-PSS layer is not encapsulated with Ag nanoparticles, so that the conversion efficiency of Comparative Example 2 is not improved as compared with Comparative Example 1. It is thought.
また、上記説明では、金属ナノ粒子はＡｇであったが、金属ナノ粒子は、Ａｕ、Ａｇ、Ａｌ、Ｃｕ、Ｐｔの群から選ばれる少なくとも１つの元素を含んでいてもよい。 In the above description, the metal nanoparticles are Ag. However, the metal nanoparticles may contain at least one element selected from the group consisting of Au, Ag, Al, Cu, and Pt.
以上の結果から、本発明者らの実験結果によると、金属ナノ粒子の表面から光電変換層までの距離がその粒径よりも十分大きいにもかかわらず、変換効率の向上が確認された。この実験結果は、金属ナノ粒子が作る局在表面プラズモンでは、変換効率の向上が説明できない現象である。 From the above results, according to the experiment results of the present inventors, it was confirmed that the conversion efficiency was improved even though the distance from the surface of the metal nanoparticles to the photoelectric conversion layer was sufficiently larger than the particle size. This experimental result is a phenomenon in which the improvement in conversion efficiency cannot be explained by localized surface plasmons produced by metal nanoparticles.
なお、本発明者らは、上記現象は金属ナノ粒子の光散乱強度が何らかの形で寄与していると推察している。 The present inventors presume that the above phenomenon contributes in some way to the light scattering intensity of the metal nanoparticles.
以上説明したように、本実施形態および各実施例によれば、有機光電変換素子の導電性基板上に金属ナノ粒子を内包した正孔輸送層を形成するため、変換効率を向上させることができる。また、導電性高分子溶液の塗布によって導電性基板上に金属ナノ粒子を内包した正孔輸送層を形成するので、真空設備が不要であり、製造コストを削減することができる。さらに、既存のプロセスラインに導電性基板上に金属ナノ粒子を内包した正孔輸送層を形成する工程を追加することで有機光電変換素子を作製できるため、既存のプロセスラインの大幅な変更を必要としないという利点がある。 As described above, according to the present embodiment and each example, since the hole transport layer including the metal nanoparticles is formed on the conductive substrate of the organic photoelectric conversion element, the conversion efficiency can be improved. . In addition, since the hole transport layer including the metal nanoparticles is formed on the conductive substrate by applying the conductive polymer solution, a vacuum facility is unnecessary, and the manufacturing cost can be reduced. In addition, it is possible to produce organic photoelectric conversion elements by adding a process for forming a hole transport layer containing metal nanoparticles on a conductive substrate to an existing process line, which requires significant changes to the existing process line. There is an advantage of not.
以上により、本実施形態によれば、変換効率が高く、低コスト、かつ既存のプロセスラインの大幅な変更を必要としない有機光電変換素子を提供することができる。 As described above, according to the present embodiment, it is possible to provide an organic photoelectric conversion element that has high conversion efficiency, low cost, and does not require a significant change of an existing process line.
本実施形態の有機光電変換素子を備えた有機薄膜太陽電池は、低照度な室内光において発電効率が高い。このため、この有機薄膜太陽電池は、図７に示すように、サーバＰＣまたはラジオ放送局からの信号に基づいて表示する電子棚札２００の電源２１０として用いることができる。また、図８に示すように、センサー２５０、例えば動きセンサー、温度センサー、湿度センサー、照明センサー等の電源２１０として用いることができる。さらに、図９に示すように、腕時計２６０の電源２１０として用いることができる。 The organic thin-film solar cell provided with the organic photoelectric conversion element of this embodiment has high power generation efficiency in low-intensity indoor light. Therefore, as shown in FIG. 7, the organic thin film solar cell can be used as a power source 210 of an electronic shelf label 200 that is displayed based on a signal from a server PC or a radio broadcast station. Further, as shown in FIG. 8, the sensor 250 can be used as a power source 210 such as a motion sensor, a temperature sensor, a humidity sensor, and a lighting sensor. Furthermore, as shown in FIG. 9, it can be used as the power source 210 of the wristwatch 260.
本発明のいくつかの実施形態を説明したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これらの実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これらの実施形態やその変形は、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。 Although several embodiments of the present invention have been described, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the invention described in the claims and equivalents thereof as well as included in the scope and gist of the invention.
１ 有機薄膜太陽電池のセル
１１ 基板
１２ 透明電極
１３ 金属ナノ粒子
１４ 正孔輸送層
１５ 光電変換層
１６ 電子輸送層
１７ 対向電極
１８ 反射防止膜
DESCRIPTION OF SYMBOLS 1 Cell of organic thin film solar cell 11 Substrate 12 Transparent electrode 13 Metal nanoparticle 14 Hole transport layer 15 Photoelectric conversion layer 16 Electron transport layer 17 Counter electrode 18 Antireflection film
Claims (8)
前記正孔輸送層は、金属ナノ粒子とポリエチレンジオキシチオフェン／ポリスチレンスルホン酸（ＰＥＤＯＴ／ＰＳＳ）を含み、前記金属ナノ粒子の平均粒径ｄと前記正孔輸送層の膜厚ｔとの間にｄ＜ｔの関係が成立し、かつ、前記金属ナノ粒子が前記第１電極側に偏在し、前記第１電極側に配置されている前記金属ナノ粒子の密度が６〜５５粒子／μｍ２の範囲内にある有機光電変換素子。 A first electrode; a hole transport layer provided on the first electrode; an organic photoelectric conversion layer provided on the hole transport layer and having an organic p-type semiconductor and an organic n-type semiconductor; An electron transport layer provided on the conversion layer, and a second electrode provided on the electron transport layer,
The hole transport layer includes metal nanoparticles and polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT / PSS), and is between an average particle diameter d of the metal nanoparticles and a film thickness t of the hole transport layer. d <t is satisfied, the metal nanoparticles are unevenly distributed on the first electrode side, and the density of the metal nanoparticles arranged on the first electrode side is 6 to 55 particles / μm 2 . Organic photoelectric conversion element in the range.
前記正孔輸送層は、前記金属ナノ粒子を含む溶液を前記第１電極に塗布することにより配置してから前記ポリエチレンジオキシチオフェン／ポリスチレンスルホン酸を含む溶液を塗布して形成する有機光電変換素子の製造方法。 It is a manufacturing method which manufactures the organic photoelectric conversion element in any one of Claims 1 thru | or 7, Comprising:
The hole transport layer is formed by applying the solution containing the metal nanoparticles to the first electrode, and then applying the solution containing the polyethylene dioxythiophene / polystyrene sulfonic acid. Manufacturing method.
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| JP2019067817A (en) * | 2017-09-28 | 2019-04-25 | 積水化学工業株式会社 | Solar cell |
| CN109346603A (en) * | 2018-09-18 | 2019-02-15 | 张军 | A kind of organic solar batteries and preparation method thereof |
| CN109390474A (en) * | 2018-11-15 | 2019-02-26 | 南京邮电大学 | A method of improving inverted structure perovskite solar battery open-circuit voltage and fill factor |
| CN111276623B (en) * | 2020-01-19 | 2023-04-18 | 中国工程物理研究院流体物理研究所 | Modified hole transport layer and blue-light perovskite light-emitting diode based on same |
| CN115485872A (en) | 2020-04-27 | 2022-12-16 | 松下知识产权经营株式会社 | Solar cell |
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