JP2013149784A - Organic thin film solar cell and manufacturing method of the same - Google Patents
Organic thin film solar cell and manufacturing method of the same Download PDFInfo
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- JP2013149784A JP2013149784A JP2012009021A JP2012009021A JP2013149784A JP 2013149784 A JP2013149784 A JP 2013149784A JP 2012009021 A JP2012009021 A JP 2012009021A JP 2012009021 A JP2012009021 A JP 2012009021A JP 2013149784 A JP2013149784 A JP 2013149784A
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- solar cell
- organic thin
- film solar
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- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003518 tetracenes Chemical class 0.000 description 1
- VELSFHQDWXAPNK-UHFFFAOYSA-N tetracontacyclo[25.6.5.516,28.44,32.35,11.321,34.28,10.212,15.222,35.229,31.113,20.124,38.02,6.014,19.017,25.018,23.030,37.033,36.547,54.446,53.448,58.126,51.150,52.03,45.07,42.09,61.039,40.041,43.044,63.049,76.055,78.056,62.057,68.059,64.060,67.065,69.066,71.070,73.072,75.074,77]octaheptaconta-1,3(45),4(48),5(61),6,8,10,12,14,16,18,20,22,24(39),25,27(38),28,30,32,34(42),35(40),36,41(43),44(63),46,49(76),50(77),51,53,55(78),56(62),57,59,64,66,68,70(73),71,74-nonatriacontaene Chemical compound c12c3c4c5c6c1c1c7c8c2c2c3c3c9c4c4c5c5c%10c%11c%12c%13c%14c%15c%12c%12c%16c%17c%18c%19c%20c%21c%17c%17c%22c%21c%21c%23c%20c%20c%19c%19c%24c%18c%16c%15c%15c%24c%16c(c7c%15c%14c1c6c5%13)c8c1c2c2c3c3c(c%21c5c%22c(c%11c%12%17)c%10c4c5c93)c%23c2c%20c1c%19%16 VELSFHQDWXAPNK-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- QKTRRACPJVYJNU-UHFFFAOYSA-N thiadiazolo[5,4-b]pyridine Chemical compound C1=CN=C2SN=NC2=C1 QKTRRACPJVYJNU-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YWBFPKPWMSWWEA-UHFFFAOYSA-O triazolopyrimidine Chemical compound BrC1=CC=CC(C=2N=C3N=CN[N+]3=C(NCC=3C=CN=CC=3)C=2)=C1 YWBFPKPWMSWWEA-UHFFFAOYSA-O 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 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
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- Photovoltaic Devices (AREA)
Abstract
Description
本発明は、有機薄膜太陽電池およびその製造方法に関する。さらに詳しくは、本発明は、光電変換層が特定の構造を有する有機薄膜太陽電池およ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. More specifically, the present invention relates to an organic thin-film solar cell in which a photoelectric conversion layer has a specific structure and a method for producing the same.
近年、地球規模で問題となっているエネルギー問題を解決するための自然エネルギー源の一つとして、環境負荷が少なく、半永久的に供給される太陽光エネルギーの利用が活発に研究されている。中でも、太陽電池、特に、原料の低コスト化、柔軟性、形成の容易性等の観点から、光電変換層に有機化合物を用いた有機薄膜太陽電池が注目されている。
ところで、ｐ型有機半導体とｎ型有機半導体とのｐｎ接合型の有機薄膜太陽電池は、光吸収により、生成した励起子が、ｐｎ接合の界面に拡散移動して、電子と正孔に電荷分離し、それぞれ異なる電極に輸送されて、起電力を発生させるものである。
しかしながら、このときの励起子の拡散長は短く、ｐｎ接合界面からの距離が数十ｎｍの領域内でしか有効なキャリアが生成されず、従来は、十分なエネルギー（光電）変換効率が得られなかった。
エネルギー変換効率を向上させるために、例えば、非特許文献１に、銅フタロシアニン（ＣｕＰｃ）／フラーレン（Ｃ60）による有機薄膜太陽電池において、生成した励起子が失活するのを防止するために、バソクプロイン（4,7-ジフェニル-2,9-ジメチル-1,10-フェナントロリン、ＢＣＰ）を用いた励起子失活防止層を導入する方法が記載されている。
一方、最近では、光電変換効率を向上させるために、ｐｎ接合部分を拡張させる方法として、電子供与性材料と電子受容性材料とを単純積層するのではなく、混合することにより、分子レベルでのｐｎ接合が膜中に広く形成され、光電変換に寄与できる体積が増すバルクヘテロ型の有機薄膜太陽電池が提案されている（特許文献１〜６）。
さらに、非特許文献２には、ｐ型半導体層とｎ型半導体層の間にｐ型半導体とｎ型半導体の混合物からなる傾斜層を有する有機薄膜太陽電池が提案されている。
しかしながら、有機薄膜太陽電池の実用化のためには、さらなるエネルギー変換効率の向上が求められており、層構造や層の厚さ、その形成方法を工夫することにより、エネルギー変換効率を向上させることができることがわかった。
In recent years, as one of natural energy sources for solving energy problems that have become a problem on a global scale, the use of solar energy that has a low environmental impact and is supplied semipermanently has been actively studied. Among them, solar cells, particularly organic thin-film solar cells using an organic compound for the photoelectric conversion layer, have attracted attention from the viewpoints of cost reduction, flexibility, ease of formation, and the like.
By the way, in the pn junction type organic thin film solar cell of the p-type organic semiconductor and the n-type organic semiconductor, the generated excitons are diffused and moved to the interface of the pn junction by light absorption, and charge separation into electrons and holes is performed. Then, they are transported to different electrodes to generate an electromotive force.
However, the diffusion length of excitons at this time is short, and effective carriers are generated only in a region where the distance from the pn junction interface is several tens of nanometers. Conventionally, sufficient energy (photoelectric) conversion efficiency is obtained. There wasn't.
In order to improve energy conversion efficiency, for example, in Non-Patent Document 1, in order to prevent the generated excitons from being deactivated in an organic thin film solar cell using copper phthalocyanine (CuPc) / fullerene (C 60 ), A method of introducing an exciton deactivation preventing layer using bathocuproine (4,7-diphenyl-2,9-dimethyl-1,10-phenanthroline, BCP) is described.
On the other hand, recently, in order to improve the photoelectric conversion efficiency, as a method of expanding the pn junction part, the electron donating material and the electron accepting material are not simply laminated but mixed, so that at the molecular level. A bulk hetero type organic thin film solar cell in which a pn junction is widely formed in a film and a volume capable of contributing to photoelectric conversion is increased has been proposed (Patent Documents 1 to 6).
Further, Non-Patent Document 2 proposes an organic thin-film solar cell having an inclined layer made of a mixture of a p-type semiconductor and an n-type semiconductor between a p-type semiconductor layer and an n-type semiconductor layer.
However, further improvement of energy conversion efficiency is required for practical use of organic thin-film solar cells, and energy conversion efficiency should be improved by devising the layer structure, layer thickness, and formation method. I found out that
本発明はこのような事情に鑑みてなされたもので、本発明の目的は、上記のような問題を解決した、優れた有機薄膜太陽電池を提供することにある。 This invention is made | formed in view of such a situation, and the objective of this invention is providing the outstanding organic thin-film solar cell which solved the above problems.
上記のような問題を解決するため、本発明者らは鋭意検討した結果、下記のような層（領域）構成とすることにより、上記問題を解決することができることを見出し、本発明を完成させた。
すなわち、本発明は、下記
（1）透明電極と金属電極との間に光電変換層を有する有機薄膜太陽電池において、前記光電変換層が濃度勾配を有する混合半導体領域を含むことを特徴とする有機薄膜太陽電池、
（2）前記光電変換層がｐ型半導体領域、前記濃度勾配を有する混合半導体領域、ｎ型半導体領域の順に積層されてなる上記（1）に記載の有機薄膜太陽電池、
（3）前記混合半導体領域の濃度勾配が、前記ｐ型半導体領域から前記ｎ型半導体領域に向かって前記ｐ型半導体の量が０まで減少するとともに、前記ｎ型半導体の量が０から増加する濃度勾配である上記（2）に記載の有機薄膜太陽電池、
（4）前記混合半導体領域の厚さが前記ｐ型半導体領域およびｎ型半導体領域いずれの厚さよりも薄い厚さである上記（1）〜（3）のいずれかに記載の有機薄膜太陽電池、
（5）前記光電変換層が、ｐ型半導体領域、濃度勾配〔Ｃ１〕を有する混合半導体領域（Ａ）、i型半導体領域、濃度勾配〔Ｃ２〕を有する混合半導体領域（Ｂ）、およびｎ型半導体領域の順に積層されてなる上記（1）に記載の有機薄膜太陽電池、
（6）前記濃度勾配〔Ｃ１〕が、前記ｐ型半導体領域から前記i型半導体領域に向かって前記ｐ型半導体の量が減少するとともに、前記ｎ型半導体の量が０から増加する濃度勾配であり、前記濃度勾配〔Ｃ２〕が、前記ｉ型半導体領域から前記ｎ型半導体領域に向かって前記ｐ型半導体の量が０まで減少するとともに、前記ｎ型半導体の量が増加する濃度勾配である上記（5）に記載の有機薄膜太陽電池、
（7）前記混合半導体領域（Ａ）の厚さが前記ｐ型半導体領域およびｉ型半導体領域いずれの厚さよりも薄い厚さであり、前記混合半導体領域（Ｂ）の厚さが前記ｉ型半導体領域およびｎ型半導体領域いずれの厚さよりも薄い厚さである上記（5）または（6）に記載の有機薄膜太陽電池、
（8）前記ｐ型半導体領域およびｎ型半導体領域の厚さが、それぞれ５ｎｍ〜１μｍである上記（2）〜（7）のいずれかに記載の有機薄膜太陽電池、
（9）前記ｉ型半導体領域の厚さが５ｎｍ〜1μｍである上記（5）〜（7）のいずれかに記載の有機薄膜太陽電池、
（10）前記混合半導体領域の厚さが２〜１５ｎｍである上記（1）〜（4）のいずれかに記載の有機薄膜太陽電池、
（11）前記混合半導体領域（Ａ）および混合半導体領域（Ｂ）の厚さがそれぞれ２〜１５ｎｍである上記（5）〜（7）のいずれかに記載の有機薄膜太陽電池、
（12）透明電極と金属電極との間に光電変換層を有する有機薄膜太陽電池の製造方法であって、下記工程Ｓ１〜工程Ｓ４、
工程Ｓ１：透明電極の一方の面にｐ型半導体を一定の蒸着速度〔Ｒ１〕で一定時間〔Ｔ１〕かけて蒸着してｐ型半導体領域を形成する工程、
工程Ｓ２：前記工程１に続いて、前記ｐ型半導体を一定の蒸着速度〔Ｒ２〕から０まで一定時間〔Ｔ２〕かけて徐々に減速させるとともに、ｎ型半導体を０から一定の蒸着速度〔Ｒ２〕まで一定時間〔Ｔ２〕かけて徐々に増加させながら蒸着してｐ型半導体とｎ型半導体の濃度勾配を有する混合半導体領域を形成する工程、
工程Ｓ３：前記工程２に続いて、ｎ型半導体を一定の蒸着速度〔Ｒ３〕で一定時間〔Ｔ３〕かけて蒸着することによりｎ型半導体領域を形成する工程および
工程Ｓ４：金属電極を形成する工程
からなることを特徴とする有機薄膜太陽電池の製造方法（I）、
（１３）透明電極と金属電極との間に光電変換層を有する有機薄膜太陽電池の製造方法であって、下記工程Ｓ１１〜工程Ｓ１６、
工程Ｓ１１：透明電極の一方の面にｐ型半導体を一定の蒸着速度〔Ｒ11〕で一定時間〔Ｔ11〕かけて蒸着してｐ型半導体領域を形成する工程、
工程Ｓ１２：前記工程１１に続いて、前記ｐ型半導体を蒸着速度〔Ｒ11〕から蒸着速度〔Ｒ12〕まで一定時間〔Ｔ12〕かけて徐々に減速させるとともに、ｎ型半導体を０から一定の蒸着速度〔Ｒ13〕まで一定時間〔Ｔ12〕かけて徐々に増加させながら蒸着してｐ型半導体とｎ型半導体の濃度勾配〔Ｃ１〕を有する混合半導体領域（Ａ）を形成する工程、
工程Ｓ１３：前記工程１２に続いて、ｐ型半導体を一定の蒸着速度〔Ｒ12〕、ｎ型半導体を一定の蒸着速度〔Ｒ13〕で一定時間〔Ｔ13〕かけて共蒸着することによりｉ型半導体領域を形成する工程、
工程Ｓ１４：前記工程１３に続いて、前記ｐ型半導体の蒸着速度〔Ｒ12〕を一定時間〔Ｔ14〕かけて０まで徐々に減速させるとともに、ｎ型半導体の蒸着速度〔Ｒ13〕から一定の蒸着速度〔Ｒ14〕まで一定時間〔Ｔ14〕かけて徐々に増加させながら蒸着してｐ型半導体とｎ型半導体の濃度勾配〔Ｃ２〕を有する混合半導体領域（Ｂ）を形成する工程、
工程Ｓ１５：前記工程１４に続いて、ｎ型半導体を一定の蒸着速度〔Ｒ14〕で一定時間〔Ｔ15〕かけて蒸着することによりｎ型半導体領域を形成する工程および工程Ｓ１６：金属電極を形成する工程からなることを特徴とする有機薄膜太陽電池の製造方法（II）を提供する。
In order to solve the above problems, the present inventors have intensively studied. As a result, the inventors have found that the above problems can be solved by adopting the following layer (region) configuration, and completed the present invention. It was.
That is, the present invention provides (1) an organic thin film solar cell having a photoelectric conversion layer between a transparent electrode and a metal electrode, wherein the photoelectric conversion layer includes a mixed semiconductor region having a concentration gradient. Thin film solar cells,
(2) The organic thin film solar cell according to (1), wherein the photoelectric conversion layer is laminated in the order of a p-type semiconductor region, a mixed semiconductor region having the concentration gradient, and an n-type semiconductor region,
(3) The concentration gradient of the mixed semiconductor region is such that the amount of the p-type semiconductor decreases from 0 toward the n-type semiconductor region from the p-type semiconductor region, and the amount of the n-type semiconductor increases from 0. The organic thin-film solar cell according to (2) above, which is a concentration gradient,
(4) The organic thin-film solar cell according to any one of (1) to (3), wherein the thickness of the mixed semiconductor region is thinner than any of the p-type semiconductor region and the n-type semiconductor region,
(5) The photoelectric conversion layer includes a p-type semiconductor region, a mixed semiconductor region (A) having a concentration gradient [C1], an i-type semiconductor region, a mixed semiconductor region (B) having a concentration gradient [C2], and an n-type The organic thin-film solar cell according to (1), which is laminated in the order of the semiconductor region,
(6) The concentration gradient [C1] is a concentration gradient in which the amount of the p-type semiconductor decreases from the p-type semiconductor region to the i-type semiconductor region and the amount of the n-type semiconductor increases from 0. And the concentration gradient [C2] is a concentration gradient in which the amount of the p-type semiconductor decreases from the i-type semiconductor region to the n-type semiconductor region and the amount of the n-type semiconductor increases. The organic thin film solar cell according to (5) above,
(7) The thickness of the mixed semiconductor region (A) is thinner than both the p-type semiconductor region and the i-type semiconductor region, and the thickness of the mixed semiconductor region (B) is the i-type semiconductor. The organic thin-film solar cell according to the above (5) or (6), which is thinner than any of the region and the n-type semiconductor region,
(8) The organic thin-film solar cell according to any one of (2) to (7), wherein the p-type semiconductor region and the n-type semiconductor region each have a thickness of 5 nm to 1 μm.
(9) The organic thin-film solar cell according to any one of (5) to (7), wherein the i-type semiconductor region has a thickness of 5 nm to 1 μm.
(10) The organic thin film solar cell according to any one of (1) to (4), wherein the mixed semiconductor region has a thickness of 2 to 15 nm.
(11) The organic thin-film solar cell according to any one of (5) to (7), wherein the mixed semiconductor region (A) and the mixed semiconductor region (B) each have a thickness of 2 to 15 nm.
(12) A method for producing an organic thin-film solar cell having a photoelectric conversion layer between a transparent electrode and a metal electrode, comprising the following steps S1 to S4,
Step S1: A step of forming a p-type semiconductor region by depositing a p-type semiconductor on one surface of a transparent electrode at a constant deposition rate [R1] over a predetermined time [T1].
Step S2: Following the step 1, the p-type semiconductor is gradually decelerated from a constant deposition rate [R2] to 0 over a fixed time [T2], and the n-type semiconductor is reduced from 0 to a constant deposition rate [R2 A step of forming a mixed semiconductor region having a concentration gradient of the p-type semiconductor and the n-type semiconductor by vapor deposition while gradually increasing over a certain time [T2]
Step S3: Subsequent to Step 2, the step of forming an n-type semiconductor region by depositing an n-type semiconductor at a constant deposition rate [R3] for a predetermined time [T3] and Step S4: forming a metal electrode A method (I) for producing an organic thin-film solar cell, characterized by comprising steps
(13) A method for producing an organic thin-film solar cell having a photoelectric conversion layer between a transparent electrode and a metal electrode, the following steps S11 to S16,
Step S11: forming a p-type semiconductor region by depositing a p-type semiconductor on one surface of the transparent electrode at a constant deposition rate [R11] over a predetermined time [T11].
Step S12: Following the step 11, the p-type semiconductor is gradually decelerated from the deposition rate [R11] to the deposition rate [R12] over a predetermined time [T12], and the n-type semiconductor is reduced from 0 to a constant deposition rate. Forming a mixed semiconductor region (A) having a concentration gradient [C1] of a p-type semiconductor and an n-type semiconductor by vapor deposition while gradually increasing to [R13] over a certain time [T12];
Step S13: Following the step 12, the i-type semiconductor region is formed by co-depositing the p-type semiconductor at a constant deposition rate [R12] and the n-type semiconductor at a constant deposition rate [R13] over a predetermined time [T13]. Forming a process,
Step S14: Following the step 13, the deposition rate [R12] of the p-type semiconductor is gradually reduced to 0 over a predetermined time [T14], and the deposition rate [R13] is constant from the deposition rate [R13] of the n-type semiconductor. Forming a mixed semiconductor region (B) having a concentration gradient [C2] of a p-type semiconductor and an n-type semiconductor by vapor deposition while gradually increasing to [R14] over a predetermined time [T14];
Step S15: Following the step 14, the n-type semiconductor is deposited at a constant deposition rate [R14] over a predetermined time [T15] to form an n-type semiconductor region, and step S16: a metal electrode is formed. Provided is a method (II) for producing an organic thin-film solar cell comprising steps.
本発明の有機薄膜太陽電池（以下、ＯＳＣと記載することがある）は、混合半導体領域が両側に隣接する各半導体材料の濃度勾配を有することにより、従来のｐｎ接合型有機薄膜太陽電池と比べて光電変換効率が向上した有機薄膜太陽電池を得ることができる。 The organic thin film solar cell of the present invention (hereinafter sometimes referred to as OSC) has a concentration gradient of each semiconductor material adjacent to both sides of the mixed semiconductor region, so that it is compared with a conventional pn junction type organic thin film solar cell. Thus, an organic thin film solar cell with improved photoelectric conversion efficiency can be obtained.
以下、本発明について、詳細に説明する。
本発明のＯＳＣは、透明電極と金属電極との間に光電変換層を有する有機薄膜太陽電池であって、前記光電変換層が濃度勾配を有する混合半導体領域を含むことを特徴とする。また、前記光電変換層がｐ型半導体領域、i型半導体領域、ｎ型半導体領域等の半導体領域を複数有し、これら複数の半導体領域の間に濃度勾配を形成している混合半導体領域が存在していることを特徴としている。
以下、本発明のＯＳＣの構成材料およびその製造方法について図１〜図３を用いて説明する。
Hereinafter, the present invention will be described in detail.
The OSC of the present invention is an organic thin film solar cell having a photoelectric conversion layer between a transparent electrode and a metal electrode, wherein the photoelectric conversion layer includes a mixed semiconductor region having a concentration gradient. The photoelectric conversion layer has a plurality of semiconductor regions such as a p-type semiconductor region, an i-type semiconductor region, and an n-type semiconductor region, and there is a mixed semiconductor region in which a concentration gradient is formed between the plurality of semiconductor regions. It is characterized by that.
Hereinafter, the constituent material of the OSC of the present invention and the manufacturing method thereof will be described with reference to FIGS.
〔透明電極〕
図２（a）および図３（a）における透明電極２または１２として用いられる材料は、透明性を有し、かつ導電性を有するものであれば特に限定されるものではないが、例えば、酸化ニッケル、酸化錫、酸化インジウム、錫ドープ酸化インジウム（ＩＴＯ）、酸化インジウム亜鉛（ＩＺＯ）、ガリウムドープ酸化亜鉛（ＧＺＯ）、酸化チタン、酸化インジウム、酸化亜鉛などの導電性金属酸化物、あるいは金、白金、銀、クロムなどの金属およびその合金、ポリチオフェン誘導体にポリスチレンスルフォン酸をドーピングしたＰＥＤＯＴ／ＰＳＳや、ポリピロールおよびポリアニリンなどにヨウ素などのドーピングした導電性ポリマーなどが挙げられる。これらの透明電極用材料は、単独で用いてもよいが、複数の材料を混合して用いてもよい。中でも、光が透過する位置にある電極は、ＩＴＯ、酸化スズ、酸化亜鉛、ＩＺＯ等の酸化物等の透明電極を用いることが好ましい。また、ＩＴＯ、ＧＺＯ、酸化スズ、酸化亜鉛、金、コバルト、ニッケル、白金等の仕事関数の高い材料と、アルミニウム、銀、リチウム、インジウム、カルシウム、マグネシウム等を組み合わせて用いてもよい。透明電極２または１２の膜厚に制限はなく、抵抗値に合わせて任意に選ぶことが出来る。ただし、通常１０ｎｍ以上、中でも５０ｎｍ以上、また、通常１０００ｎｍ以下、中でも５００ｎｍ以下、さらには３００ｎｍ以下、特には１００ｎｍ以下とすることが好ましい。透明電極が厚すぎると透明性が低下し、高コストとなる可能性があり、薄すぎると直列抵抗が大きく、性能が低下する可能性がある。透明電極２または１２のシート抵抗は、短絡電流密度を大きくする観点から、５０Ω／□以下、１０Ω／□以下が好ましい。透明電極２または１２は、通常、ガラス板のような透明な無機材料や透明なプラスチックフィルム等の透明基材１または１１の一方の面に形成されている。
[Transparent electrode]
The material used as the transparent electrode 2 or 12 in FIG. 2 (a) and FIG. 3 (a) is not particularly limited as long as it has transparency and conductivity. Conductive metal oxides such as nickel, tin oxide, indium oxide, tin-doped indium oxide (ITO), indium zinc oxide (IZO), gallium-doped zinc oxide (GZO), titanium oxide, indium oxide, zinc oxide, or gold, Examples thereof include metals such as platinum, silver and chromium and alloys thereof, PEDOT / PSS in which polythiophene derivatives are doped with polystyrene sulfonic acid, and conductive polymers in which polypyrrole and polyaniline are doped with iodine or the like. These transparent electrode materials may be used alone, or a plurality of materials may be mixed and used. Especially, it is preferable to use transparent electrodes, such as oxides, such as ITO, a tin oxide, zinc oxide, and IZO, for the electrode in the position which permeate | transmits light. Alternatively, a material having a high work function such as ITO, GZO, tin oxide, zinc oxide, gold, cobalt, nickel, or platinum may be used in combination with aluminum, silver, lithium, indium, calcium, magnesium, or the like. There is no restriction | limiting in the film thickness of the transparent electrode 2 or 12, It can select arbitrarily according to resistance value. However, it is preferably 10 nm or more, particularly 50 nm or more, and usually 1000 nm or less, particularly 500 nm or less, more preferably 300 nm or less, and particularly preferably 100 nm or less. If the transparent electrode is too thick, the transparency may be reduced and the cost may be high. If the transparent electrode is too thin, the series resistance may be large and the performance may be reduced. The sheet resistance of the transparent electrode 2 or 12 is preferably 50Ω / □ or less and 10Ω / □ or less from the viewpoint of increasing the short-circuit current density. The transparent electrode 2 or 12 is usually formed on one surface of the transparent substrate 1 or 11 such as a transparent inorganic material such as a glass plate or a transparent plastic film.
〔ｐ型半導体領域〕
ｐ型半導体領域３または１３の材料としては、電子供与性を有するものであれば特に限定されず、例えば、光電変換効率の観点から、金属を含有していないフタロシアニン（Ｈ2Ｐｃ）、銅フタロシアニンのように中心に種々の金属をもつフタロシアニン誘導体、ポルフィリン誘導体、キナクリドン顔料、ペリレン顔料、メロシアニン等とその誘導体、トリフェニルアミン、ジフェニルアミン、フェニレンジアミンなどの芳香族アミン化合物、ナフタレン、アントラセンなどの縮合多環炭化水素、アゾベンゼンなどのアゾ化合物、スチルベンなどの芳香環をエチレン結合やアセチレン結合で連結した構造を有する化合物、アミノ基で置換されたヘテロ芳香環化合物、キノン類、テトラシアノキノジメタン類、ジシアノキノンジイミン類、テトラシアノエチレン、ビオローゲン類、ジチオール金属錯体などが挙げられる。また、上記化合物の混合物であってもよい。
ｐ型半導体領域３または１３の厚さは、好ましくは５ｎｍ〜１μｍ、より好ましくは１０〜１００ｎｍである。該膜厚が５ｎｍ以上であることにより、十分に光を吸収できるため好ましく、１μｍ以下であることにより素子抵抗の観点から低抵抗であり好ましい。
[P-type semiconductor region]
The material of the p-type semiconductor region 3 or 13 is not particularly limited as long as it has an electron donating property. For example, from the viewpoint of photoelectric conversion efficiency, phthalocyanine (H 2 Pc) or copper phthalocyanine which does not contain a metal is used. Phthalocyanine derivatives, porphyrin derivatives, quinacridone pigments, perylene pigments, merocyanines and their derivatives having various metals at the center, aromatic amine compounds such as triphenylamine, diphenylamine, and phenylenediamine, and condensed polyvalent compounds such as naphthalene and anthracene. Ring hydrocarbons, azo compounds such as azobenzene, compounds having a structure in which aromatic rings such as stilbene are linked by ethylene bond or acetylene bond, heteroaromatic compounds substituted with amino groups, quinones, tetracyanoquinodimethanes, Dicyanoquinone diimines, Tet Cyano ethylene, viologen compounds, such as dithiol metal complexes. Moreover, the mixture of the said compound may be sufficient.
The thickness of the p-type semiconductor region 3 or 13 is preferably 5 nm to 1 μm, more preferably 10 to 100 nm. The film thickness of 5 nm or more is preferable because light can be sufficiently absorbed, and the film thickness of 1 μm or less is preferable from the viewpoint of device resistance because of low resistance.
〔ｎ型半導体領域〕
ｎ型半導体領域５または１７の材料としては、フラーレン又はフラーレン化合物、カーボンナノチューブ、カーボンナノチューブ誘導体、縮合芳香族炭素環化合物（ナフタレン誘導体、アントラセン誘導体、フェナントレン誘導体、テトラセン誘導体、ピレン誘導体、ペリレン誘導体、ペリレンイミド誘導体、ナフタレンイミド誘導体、フルオランテン誘導体）、窒素原子、酸素原子、硫黄原子を含有する５〜７員のヘテロ環化合物（例えばピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、キノリン、キノキサリン、キナゾリン、フタラジン、シンノリン、イソキノリン、プテリジン、アクリジン、フェナジン、フェナントロリン、テトラゾール、ピラゾール、イミダゾール、チアゾール、オキサゾール、インダゾール、ベンズイミダゾール、ベンゾトリアゾール、ベンゾオキサゾール、ベンゾチアゾール、カルバゾール、プリン、トリアゾロピリダジン、トリアゾロピリミジン、テトラザインデン、オキサジアゾール、イミダゾピリジン、ピラリジン、ピロロピリジン、チアジアゾロピリジン、ジベンズアゼピン、トリベンズアゼピン、オキサジアゾール誘導体等）、ポリアリーレン化合物、フルオレン化合物、シクロペンタジエン化合物、シリル化合物、キノリン金属錯体、ベンゾチアゾール金属錯体、ベンゾオキサゾール金属錯体、ベンゾイミダゾール金属錯体等の含窒素ヘテロ環化合物を配位子として有する金属錯体のような有機半導体が挙げられる。また、上記化合物の混合物であってもよい。
好ましくは、フラーレンまたはフラーレン化合物である。フラーレンとしては、フラーレンＣ60、フラーレンＣ70、フラーレンＣ76、フラーレンＣ78、フラーレンＣ80、フラーレンＣ82、フラーレンＣ84、フラーレンＣ90、フラーレンＣ96、フラーレンＣ240、フラーレンＣ540、ミックスドフラーレン、フラーレンナノチューブ等が挙げられ、フラーレン化合物としてはこれらに置換基が付加された化合物が挙げられる。これらのフラーレンのうち、Ｃ60は入手しやすく、コスト面で有利であるなどの利点を有している。
ｎ型半導体領域５または１７の厚さは、好ましくは５ｎｍ〜１μｍ、より好ましくは１０〜１００ｎｍである。該膜厚が５ｎｍ以上であることにより吸光度の観点から十分に光を吸収できるため好ましく、１μｍ以下であることにより素子抵抗の観点から低抵抗であり好ましい。
[N-type semiconductor region]
Examples of the material of the n-type semiconductor region 5 or 17 include fullerene or fullerene compounds, carbon nanotubes, carbon nanotube derivatives, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, perylene imides. Derivatives, naphthaleneimide derivatives, fluoranthene derivatives), 5- to 7-membered heterocyclic compounds containing nitrogen, oxygen, and sulfur atoms (eg, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline) , Isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benz Midazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, oxadiazole, imidazopyridine, pyralidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine, Oxadiazole derivatives, etc.), polyarylene compounds, fluorene compounds, cyclopentadiene compounds, silyl compounds, quinoline metal complexes, benzothiazole metal complexes, benzoxazole metal complexes, benzimidazole metal complexes and other nitrogen-containing heterocyclic compounds as ligands And an organic semiconductor such as a metal complex. Moreover, the mixture of the said compound may be sufficient.
Preferably, it is fullerene or a fullerene compound. Fullerene C 60 , fullerene C 70 , fullerene C 76 , fullerene C 78 , fullerene C 80 , fullerene C 82 , fullerene C 84 , fullerene C 90 , fullerene C 96 , fullerene C 240 , fullerene C 540 , mixed Fullerenes, fullerene nanotubes and the like can be mentioned, and examples of the fullerene compounds include compounds having a substituent added thereto. Among these fullerenes, C 60 is easily available, has advantages such as is advantageous in cost.
The thickness of the n-type semiconductor region 5 or 17 is preferably 5 nm to 1 μm, more preferably 10 to 100 nm. When the film thickness is 5 nm or more, light can be sufficiently absorbed from the viewpoint of absorbance, and when it is 1 μm or less, low resistance is preferable from the viewpoint of element resistance.
〔真性（ｉ型）半導体領域〕
図３（a）に示されているように、後で述べる混合半導体領域（Ａ）１４を介してｐ型半導体領域１３に形成されるｉ型半導体領域１５の材料としては、例えば、フラーレン、フラーレン誘導体、半導体性を有するカーボンナノチューブ（ＣＮＴ）およびＣＮＴ化合物等のｎ型半導体材料から選ばれるのは少なくとも１種類からなる第１の材料と、金属を含有していないフタロシアニン（Ｈ2Ｐｃ）、銅フタロシアニンのように中心に種々の金属をもつフタロシアニン誘導体などのｐ型半導体材料から選ばれる少なくとも１種類の第２の材料とを、得られる半導体が真性半導体となるように混合した混合物を使用することができる。
真性半導体領域１５の厚さは、好ましくは５ｎｍ〜１μｍ、より好ましくは１０〜１００ｎｍである。該膜厚が５ｎｍ以上であることにより吸光度の観点から十分に光を吸収できるため好ましく、１μｍ以下であることにより素子抵抗の観点から低抵抗であり好ましい。
[Intrinsic (i-type) semiconductor region]
As shown in FIG. 3A, examples of the material of the i-type semiconductor region 15 formed in the p-type semiconductor region 13 through the mixed semiconductor region (A) 14 described later include fullerene and fullerene. At least one first material selected from n-type semiconductor materials such as derivatives, semiconducting carbon nanotubes (CNT) and CNT compounds, phthalocyanine (H 2 Pc), copper containing no metal Use a mixture in which at least one second material selected from p-type semiconductor materials such as phthalocyanine derivatives having various metals at the center, such as phthalocyanine, is mixed so that the obtained semiconductor becomes an intrinsic semiconductor. Can do.
The thickness of the intrinsic semiconductor region 15 is preferably 5 nm to 1 μm, more preferably 10 to 100 nm. When the film thickness is 5 nm or more, light can be sufficiently absorbed from the viewpoint of absorbance, and when it is 1 μm or less, low resistance is preferable from the viewpoint of element resistance.
〔混合半導体領域〕
（1）第１の実施形態
本発明の第１の実施形態において、図２（a）に示すように、混合半導体領域４は、ｐ型半導体領域３とｎ型半導体領域５の間に形成される領域であり、以下のような濃度勾配を有する。
すなわち、混合半導体領域４における濃度勾配は、前記ｐ型半導体領域３から前記ｎ型半導体領域５に向かってｐ型半導体の量が０まで減少するとともに、前記ｎ型半導体の量が０から増加する濃度勾配である。濃度勾配は連続的に形成されていることが好ましい。この混合半導体領域４は後で述べる製造方法（I）における工程Ｓ２で形成される。
混合半導体領域４の厚さは２〜１５ｎｍ、好ましくは３〜１０ｎｍである。混合半導体領域４の厚さを上記範囲とすることにより、成膜時間が短縮され、かつ、ｐ型半導体領域３とｎ型半導体領域５の隣接部分に混合半導体領域４を存在させることにより、電流がより流れやすくなり、変換効率が向上する。
[Mixed semiconductor area]
(1) First Embodiment In the first embodiment of the present invention, the mixed semiconductor region 4 is formed between the p-type semiconductor region 3 and the n-type semiconductor region 5 as shown in FIG. And has a concentration gradient as follows.
That is, the concentration gradient in the mixed semiconductor region 4 is such that the amount of p-type semiconductor decreases from 0 toward the n-type semiconductor region 5 from the p-type semiconductor region 3 and the amount of n-type semiconductor increases from 0. Concentration gradient. The concentration gradient is preferably formed continuously. The mixed semiconductor region 4 is formed in step S2 in the manufacturing method (I) described later.
The thickness of the mixed semiconductor region 4 is 2 to 15 nm, preferably 3 to 10 nm. By setting the thickness of the mixed semiconductor region 4 within the above range, the film formation time is shortened, and by allowing the mixed semiconductor region 4 to exist in the adjacent portion of the p-type semiconductor region 3 and the n-type semiconductor region 5, the current Becomes easier to flow and conversion efficiency is improved.
本発明の第１の実施形態であるＯＳＣは、前記混合半導体領域４の厚さが前記ｐ型半導体領域３の厚さおよびｎ型半導体領域５の厚さより薄くなるように形成されることが好ましい。各領域の厚さを上記のような関係とすることにより、混合半導体領域４による界面の形成により光電変換効率を向上させることができる。 The OSC according to the first embodiment of the present invention is preferably formed such that the thickness of the mixed semiconductor region 4 is smaller than the thickness of the p-type semiconductor region 3 and the thickness of the n-type semiconductor region 5. . By setting the thickness of each region as described above, the photoelectric conversion efficiency can be improved by the formation of the interface by the mixed semiconductor region 4.
本発明のＯＳＣにおいて、「層」という用語を使用せずに「領域」という用語を使用している理由は下記のとおりである。
すなわち、図２(a)で示されるように、隣接したそれぞれの半導体領域３および５と混合半導体領域４との間で明確な境界（界面）を有していないからである。
比較のため、図２(b)について説明する。図２(b)は従来のＯＳＣの層構成を示す模式図である。
透明基材１、透明電極２は前記図２（a）で説明したものと同じである。
図２(b)におけるｐ型半導体層３′とｎ型半導体層５′は図２(a)におけるｐ型半導体領域３とｎ型半導体領域５とは異なっている。すなわち、図２(b)においては、ｐ型半導体層３′とｎ型半導体層５′の間で、明確な境界（界面）を有しており、図２（a)に示すような濃度勾配を有するｐ型半導体とｎ型半導体からなる混合半導体領域４が存在していない。
The reason why the term “region” is used instead of the term “layer” in the OSC of the present invention is as follows.
That is, as shown in FIG. 2A, there is no clear boundary (interface) between the adjacent semiconductor regions 3 and 5 and the mixed semiconductor region 4.
For comparison, FIG. 2B will be described. FIG. 2B is a schematic diagram showing a layer structure of a conventional OSC.
The transparent substrate 1 and the transparent electrode 2 are the same as those described with reference to FIG.
The p-type semiconductor layer 3 ′ and the n-type semiconductor layer 5 ′ in FIG. 2B are different from the p-type semiconductor region 3 and the n-type semiconductor region 5 in FIG. That is, in FIG. 2B, there is a clear boundary (interface) between the p-type semiconductor layer 3 ′ and the n-type semiconductor layer 5 ′, and the concentration gradient as shown in FIG. There is no mixed semiconductor region 4 made of a p-type semiconductor and an n-type semiconductor.
（2）第２の実施形態
本発明の第２の実施形態においては、図３（a）に示すように、透明電極１２と金属電極７との間に光電変換層を有する有機薄膜太陽電池において、前記光電変換層が、ｐ型半導体領域１３、混合半導体領域（Ａ）、i型半導体領域１５、混合半導体領域（Ｂ）、およびｎ型半導体領域１７の順に積層されてなる。
〔混合半導体領域（Ａ）〕
図３（a）における混合半導体領域（Ａ）１４はｐ型半導体領域１３とｉ型半導体領域１５の間に形成される領域であり、以下のような濃度勾配（Ｃ１）を有する。すなわち、混合半導体領域（Ａ）１４における濃度勾配〔Ｃ１〕は、ｐ型半導体領域１３から前記ｉ型半導体領域１５に向かって前記ｐ型半導体の量が減少するとともに、前記ｎ型半導体の量が０から増加する濃度勾配である。濃度勾配は連続的に形成されていることが好ましい。混合半導体領域（Ａ）１４は後で述べる製造方法（II）における工程Ｓ１２で形成される。
混合半導体領域（Ａ）１４の厚さは２〜１５ｎｍ、好ましくは３〜１０ｎｍである。
混合半導体領域（Ａ）１４の厚さを上記範囲とすることにより、成膜時間が短縮され、かつ、ｐ型半導体領域１３とi型半導体領域１５の隣接部分に混合半導体領域（Ａ）１４を存在させることにより、電流がより流れやすくなり、変換効率が向上する。
(2) Second Embodiment In the second embodiment of the present invention, as shown in FIG. 3A, in an organic thin-film solar cell having a photoelectric conversion layer between a transparent electrode 12 and a metal electrode 7 The photoelectric conversion layer is formed by sequentially stacking a p-type semiconductor region 13, a mixed semiconductor region (A), an i-type semiconductor region 15, a mixed semiconductor region (B), and an n-type semiconductor region 17.
[Mixed semiconductor region (A)]
The mixed semiconductor region (A) 14 in FIG. 3A is a region formed between the p-type semiconductor region 13 and the i-type semiconductor region 15 and has the following concentration gradient (C1). That is, the concentration gradient [C1] in the mixed semiconductor region (A) 14 decreases the amount of the p-type semiconductor from the p-type semiconductor region 13 toward the i-type semiconductor region 15 and increases the amount of the n-type semiconductor. Concentration gradient increasing from zero. The concentration gradient is preferably formed continuously. The mixed semiconductor region (A) 14 is formed in step S12 in the manufacturing method (II) described later.
The thickness of the mixed semiconductor region (A) 14 is 2 to 15 nm, preferably 3 to 10 nm.
By setting the thickness of the mixed semiconductor region (A) 14 in the above range, the film formation time is shortened, and the mixed semiconductor region (A) 14 is provided adjacent to the p-type semiconductor region 13 and the i-type semiconductor region 15. By making it exist, an electric current flows more easily and conversion efficiency improves.
〔混合半導体領域（Ｂ）〕
図３（a）における混合半導体領域（Ｂ）１６はi型半導体領域１５とｎ型半導体領域１７の間に形成される領域であり、以下のような濃度勾配〔Ｃ２〕を有する。
すなわち、混合半導体領域（Ｂ）１６における濃度勾配〔Ｃ２〕はi型半導体領域１５から前記ｎ型半導体領域１７に向かって前記ｐ型半導体の量が０まで減少するとともに、前記ｎ型半導体の量が増加する濃度勾配である。濃度勾配は連続的に形成されていることが好ましい。
混合半導体領域（Ｂ）１６は後で述べる製造方法（II）における工程Ｓ１４で形成される。
混合半導体領域（Ｂ）１６の厚さは２〜１５ｎｍ、好ましくは３〜１０ｎｍである。混合半導体領域（Ｂ）１６の厚さを上記範囲とすることにより、成膜時間が短縮され、かつ、i型半導体領域１５とｎ型半導体領域１７の隣接部分に混合半導体領域（Ｂ）１６を存在させることにより、電流がより流れやすくなり、変換効率が向上する。
[Mixed semiconductor region (B)]
The mixed semiconductor region (B) 16 in FIG. 3A is a region formed between the i-type semiconductor region 15 and the n-type semiconductor region 17 and has the following concentration gradient [C2].
That is, the concentration gradient [C2] in the mixed semiconductor region (B) 16 reduces the amount of the p-type semiconductor from the i-type semiconductor region 15 toward the n-type semiconductor region 17, and reduces the amount of the n-type semiconductor. Is a concentration gradient that increases. The concentration gradient is preferably formed continuously.
The mixed semiconductor region (B) 16 is formed in step S14 in the manufacturing method (II) described later.
The thickness of the mixed semiconductor region (B) 16 is 2 to 15 nm, preferably 3 to 10 nm. By setting the thickness of the mixed semiconductor region (B) 16 in the above range, the film formation time is shortened, and the mixed semiconductor region (B) 16 is provided adjacent to the i-type semiconductor region 15 and the n-type semiconductor region 17. By making it exist, an electric current flows more easily and conversion efficiency improves.
本発明の第２の実施形態であるＯＳＣにおいては、前記混合半導体領域１４の厚さが前記ｐ型半導体領域１３およびi型半導体領域１５いずれの厚さより薄い厚さで、前記混合半導体領域（Ｂ）１６の厚さが前記i型半導体領域１５およびｎ型半導体領域１７いずれの厚さより薄い厚さであることが好ましい。各領域の厚さを上記のような関係とすることにより、光電変換効率を向上させることができる。
本発明のＯＳＣにおいて、「層」という用語を使用せずに「領域」という用語を使用している理由は下記のとおりである。
すなわち、図３(a)で示されるように、ｐ型半導体領域１３、混合半導体領域（Ａ）１４、i型半導体領域１５、混合半導体領域（Ｂ）１６及びｎ型半導体領域１７との間で明確な境界（界面）を有していない。
比較のため、図３(b)について説明する。図３(b)は従来のＯＳＣの層構成を示す模式図である。
透明基材１１、透明電極１２は前記図３（a）で説明したものと同じである。
図３(b)におけるｐ型半導体層１３′、i型半導体層１５′、ｎ型半導体層１７′は図３(a)におけるｐ型半導体領域１３、i型半導体層１５およびｎ型半導体領域１７とは異なっている。
すなわち、図３(b)においては、ｐ型半導体層１３′とi型半導体層１５′の間、およびi型半導体層１５′とｎ型半導体層１７′との間で、それぞれ明確な境界（界面）を有している。すなわち、図３（a)に示すような、濃度勾配を有する混合半導体領域（Ａ）１４および濃度勾配を有する混合半導体領域（Ｂ）１６が存在しない。
In the OSC according to the second embodiment of the present invention, the thickness of the mixed semiconductor region 14 is smaller than the thickness of either the p-type semiconductor region 13 or the i-type semiconductor region 15, and the mixed semiconductor region (B ) 16 is preferably thinner than both the i-type semiconductor region 15 and the n-type semiconductor region 17. The photoelectric conversion efficiency can be improved by setting the thickness of each region as described above.
The reason why the term “region” is used instead of the term “layer” in the OSC of the present invention is as follows.
That is, as shown in FIG. 3A, between the p-type semiconductor region 13, the mixed semiconductor region (A) 14, the i-type semiconductor region 15, the mixed semiconductor region (B) 16, and the n-type semiconductor region 17. It does not have a clear boundary (interface).
For comparison, FIG. 3B will be described. FIG. 3B is a schematic diagram showing a layer structure of a conventional OSC.
The transparent substrate 11 and the transparent electrode 12 are the same as those described with reference to FIG.
The p-type semiconductor layer 13 ', i-type semiconductor layer 15', and n-type semiconductor layer 17 'in FIG. 3B are the p-type semiconductor region 13, i-type semiconductor layer 15, and n-type semiconductor region 17 in FIG. Is different.
That is, in FIG. 3B, clear boundaries (between the p-type semiconductor layer 13 'and the i-type semiconductor layer 15' and between the i-type semiconductor layer 15 'and the n-type semiconductor layer 17') ( Interface). That is, the mixed semiconductor region (A) 14 having a concentration gradient and the mixed semiconductor region (B) 16 having a concentration gradient as shown in FIG.
〔バッファ層〕
また、本発明のＯＳＣにおいては、図２、図３に示すように、バッファ層６及び１８を有していてもよい。このようなバッファ層６及び１８び１０を設けることで、生成した励起子が失活するのを防止することができるため、ＴＯＳＣの変換効率をさらに向上させることができる。バッファ層６または１８の材料としては、バソクプロイン等の公知のものを使用することができる。
[Buffer layer]
The OSC of the present invention may have buffer layers 6 and 18 as shown in FIGS. By providing such buffer layers 6, 18 and 10, it is possible to prevent the generated excitons from being deactivated, so that the TOSC conversion efficiency can be further improved. As a material of the buffer layer 6 or 18, a known material such as bathocuproine can be used.
〔金属電極〕
金属電極７または１９は、前記ｎ型半導体領域５または１７もしくは必要に応じて形成されるバッファ層６または１上に形成される。
金属電極用の材料としては、対向電極となる前記透明電極２または１２の材料（例えばＩＴＯ電極）に比べて仕事関数の差が大きいものが好ましい。例えば、銀、アルミニウム、銅、ニッケル、白金、金、イリジウム、クロム、酸化亜鉛、ルテニウム、チタン、タンタル、モリブデン、ニオブ、ジルコニウム、バナジウム又はこれらのうちのいずれかを含む合金、金属酸化物もしくは合金の他、上記金属、金属酸化物もしくは合金との複合体が挙げられる。
金属電極７または１９の厚さは、２０ｎｍ〜３００nmであることが好ましく、特に３０〜１５０ｎｍであることがより好ましい。
金属電極７または１９を形成する方法としては、プラズマＣＶＤ法や熱化学蒸着法等の化学気相成長法や、真空蒸着、スパッタリング、イオンプレーティング等のＰＶＤ（物理気相蒸着）が挙げられ、適宜選択される。
[Metal electrode]
The metal electrode 7 or 19 is formed on the n-type semiconductor region 5 or 17 or the buffer layer 6 or 1 formed as necessary.
As the material for the metal electrode, a material having a large work function difference as compared with the material of the transparent electrode 2 or 12 (for example, ITO electrode) to be the counter electrode is preferable. For example, silver, aluminum, copper, nickel, platinum, gold, iridium, chromium, zinc oxide, ruthenium, titanium, tantalum, molybdenum, niobium, zirconium, vanadium, or an alloy, metal oxide or alloy containing any of these In addition, the composite with the said metal, a metal oxide, or an alloy is mentioned.
The thickness of the metal electrode 7 or 19 is preferably 20 nm to 300 nm, and more preferably 30 to 150 nm.
Examples of the method for forming the metal electrode 7 or 19 include chemical vapor deposition methods such as plasma CVD and thermochemical vapor deposition, and PVD (physical vapor deposition) such as vacuum vapor deposition, sputtering, and ion plating. It is selected appropriately.
前記各層、領域等を形成する方法は、特に限定されず、公知の方法を用いることができる。例えば、真空蒸着、スパッタリング、イオンプレーティング等のＰＶＤ（物理気相蒸着）、もしくは熱ＣＶＤ、原子層堆積（ＡＬＤ）等のＣＶＤ（化学気相蒸着）などのドライプロセス、等の公知の方法により形成することができ、透明電極２または１２やｐ型、ｎ型、i型半導体の材料に応じて適宜選択される。ただし、ｐ型半導体領域３、濃度勾配を有する混合半導体領域４、ｎ型半導体領域をそれぞれ連続して形成するには真空蒸着が用いられ、混合半導体領域４を形成するためには真空共蒸着が用いられる。
同様に、ｐ型半導体領域１３、濃度勾配を有する混合半導体領域（Ａ）１４、i型半導体領域１５およびi型半導体領域１３、濃度勾配を有する混合半導体領域（Ｂ）１６、ｎ型半導体領域１７をそれぞれ連続して形成するには真空蒸着が用いられ、混合半導体領域（Ｂ）１６を形成するためには真空共蒸着が用いられる。
The method for forming each layer, region, etc. is not particularly limited, and a known method can be used. For example, by a known method such as PVD (physical vapor deposition) such as vacuum deposition, sputtering, ion plating, or dry process such as CVD (chemical vapor deposition) such as thermal CVD or atomic layer deposition (ALD). It can be formed, and is appropriately selected according to the material of the transparent electrode 2 or 12 and the p-type, n-type, and i-type semiconductor. However, vacuum deposition is used to continuously form the p-type semiconductor region 3, the mixed semiconductor region 4 having a concentration gradient, and the n-type semiconductor region, and vacuum co-evaporation is used to form the mixed semiconductor region 4. Used.
Similarly, a p-type semiconductor region 13, a mixed semiconductor region (A) 14 having a concentration gradient, an i-type semiconductor region 15 and an i-type semiconductor region 13, a mixed semiconductor region (B) 16 having a concentration gradient, and an n-type semiconductor region 17 Are continuously formed, and vacuum co-evaporation is used to form the mixed semiconductor region (B) 16.
各領域は表面抵抗率が５０Ω／□以下であることが好ましく、１０Ω／□以下であることがさらに好ましい。
表面抵抗率が５０Ω／□を超えると、内部抵抗が大きいため、光電変換効率が低下することがあるので好ましくない。
Each region preferably has a surface resistivity of 50Ω / □ or less, and more preferably 10Ω / □ or less.
When the surface resistivity exceeds 50 Ω / □, the internal resistance is large, which is not preferable because the photoelectric conversion efficiency may be lowered.
次に、本発明のＯＳＣの製造方法（I）および（II）を図１〜３に基づいて説明する。 Next, the manufacturing method (I) and (II) of OSC of this invention is demonstrated based on FIGS.
図１は２つの半導体材料を真空共蒸着により、連続して各領域を形成するための装置の一例を示す模式図である。
図１の蒸着源Ａより、透明電極（図１では基板と記載）にｐ型半導体を蒸着させ、ｐ型半導体領域を形成する。また、蒸着源Ｂにより、ｎ型半導体を透明電極（図１では基板と記載）に蒸着させ、ｎ型半導体領域を形成する。この際、蒸着源Ａと蒸着源Ｂの蒸着速度および蒸着時間を変化させることで、濃度勾配を有する混合半導体領域を含む光電変換層を成膜することができる。
FIG. 1 is a schematic view showing an example of an apparatus for continuously forming each region by vacuum co-evaporation of two semiconductor materials.
A p-type semiconductor is deposited on a transparent electrode (described as a substrate in FIG. 1) from the deposition source A in FIG. 1 to form a p-type semiconductor region. In addition, an n-type semiconductor is deposited on a transparent electrode (described as a substrate in FIG. 1) by the deposition source B to form an n-type semiconductor region. Under the present circumstances, the photoelectric converting layer containing the mixed semiconductor area | region which has a concentration gradient can be formed into a film by changing the vapor deposition rate and vapor deposition time of the vapor deposition source A and the vapor deposition source B. FIG.
まず、本発明のＯＳＣの製造方法（I）について説明する。
本発明のＯＳＣの製造方法（I）は、下記の工程Ｓ１〜工程Ｓ４を含む。
工程Ｓ１は、その一方の面にｐ型半導体を一定の蒸着速度〔Ｒ１〕で一定時間〔Ｔ１〕かけて蒸着してｐ型半導体領域３を形成するための工程である。この時、図１における蒸着源ＡまたはＢからのみ蒸着が行なわれる。
工程Ｓ２は前記工程Ｓ１に続いて、前記ｐ型半導体を蒸着速度〔Ｒ２〕から０まで一定時間〔Ｔ２〕かけて徐々に減速させるとともに、ｎ型半導体を０から一定の蒸着速度〔Ｒ２〕まで一定時間〔Ｔ２〕かけて徐々に増加させながら蒸着してｐ型半導体とｎ型半導体の濃度勾配を有する混合半導体領域４を形成するための工程である。この工程Ｓ２は図１に示されているように、２つの蒸着源ＡおよびＢからｐ型半導体とｎ型半導体が同時に蒸着される、すなわち、共蒸着が行なわれる工程である。〔Ｔ２〕の間、ｐ型半導体とｎ型半導体の各蒸着速度の合計は〔Ｒ２〕である。
工程Ｓ３は前記工程Ｓ２に続いて、ｎ型半導体を一定の蒸着速度〔Ｒ３〕で一定時間〔Ｔ３〕かけて蒸着することによりｎ型半導体領域５を形成するための工程であり、図１における蒸着源ＢまたはＡからのみ蒸着が行なわれる。
工程Ｓ４は形成されたｎ型半導体領域５に金属電極７を形成するための工程であり、真空蒸着等前記各種の方法により形成することができる。
本発明の製造方法（I）において、各半導体の蒸着速度および蒸着時間は特に限定されず、領域の膜厚に応じて適宜設定することができる。透明電極と金属電極との間に光電変換層を有する有機薄膜太陽電池を容易に製造することができることから、工程Ｓ１〜工程３を連続で行うことが好ましい。
この場合、〔Ｒ１〕＝〔Ｒ２〕＝〔Ｒ３〕であることが好ましい。
上記工程Ｓ３で形成されたｎ型半導体領域５には、金属電極７を形成する前に、必要に応じて、バッファ層６を形成させても良い。バッファ層６の形成は前記真空蒸着等各種の方法により行なうことができる。
First, the manufacturing method (I) of OSC of this invention is demonstrated.
The OSC manufacturing method (I) of the present invention includes the following steps S1 to S4.
Step S1 is a step for forming a p-type semiconductor region 3 by depositing a p-type semiconductor on one surface thereof at a constant deposition rate [R1] over a predetermined time [T1]. At this time, vapor deposition is performed only from the vapor deposition source A or B in FIG.
In step S2, following the step S1, the p-type semiconductor is gradually decelerated from the deposition rate [R2] to 0 over a predetermined time [T2], and the n-type semiconductor is reduced from 0 to a constant deposition rate [R2]. This is a step for forming a mixed semiconductor region 4 having a concentration gradient of a p-type semiconductor and an n-type semiconductor by vapor deposition while gradually increasing over a certain time [T2]. As shown in FIG. 1, this step S2 is a step in which a p-type semiconductor and an n-type semiconductor are simultaneously deposited from two deposition sources A and B, that is, a co-deposition is performed. During [T2], the total deposition rate of the p-type semiconductor and the n-type semiconductor is [R2].
Step S3 is a step for forming the n-type semiconductor region 5 by depositing an n-type semiconductor at a constant deposition rate [R3] over a predetermined time [T3] following the step S2, and in FIG. Deposition is performed only from the deposition source B or A.
Step S4 is a step for forming the metal electrode 7 in the formed n-type semiconductor region 5, and can be formed by the various methods such as vacuum deposition.
In the production method (I) of the present invention, the deposition rate and deposition time of each semiconductor are not particularly limited, and can be appropriately set according to the film thickness of the region. Since the organic thin-film solar cell which has a photoelectric converting layer between a transparent electrode and a metal electrode can be manufactured easily, it is preferable to perform process S1-process 3 continuously.
In this case, it is preferable that [R1] = [R2] = [R3].
In the n-type semiconductor region 5 formed in the step S3, a buffer layer 6 may be formed as necessary before the metal electrode 7 is formed. The buffer layer 6 can be formed by various methods such as vacuum evaporation.
次に、本発明のＯＳＣの製造方法（II）について説明する。
本発明のＯＳＣの製造方法（II）は、下記の工程Ｓ１１〜工程Ｓ１６を含む。
工程Ｓ１１は、その一方の面にｐ型半導体を一定の蒸着速度〔Ｒ11〕で一定時間〔Ｔ11〕蒸着してｐ型半導体領域１３を形成するための工程である。
工程Ｓ１２は前記工程１１に続いて、前記ｐ型半導体を一定の蒸着速度〔Ｒ11〕から〔Ｒ12〕まで一定時間〔Ｔ12〕かけて徐々に減速させるとともに、ｎ型半導体を０から一定の蒸着速度〔Ｒ13〕まで一定時間〔Ｔ12〕かけて徐々に増加させながら蒸着してｐ型半導体とｎ型半導体の濃度勾配（Ｃ１）を有する混合半導体領域（Ａ）１４を形成するための工程である。この工程Ｓ１２は図１に示されているように、２つの蒸着源ＡおよびＢからｐ型半導体とｉ型半導体が同時に蒸着される、すなわち、共蒸着が行なわれる工程である。
工程Ｓ１３は前記工程１２に続いて、ｐ型半導体を一定の蒸着速度〔Ｒ12〕、ｎ型半導体を一定の蒸着速度〔Ｒ13〕で一定時間〔Ｔ13〕蒸着することによりｉ型半導体領域１５を形成するための工程である。
工程Ｓ１４は前記工程１３に続いて、前記ｐ型半導体の蒸着速度〔Ｒ12〕を０まで一定時間〔Ｔ14〕かけて徐々に減速させるとともに、ｎ型半導体を一定の蒸着速度〔Ｒ13〕から一定の蒸着速度〔Ｒ14〕まで一定時間〔Ｔ14〕かけて徐々に増加させながら蒸着してｐ型半導体とｎ型半導体の濃度勾配（Ｃ２）を有する混合半導体領域（Ｂ）１６を形成するための工程である。この工程Ｓ１４は図１に示されているように、２つの蒸着源ＡおよびＢからｐ型半導体とｎ型半導体が同時に蒸着される、すなわち、共蒸着が行なわれる工程である。
工程Ｓ１５は前記工程Ｓ１４に続いて、ｎ型半導体を一定の蒸着速度〔Ｒ14〕で一定時間〔Ｔ15〕蒸着することによりｎ型半導体領域１７を形成するための工程である。
工程Ｓ１６は金属電極１９を形成するための工程であり、金属電極１９の形成は前記真空蒸着等各種の方法により行なうことができる。
本発明の製造方法（II）において、各半導体の蒸着速度および蒸着時間は特に限定されず、領域の膜厚に応じて適宜設定することができる。透明電極と金属電極との間に光電変換層を有する有機薄膜太陽電池を容易に製造することができることから、工程Ｓ１１〜工程Ｓ１５を連続で行うことが好ましい。
上記工程Ｓ１５で形成されたｎ型半導体領域１７には、金属電極１９を形成する前に、必要に応じて、バッファ層１８を形成しても良い。バッファ層１８の形成は前記真空蒸着等各種の方法により行なうことができる。
Next, the manufacturing method (II) of OSC of this invention is demonstrated.
The OSC manufacturing method (II) of the present invention includes the following steps S11 to S16.
Step S11 is a step for forming a p-type semiconductor region 13 by depositing a p-type semiconductor on one surface thereof at a constant deposition rate [R11] for a predetermined time [T11].
In step S12, following step 11, the p-type semiconductor is gradually decelerated from a constant deposition rate [R11] to [R12] over a fixed time [T12], and the n-type semiconductor is reduced from 0 to a constant deposition rate. This is a step for forming the mixed semiconductor region (A) 14 having the concentration gradient (C1) of the p-type semiconductor and the n-type semiconductor by vapor deposition while gradually increasing over [T12] for a certain time [R12]. As shown in FIG. 1, this step S12 is a step in which a p-type semiconductor and an i-type semiconductor are simultaneously deposited from two deposition sources A and B, that is, a co-deposition is performed.
In step S13, following step 12, the i-type semiconductor region 15 is formed by evaporating the p-type semiconductor at a constant deposition rate [R12] and the n-type semiconductor at a constant deposition rate [R13] for a predetermined time [T13]. It is a process for doing.
In step S14, following the step 13, the deposition rate [R12] of the p-type semiconductor is gradually reduced to 0 over a predetermined time [T14], and the n-type semiconductor is fixed from the constant deposition rate [R13] to a constant. A process for forming a mixed semiconductor region (B) 16 having a concentration gradient (C2) of a p-type semiconductor and an n-type semiconductor by vapor deposition while gradually increasing to a vapor deposition rate [R14] over a predetermined time [T14]. is there. As shown in FIG. 1, this step S14 is a step in which a p-type semiconductor and an n-type semiconductor are simultaneously deposited from two deposition sources A and B, that is, a co-deposition is performed.
Step S15 is a step for forming the n-type semiconductor region 17 by depositing an n-type semiconductor at a constant deposition rate [R14] for a predetermined time [T15] following the step S14.
Step S16 is a step for forming the metal electrode 19, and the metal electrode 19 can be formed by various methods such as vacuum deposition.
In the production method (II) of the present invention, the vapor deposition rate and vapor deposition time of each semiconductor are not particularly limited, and can be appropriately set according to the film thickness of the region. Since the organic thin-film solar cell which has a photoelectric converting layer between a transparent electrode and a metal electrode can be manufactured easily, it is preferable to perform process S11-process S15 continuously.
In the n-type semiconductor region 17 formed in the step S15, a buffer layer 18 may be formed as necessary before the metal electrode 19 is formed. The buffer layer 18 can be formed by various methods such as vacuum evaporation.
以下、実施例及び比較例により、本発明をさらに詳しく説明するが、本発明はこれらにより何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these.
＜実施例１＞
ｐ型半導体である銅フタロシアニン（ＣｕＰｃ）とｎ型半導体であるフラーレン（Ｃ60）を用いて有機薄膜太陽電池用素子を作製した。
透明電極としてＩＴＯ膜がパターニングされた２５ｍｍ×２５ｍｍガラス基板〔ＩＴＯ膜の厚さ１５０ｎｍ、三容真空工業製〕そのＩＴＯ膜の表面に、真空蒸着方法（真空蒸着装置は株式会社エイエルエステクノロジー製の有機ＥＬ蒸着装置、品番Ｅ-２００ＬＬ）によりＣｕＰｃを蒸着速度０．１ｎｍ/秒〔Ｒ１〕で、６００秒間〔Ｔ１〕真空蒸着して厚さ６０ｎｍを有するｐ型半導体領域を形成した。引き続いて、ＣｕＰｃの蒸着速度を０まで徐々に減少させながら、Ｃ60の蒸着速度を０から０．１ｎｍ/秒まで徐々に増加させた。即ち、ＣｕＰｃの蒸着速度を０．１ｎｍ/秒〔Ｒ２〕から〜０まで５０秒間〔Ｔ２〕徐々に減少させるとともに、ＣｕＰｃの蒸着速度が減少し始めた時点でＣ60の蒸着速度を０から０．１ｎｍ/秒〔Ｒ２〕まで、５０秒間〔Ｔ２〕徐々に増加させて共蒸着することにより、ＣｕＰｃとＣ60の濃度勾配を有する混合半導体領域（ＣｕＰｃ：Ｃ60）を形成した。
このように共蒸着により混合半導体領域の厚さが５ｎｍに到達した時点で、ＣｕＰｃの蒸着速度を０にし、Ｃ60は蒸着速度０．１ｎｍ/秒〔Ｒ３〕で５５０秒間〔Ｔ３〕継続的に真空蒸着を行い、厚さ５５ｎｍのｎ型半導体領域を形成した。
上記のｐ型半導体領域、混合半導体領域、およびｎ型半導体領域からなる光電変換層の形成は全て連続して蒸着を行なった。
続いて、ｎ型半導体領域にホールブロッキング材料であるＢＣＰ〔バソクプロイン（4,7-ジフェニル-2,9-ジメチル-1,10-フェナントロリン）〕を蒸着して厚さ１０ｎｍのバッファ層を形成した。次いで、バッファ層に金属電極材料であるＡｇを１００ｎｍの厚さになるように蒸着速度０．１ｎｍ/秒で１００秒間蒸着して金属電極を形成した。最後にガラスキャップを用いて全体を封止した。得られた有機薄膜太陽電池用素子の各領域等を構成する材料名とその厚さは下記の通りである。
ＩＴＯ(１５０ｎｍ)/ＣｕＰｃ(６０ｎｍ)/ＣｕＰｃ:Ｃ60（５ｎｍ）/Ｃ60（５５ｎｍ）/ＢＣＰ（１０ｎｍ）/Ａｇ(１００ｎｍ)
<Example 1>
An organic thin film solar cell element was fabricated using copper phthalocyanine (CuPc) as a p-type semiconductor and fullerene (C 60 ) as an n-type semiconductor.
25 mm × 25 mm glass substrate with ITO film patterned as a transparent electrode (ITO film thickness 150 nm, manufactured by Sanyo Vacuum Industries Co., Ltd.) A vacuum deposition method (vacuum deposition apparatus is manufactured by ALS Technology, Inc.) CuPc was vacuum-deposited for 600 seconds [T1] at a deposition rate of 0.1 nm / second [R1] using an organic EL deposition apparatus, product number E-200LL, to form a p-type semiconductor region having a thickness of 60 nm. Subsequently, while gradually decreasing the deposition rate of CuPc to 0, the deposition rate of C 60 was gradually increased from 0 to 0.1 nm / second. That, together with reducing the deposition rate of the CuPc 0.1 nm / 50 seconds to ~ 0 from seconds [R2] [T2] gradually, the deposition rate of the C 60 from 0 at the time when the deposition rate of the CuPc began to decrease 0 The mixed semiconductor region (CuPc: C 60 ) having a concentration gradient of CuPc and C 60 was formed by gradually increasing the vapor deposition rate to 1 nm / second [R2] and gradually increasing it for 50 seconds [T2].
Thus when the thickness of the mixed semiconductor region by a co-evaporation has reached 5 nm, the deposition rate of the CuPc to 0, C 60 550 seconds at a deposition rate of 0.1 nm / sec [R3] [T3] continuously Vacuum deposition was performed to form an n-type semiconductor region having a thickness of 55 nm.
The formation of the photoelectric conversion layer composed of the p-type semiconductor region, the mixed semiconductor region, and the n-type semiconductor region was all performed continuously.
Subsequently, BCP [basocuproin (4,7-diphenyl-2,9-dimethyl-1,10-phenanthroline)], which is a hole blocking material, was deposited on the n-type semiconductor region to form a buffer layer having a thickness of 10 nm. Next, Ag, which is a metal electrode material, was deposited on the buffer layer at a deposition rate of 0.1 nm / second for 100 seconds to form a metal electrode. Finally, the whole was sealed with a glass cap. The names of materials constituting the respective regions of the obtained organic thin film solar cell element and the thickness thereof are as follows.
ITO (150 nm) / CuPc (60 nm) / CuPc: C 60 (5 nm) / C 60 (55 nm) / BCP (10 nm) / Ag (100 nm)
＜比較例１＞
混合半導体領域(ＣｕＰｃ:Ｃ60)を形成せず、ｐ型半導体層（ＣｕＰｃ）とｎ型半導体層（Ｃ60）の厚さがいずれも６０ｎｍになるように蒸着時間を変更した以外は実施例１と同様に行い比較用の有機薄膜太陽電池用素子を作製した。比較用素子の層等を構成する材料名とその厚さは下記の通りである。
ＩＴＯ(１５０ｎｍ)/ＣｕＰｃ(６０ｎｍ)/Ｃ60（６０ｎｍ）/ＢＣＰ（１０ｎｍ）/Ａｇ(１００ｎｍ)
<Comparative Example 1>
Example except that the mixed semiconductor region (CuPc: C 60 ) is not formed, and the deposition time is changed so that the thicknesses of the p-type semiconductor layer (CuPc) and the n-type semiconductor layer (C 60 ) are both 60 nm. The device for organic thin film solar cell for comparison was produced in the same manner as in Example 1. The names of materials constituting the layers of the comparative elements and the thickness thereof are as follows.
ITO (150 nm) / CuPc (60 nm) / C 60 (60 nm) / BCP (10 nm) / Ag (100 nm)
実施例１で得られた有機薄膜太陽電池用の素子および比較例１で得られた素子の受光面（透明電極面）の有効面積５．５ｍｍ2に、ソーラーシミュレーター〔株式会社ワコム電創製、ＷＸＳ−５０Ｓ−１．５〕により擬似太陽光（ＡＭ１．５）を１００ｍＷ/ｃｍ2で照射して、電圧−電流発生器（ＡＤＣ製、装置名「Ｒ６２４３」）を用いて開放電圧、短絡電流密度、曲線因子を測定し、光電変換効率を算出した。表１に測定結果を示す。
表１に示されているように、実施例１で得られた有機薄膜太陽電池用の素子（素子１〜４）の光電変換効率は平均１．１７％であるのに対して比較用の素子の光電変換効率は０．８３％であり、約４１％向上していることがわかる。
In an effective area of 5.5 mm 2 on the light receiving surface (transparent electrode surface) of the element for the organic thin-film solar cell obtained in Example 1 and the element obtained in Comparative Example 1, a solar simulator [WXS, manufactured by Wacom Denso Co., Ltd. −50S-1.5] is irradiated with simulated sunlight (AM1.5) at 100 mW / cm 2 , and an open-circuit voltage and a short-circuit current density using a voltage-current generator (manufactured by ADC, device name “R6243”). The curve factor was measured and the photoelectric conversion efficiency was calculated. Table 1 shows the measurement results.
As shown in Table 1, the photoelectric conversion efficiency of the organic thin film solar cell elements (elements 1 to 4) obtained in Example 1 is 1.17% on the average, whereas the comparative element It can be seen that the photoelectric conversion efficiency is 0.83%, which is an improvement of about 41%.
＜実施例２＞
透明電極としてＩＴＯ膜がパターニングされた４５ｍｍ×４５ｍｍガラス基板〔ＩＴＯ膜の厚さ１５０ｎｍ、三容真空工業製〕を用い、混合半導体領域の厚さが１０ｎｍになるように共蒸着の時間を１００秒に変更した以外は実施例１と同様に行い有機薄膜太陽電池用の素子を作製した。
得られた有機薄膜太陽電池用の素子の各領域等を構成する材料名とその厚さは下記の通りである。
ＩＴＯ(１５０ｎｍ)/ＣｕＰｃ(６０ｎｍ)/ＣｕＰｃ:Ｃ60（１０ｎｍ）/Ｃ60（５５ｎｍ）/ＢＣＰ（１０ｎｍ）/Ａｇ(１００ｎｍ)
<Example 2>
Using a 45 mm × 45 mm glass substrate (ITO film thickness 150 nm, manufactured by Sanyo Vacuum Industries Co., Ltd.) on which an ITO film is patterned as a transparent electrode, the co-deposition time is 100 seconds so that the thickness of the mixed semiconductor region is 10 nm. Except having changed into, it carried out similarly to Example 1 and produced the element for organic thin film solar cells.
The names of materials constituting the regions of the organic thin film solar cell and the thicknesses thereof are as follows.
ITO (150 nm) / CuPc (60 nm) / CuPc: C 60 (10 nm) / C 60 (55 nm) / BCP (10 nm) / Ag (100 nm)
＜比較例２＞
混合半導体領域(ＣｕＰｃ:Ｃ60)を形成せず、ｐ型半導体層（ＣｕＰｃ）とｎ型半導体層（Ｃ60）の厚さがともに６０ｎｍになるように変更した以外は実施例２と同様に行い、比較用の素子を作製した。作製された比較用の素子の層構造は下記の通りである。
ＩＴＯ(１５０ｎｍ)/ＣｕＰｃ(６０ｎｍ)/Ｃ60（６０ｎｍ）/ＢＣＰ（１０ｎｍ）/Ａｇ(１００ｎｍ)
<Comparative example 2>
The mixed semiconductor region (CuPc: C 60 ) was not formed, and the thickness of the p-type semiconductor layer (CuPc) and the n-type semiconductor layer (C 60 ) was both changed to 60 nm, as in Example 2. A comparative element was fabricated. The layer structure of the manufactured comparative device is as follows.
ITO (150 nm) / CuPc (60 nm) / C 60 (60 nm) / BCP (10 nm) / Ag (100 nm)
実施例２で得られた有機薄膜太陽電池用の素子および比較例２で得られた比較用の素子がそれぞれ２個直列に連結されているものを用いて、受光面（透明電極）の有効面積１０．６４ｍｍ2に、ソーラーシミュレーター〔株式会社ワコム電創製、ＷＸＳ−５０Ｓ−１．５〕により擬似太陽光（ＡＭ１．５）を１００ｍＷ/ｃｍ2で照射して、電流密度等の出力特性の測定を行い、電圧−電流発生器（ＡＤＣ製、装置名「Ｒ６２４３」）を用いて開放電圧、短絡電流密度、曲線因子を測定し、光電変換効率を算出した。
表２に測定結果を示す。表２に示されているように、実施例２で得られた有機薄膜太陽電池の素子の光電変換効率は１．７７％であるのに対して比較例２の素子の光電変換効率は１．５７％であり、約１２．７％向上していることがわかる。
Using the organic thin film solar cell element obtained in Example 2 and the comparative element obtained in Comparative Example 2 connected in series, the effective area of the light receiving surface (transparent electrode) 10.64 mm 2 was irradiated with simulated sunlight (AM1.5) at 100 mW / cm 2 by a solar simulator [WXS-50S-1.5, manufactured by Wacom Denso Co., Ltd.], and the output characteristics such as current density were measured. The open-circuit voltage, short-circuit current density, and fill factor were measured using a voltage-current generator (manufactured by ADC, device name “R6243”), and the photoelectric conversion efficiency was calculated.
Table 2 shows the measurement results. As shown in Table 2, the photoelectric conversion efficiency of the element of the organic thin film solar cell obtained in Example 2 is 1.77%, whereas the photoelectric conversion efficiency of the element of Comparative Example 2 is 1. It is 57%, and it can be seen that there is an improvement of about 12.7%.
本発明の有機薄膜太陽電池は太陽光エネルギーによる電力供給源の一つとして使用可能である。 The organic thin film solar cell of this invention can be used as one of the electric power supply sources by solar energy.
１：透明基材
２：透明電極
３：ｐ型半導体領域
３′：ｐ型半導体層
４：混合半導体領域
５：ｎ型半導体領域
５′：ｎ型半導体層
６：バッファ層
７：金属電極
１１：透明基材
１２：透明電極
１３：ｐ型半導体領域
１３′：ｐ型半導体層
１４：混合半導体領域（Ａ）
１５：ｉ型半導体領域
１５′：ｉ型半導体層
１６：混合半導体領域（Ｂ）
１７：ｎ型半導体領域
１７′：ｎ型半導体層
１８：バッファ層
１９：金属電極
1: transparent substrate 2: transparent electrode 3: p-type semiconductor region 3 ′: p-type semiconductor layer 4: mixed semiconductor region 5: n-type semiconductor region 5 ′: n-type semiconductor layer 6: buffer layer 7: metal electrode 11: Transparent substrate 12: Transparent electrode 13: p-type semiconductor region 13 ': p-type semiconductor layer 14: mixed semiconductor region (A)
15: i-type semiconductor region 15 ': i-type semiconductor layer 16: mixed semiconductor region (B)
17: n-type semiconductor region 17 ': n-type semiconductor layer 18: buffer layer 19: metal electrode
Claims (13)
工程Ｓ１：透明電極の一方の面にｐ型半導体を一定の蒸着速度〔Ｒ１〕で一定時間〔Ｔ１〕かけて蒸着してｐ型半導体領域を形成する工程、
工程Ｓ２：前記工程１に続いて、前記ｐ型半導体を一定の蒸着速度〔Ｒ２〕から０まで一定時間〔Ｔ２〕かけて徐々に減速させるとともに、ｎ型半導体を０から一定の蒸着速度〔Ｒ２〕まで一定時間〔Ｔ２〕かけて徐々に増加させながら蒸着してｐ型半導体とｎ型半導体の濃度勾配を有する混合半導体領域を形成する工程、
工程Ｓ３：前記工程２に続いて、ｎ型半導体を一定の蒸着速度〔Ｒ３〕で一定時間〔Ｔ３〕かけて蒸着することによりｎ型半導体領域を形成する工程および
工程Ｓ４：金属電極を形成する工程
からなることを特徴とする有機薄膜太陽電池の製造方法（I）。 It is a manufacturing method of the organic thin film solar cell which has a photoelectric converting layer between a transparent electrode and a metal electrode, Comprising: The following process S1-process S4,
Step S1: A step of forming a p-type semiconductor region by depositing a p-type semiconductor on one surface of a transparent electrode at a constant deposition rate [R1] over a predetermined time [T1].
Step S2: Following the step 1, the p-type semiconductor is gradually decelerated from a constant deposition rate [R2] to 0 over a fixed time [T2], and the n-type semiconductor is reduced from 0 to a constant deposition rate [R2 A step of forming a mixed semiconductor region having a concentration gradient of the p-type semiconductor and the n-type semiconductor by vapor deposition while gradually increasing over a certain time [T2]
Step S3: Subsequent to Step 2, the step of forming an n-type semiconductor region by depositing an n-type semiconductor at a constant deposition rate [R3] for a predetermined time [T3] and Step S4: forming a metal electrode The manufacturing method (I) of the organic thin-film solar cell characterized by consisting of a process.
工程Ｓ１１：透明電極の一方の面にｐ型半導体を一定の蒸着速度〔Ｒ11〕で一定時間〔Ｔ11〕かけて蒸着してｐ型半導体領域を形成する工程、
工程Ｓ１２：前記工程１１に続いて、前記ｐ型半導体を蒸着速度〔Ｒ11〕から〔Ｒ12〕まで一定時間〔Ｔ12〕かけて徐々に減速させるとともに、ｎ型半導体を０から一定の蒸着速度〔Ｒ13〕まで一定時間〔Ｔ12〕かけて徐々に増加させながら蒸着してｐ型半導体とｎ型半導体の濃度勾配〔Ｃ１〕を有する混合半導体領域（Ａ）を形成する工程、
工程Ｓ１３：前記工程１２に続いて、ｐ型とｎ型半導体を一定の蒸着速度〔Ｒ12〕及び〔Ｒ13〕で一定時間〔Ｔ13〕かけて蒸着することによりｉ型半導体領域を形成する工程、
工程Ｓ１４：前記工程１３に続いて、前記ｐ型半導体の蒸着速度〔Ｒ12〕を一定時間〔Ｔ14〕かけて０まで徐々に減速させるとともに、ｎ型半導体を一定の蒸着速度〔Ｒ13〕から〔Ｒ14〕まで一定時間〔Ｔ14〕かけて徐々に増加させながら蒸着してｐ型半導体とｎ型半導体の濃度勾配〔Ｃ２〕を有する混合半導体領域（Ｂ）を形成する工程、
工程Ｓ１５：前記工程１４に続いて、ｎ型半導体を一定の蒸着速度〔Ｒ14〕で一定時間〔Ｔ15〕かけて蒸着することによりｎ型半導体領域を形成する工程および
工程Ｓ１６：金属電極を形成する工程
からなることを特徴とする有機薄膜太陽電池の製造方法（II）。 It is a manufacturing method of the organic thin film solar cell which has a photoelectric converting layer between a transparent electrode and a metal electrode, Comprising: The following process S11-process S16,
Step S11: forming a p-type semiconductor region by depositing a p-type semiconductor on one surface of the transparent electrode at a constant deposition rate [R11] over a predetermined time [T11].
Step S12: Following the step 11, the p-type semiconductor is gradually decelerated from the deposition rate [R11] to [R12] over a fixed time [T12], and the n-type semiconductor is reduced from 0 to a constant deposition rate [R13. Forming a mixed semiconductor region (A) having a concentration gradient [C1] of a p-type semiconductor and an n-type semiconductor by vapor deposition while gradually increasing over a certain time [T12].
Step S13: Following the step 12, the step of forming an i-type semiconductor region by depositing p-type and n-type semiconductors at a constant deposition rate [R12] and [R13] for a predetermined time [T13],
Step S14: Following the step 13, the deposition rate of the p-type semiconductor [R12] is gradually reduced to 0 over a predetermined time [T14], and the n-type semiconductor is removed from the constant deposition rate [R13] to [R14]. Forming a mixed semiconductor region (B) having a concentration gradient [C2] of a p-type semiconductor and an n-type semiconductor by vapor deposition while gradually increasing over a certain time [T14].
Step S15: Following the step 14, the n-type semiconductor is deposited at a constant deposition rate [R14] over a predetermined time [T15] to form an n-type semiconductor region, and step S16: a metal electrode is formed. A method (II) for producing an organic thin-film solar cell comprising steps.
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| KR20160004455A (en) * | 2014-07-02 | 2016-01-13 | 삼성디스플레이 주식회사 | Organic Light Emitting Device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015190550A1 (en) * | 2014-06-12 | 2015-12-17 | シャープ株式会社 | Organic element |
| KR20160004455A (en) * | 2014-07-02 | 2016-01-13 | 삼성디스플레이 주식회사 | Organic Light Emitting Device |
| KR102269488B1 (en) * | 2014-07-02 | 2021-06-25 | 삼성디스플레이 주식회사 | Organic Light Emitting Device |
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