CN105552233A - Bulk heterojunction organic solar cell with dual-anode buffer layer and preparation method of bulk heterojunction organic solar cell - Google Patents

Bulk heterojunction organic solar cell with dual-anode buffer layer and preparation method of bulk heterojunction organic solar cell Download PDF

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CN105552233A
CN105552233A CN201610124321.1A CN201610124321A CN105552233A CN 105552233 A CN105552233 A CN 105552233A CN 201610124321 A CN201610124321 A CN 201610124321A CN 105552233 A CN105552233 A CN 105552233A
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buffer layer
anode buffer
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康博南
张盼盼
党扬
张春霞
徐旭
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Jilin University
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Abstract

本发明涉及一种双阳极缓冲层体异质结有机太阳能电池,该电池采用正型结构,自下而上依次为:透明衬底、透明导电阳极、阳极缓冲层、有机活性层、阴极缓冲层、金属阴极;其中阳极缓冲层为PTFE阳极缓冲层和MoO3阳极缓冲层构成的双阳极缓冲层;PTFE阳极缓冲层制备于透明导电阳极上,其厚度为0.3~2nm;MoO3阳极缓冲层制备于PTFE阳极缓冲层与有机活性层之间,其厚度为4~10nm。本发明通过在阳极与活性层之间引入双阳极缓冲层,提高了阳极表面功函数,极好的修饰了界面能级差;在保证对空穴的传输的同时提高了对电子的阻挡能力,极大的减少了电子与空穴的复合,从而提高了太阳能电池的能量转换效率。

The invention relates to a heterojunction organic solar cell with a double anode buffer layer. The battery adopts a positive structure, and the sequence from bottom to top is: transparent substrate, transparent conductive anode, anode buffer layer, organic active layer, and cathode buffer layer. , metal cathode; wherein the anode buffer layer is a double anode buffer layer composed of PTFE anode buffer layer and MoO 3 anode buffer layer; the PTFE anode buffer layer is prepared on a transparent conductive anode with a thickness of 0.3-2nm ; Between the PTFE anode buffer layer and the organic active layer, the thickness is 4-10nm. The present invention improves the surface work function of the anode by introducing a double anode buffer layer between the anode and the active layer, and excellently modifies the interface energy level difference; while ensuring the transmission of holes, it improves the ability to block electrons, which is extremely The recombination of electrons and holes is greatly reduced, thereby improving the energy conversion efficiency of solar cells.

Description

一种双阳极缓冲层体异质结有机太阳能电池及其制备方法A kind of double anode buffer layer bulk heterojunction organic solar cell and its preparation method

技术领域technical field

本发明属于有机光伏器件技术领域,具体涉及一种双阳极缓冲层的体异质结有机太阳能电池及其制备方法。The invention belongs to the technical field of organic photovoltaic devices, and in particular relates to a bulk heterojunction organic solar cell with double anode buffer layers and a preparation method thereof.

背景技术Background technique

现如今,传统能源日渐枯竭,环境污染日益严重,人类面临着能源危机与环境污染的双重考验。因此,寻找低能耗、低污染、低排放的绿色能源,如太阳能、风能、水能、地热能、潮汐能等成为发展低碳经济的需要。其中太阳能以其可再生、清洁、储量丰富等特点,成为解决能源与环境问题的研究重点与热点。Nowadays, traditional energy sources are depleting day by day, environmental pollution is becoming more and more serious, and human beings are facing the double test of energy crisis and environmental pollution. Therefore, looking for green energy sources with low energy consumption, low pollution, and low emissions, such as solar energy, wind energy, water energy, geothermal energy, and tidal energy, has become a need for the development of a low-carbon economy. Among them, solar energy has become a research focus and hotspot for solving energy and environmental problems due to its renewable, clean, and abundant reserves.

太阳能电池是将太阳辐射的光能转换成电能的装置,是利用太阳能最重要的方式之一。目前,传统无机太阳能电池如硅、砷化镓太阳能电池等,虽然已投入市场,但其昂贵的成本、对无机半导体的要求高等缺点限制了它的进一步发展。有机太阳能电池是近二十年发展起来的新型太阳能电池,因其具有材料来源广泛、成本低、制备工艺简单、可制成大面积柔性器件等优点,相比于传统太阳能电池更具有优势和发展空间,得到了越来越多的重视。目前报道的有机太阳能电池的能量转换效率已达到10%以上,然而这个数字远没有达到可以大规模生产的要求。因此,如何通过优化器件结构,完善制备工艺等方法来提高有机太阳能电池的能量转换效率,成为研究有机太阳能电池的重点。A solar cell is a device that converts light energy radiated by the sun into electrical energy, and is one of the most important ways to utilize solar energy. At present, although traditional inorganic solar cells such as silicon and gallium arsenide solar cells have been put into the market, their high cost and high requirements for inorganic semiconductors limit their further development. Organic solar cells are a new type of solar cells developed in the past two decades. Compared with traditional solar cells, they have more advantages and development due to their advantages such as wide source of materials, low cost, simple preparation process, and large-area flexible devices. Space has received more and more attention. The reported energy conversion efficiency of organic solar cells has reached more than 10%, but this figure is far from meeting the requirements for mass production. Therefore, how to improve the energy conversion efficiency of organic solar cells by optimizing the device structure and improving the preparation process has become the focus of research on organic solar cells.

决定有机太阳能电池器件性能的重要因素有很多,其中之一就是有机活性层中有效的电荷传输,这取决于活性层与阳极之间良好的界面性能。因此研究者们在活性层与阳极之间引入了一层界面层,也就是阳极缓冲层。目前常用的阳极缓冲层有PEDOT:PSS和高功函数的金属氧化物如MoO3。然而,PEDOT:PSS的酸性和吸湿性降低了器件的整体性能。另外,虽然MoO3能够有效的传输空穴,但它不能够有效地阻挡活性层到阳极的电子传输,因此器件具有较高的载流子复合。There are many important factors that determine the device performance of organic solar cells, one of which is the effective charge transport in the organic active layer, which depends on the good interfacial properties between the active layer and the anode. Therefore, the researchers introduced an interface layer between the active layer and the anode, that is, the anode buffer layer. Currently commonly used anode buffer layers include PEDOT:PSS and metal oxides with high work function such as MoO 3 . However, the acidic and hygroscopic properties of PEDOT:PSS degrade the overall performance of the device. In addition, although MoO3 can effectively transport holes, it cannot effectively block the electron transport from the active layer to the anode, so the device has high carrier recombination.

发明内容Contents of the invention

本发明要解决的技术问题是提供一种双阳极缓冲层体异质结有机太阳能电池及其制备方法。该太阳能电池引入了双阳极缓冲层,很好的修饰了活性层与阳极ITO之间的界面,降低了活性层与阳极之间的势垒。另外双阳极缓冲层有利于激子的分离和载流子的传输,减少了载流子复合的几率,因此能够有效的提高器件的能量转换效率。The technical problem to be solved by the present invention is to provide a double anode buffer layer bulk heterojunction organic solar cell and a preparation method thereof. The solar cell introduces a double anode buffer layer, which well modifies the interface between the active layer and the anode ITO, and reduces the barrier between the active layer and the anode. In addition, the dual anode buffer layer is beneficial to the separation of excitons and the transport of carriers, reducing the probability of carrier recombination, so it can effectively improve the energy conversion efficiency of the device.

为了解决上述技术问题,本发明的双阳极缓冲层体异质结有机太阳能电池采用正型结构,自下而上依次为:透明衬底、透明导电阳极、阳极缓冲层、有机活性层、阴极缓冲层、金属阴极;其特征在于所述阳极缓冲层为PTFE阳极缓冲层和MoO3阳极缓冲层构成的双阳极缓冲层;PTFE阳极缓冲层制备于透明导电阳极上;MoO3阳极缓冲层制备于PTFE阳极缓冲层与有机活性层之间;PTFE阳极缓冲层厚度为0.3~2nm,MoO3阳极缓冲层厚度为4~10nm。In order to solve the above-mentioned technical problems, the double-anode buffer layer bulk heterojunction organic solar cell of the present invention adopts a positive structure, and the order from bottom to top is: transparent substrate, transparent conductive anode, anode buffer layer, organic active layer, cathode buffer Layer, metal cathode; It is characterized in that described anode buffer layer is the dual anode buffer layer that PTFE anode buffer layer and MoO 3 anode buffer layers form; PTFE anode buffer layer is prepared on the transparent conductive anode; MoO 3 anode buffer layers are prepared in PTFE Between the anode buffer layer and the organic active layer; the thickness of the PTFE anode buffer layer is 0.3-2nm, and the thickness of the MoO 3 anode buffer layer is 4-10nm.

所述PTFE阳极缓冲层厚度优选1.5nm。The thickness of the PTFE anode buffer layer is preferably 1.5 nm.

所述的透明衬底为透明玻璃或者透明柔性聚合物,透明柔性聚合物为聚乙烯、聚对苯二甲酸乙二脂、聚甲基丙烯酸甲酯、聚碳酸酯、聚氨基甲酸酯、聚酰亚胺或聚丙烯酸中的一种,或由其中两种以上材料混合制成,或由其中两种以上材料按顺序一层层制备而成。Described transparent substrate is transparent glass or transparent flexible polymer, and transparent flexible polymer is polyethylene, polyethylene terephthalate, polymethyl methacrylate, polycarbonate, polyurethane, polyester One of imide or polyacrylic acid, or two or more of them are mixed, or two or more of them are prepared layer by layer in sequence.

所述透明导电阳极,其材料为氧化铟锡(ITO),沉积于透明衬底上;The transparent conductive anode, whose material is indium tin oxide (ITO), is deposited on a transparent substrate;

所述透明导电阳极厚度为150nm,方块电阻为15Ω/□。The transparent conductive anode has a thickness of 150nm and a sheet resistance of 15Ω/□.

所述的有机活性层是由电子给体材料PCDTBT和电子受体材料PC71BM按1:4的质量比配置的混合物,或者是由电子给体材料P3HT和电子受体材料PC61BM按1:1的质量比配置的混合物。The organic active layer is a mixture of electron donor material PCDTBT and electron acceptor material PC 71 BM at a mass ratio of 1:4, or an electron donor material P3HT and electron acceptor material PC 61 BM at a ratio of 1 :1 mass ratio configuration mixture.

所述的阴极缓冲层,其材料为Alq3、LiF、卟啉小分子、Bphen或BCP中的一种,或由其中两种以上材料按顺序一层层制备而成,厚度为1~10nm。The cathode buffer layer is made of one of Alq3, LiF, small porphyrin molecules, Bphen or BCP, or two or more of these materials are sequentially prepared layer by layer, with a thickness of 1-10 nm.

所述的金属阴极,其材料为Al、Ca、Ag或Au中的一种,或由其中两种以上材料按顺序一层层制备而成,厚度为100nm~200nm。The metal cathode is made of one of Al, Ca, Ag or Au, or two or more of these materials are prepared layer by layer in sequence, and the thickness is 100nm-200nm.

本发明的双阳极缓冲层体异质结有机太阳能电池的制备方法,包括以下步骤:The preparation method of the dual anode buffer layer body heterojunction organic solar cell of the present invention comprises the following steps:

①依次使用甲苯、丙酮、洗涤剂、去离子水、异丙醇对透明导电阳极与透明衬底构成的基片进行超声清洗,清洗过后的基片保存在异丙醇中备用;① Use toluene, acetone, detergent, deionized water, and isopropanol in sequence to ultrasonically clean the substrate composed of the transparent conductive anode and the transparent substrate, and store the cleaned substrate in isopropanol for later use;

②清洗后的基片用氮气吹干,移入干燥箱中烘干,然后用Plasma清洗机进行等离子体处理;②The cleaned substrate is blown dry with nitrogen, moved into a drying oven for drying, and then plasma treated with a Plasma cleaning machine;

③将处理好的基片移入真空镀膜机里,在透明导电阳极上蒸镀PTFE阳极缓冲层,然后在PTFE阳极缓冲层上蒸镀MoO3阳极缓冲层;其中PTFE的蒸发速率为厚度为0.3~2nm,MoO3的蒸发速率为厚度为4~10nm;③ Move the treated substrate into the vacuum coating machine, evaporate the PTFE anode buffer layer on the transparent conductive anode, and then evaporate the MoO3 anode buffer layer on the PTFE anode buffer layer; wherein the evaporation rate of PTFE is The thickness is 0.3~2nm, the evaporation rate of MoO 3 is The thickness is 4~10nm;

④将上述蒸镀了双阳极缓冲层的基片移入Plasma清洗机,进行等离子体处理;④ Move the above-mentioned substrate on which the double anode buffer layer has been vapor-deposited into the Plasma cleaning machine for plasma treatment;

⑤在MoO3阳极缓冲层上制备有机活性层;⑤ Prepare an organic active layer on the MoO 3 anode buffer layer;

⑥将步骤⑤获得的基片移入真空镀膜机里,依次在有机活性层上蒸镀阴极缓冲层和金属阴极。⑥ Move the substrate obtained in step ⑤ into a vacuum coating machine, and sequentially vapor-deposit a cathode buffer layer and a metal cathode on the organic active layer.

所述步骤⑤中采用旋涂的方法在氮气氛围中将电子给体材料PCDTBT和电子受体材料PC71BM按1:4的质量比配置的混合溶液旋涂在MoO3阳极缓冲层上,匀胶机转速为1500rpm/s,旋涂时间为40s;所述混合溶液的溶剂为邻二氯苯,溶液的浓度为PCDTBT:PC71BM=8mg/ml:32mg/ml;然后在70℃的条件下退火30min蒸发掉溶剂,得到有机活性层。In the step 5., spin-coat the mixed solution of the electron donor material PCDTBT and the electron acceptor material PC 71 BM at a mass ratio of 1: 4 on the MoO anode buffer layer in a nitrogen atmosphere by spin coating, and evenly The speed of the glue machine is 1500rpm/s, and the spin coating time is 40s; the solvent of the mixed solution is o-dichlorobenzene, and the concentration of the solution is PCDTBT:PC 71 BM=8mg/ml:32mg/ml; The solvent was evaporated by lower annealing for 30 minutes to obtain an organic active layer.

所述步骤⑤中,采用旋涂的方法在氮气氛围中将电子给体材料P3HT和电子受体材料PC61BM按1:1的质量比配置的混合溶液旋涂在MoO3阳极缓冲层上,匀胶机转速为700rpm/s,旋涂时间为36s;所述混合溶液的溶剂为邻二氯苯,溶液的浓度为P3HT:PC61BM=17mg/ml:17mg/ml;然后室温退火3h蒸发掉溶剂,得到有机活性层。In the step ⑤, the electron donor material P3HT and the electron acceptor material PC 61 BM are spin - coated on the MoO anode buffer layer in a nitrogen atmosphere by spin-coating a mixed solution configured in a mass ratio of 1:1, The speed of the homogenizer is 700rpm/s, and the spin coating time is 36s; the solvent of the mixed solution is o-dichlorobenzene, and the concentration of the solution is P3HT:PC 61 BM=17mg/ml:17mg/ml; then annealed at room temperature for 3h and evaporated The solvent was removed to obtain an organic active layer.

所述⑥步骤中,在有机活性层上蒸镀Alq3阴极缓冲层,蒸发速率为Alq3厚度为1nm;在Alq3阴极缓冲层上蒸镀Al金属电极,蒸发速率约为Al厚度为100nm-200nm。In the described 6. step, Alq is vapor-deposited on the organic active layer Cathode buffer layer, evaporation rate is The thickness of Alq3 is 1nm; the Al metal electrode is evaporated on the Alq3 cathode buffer layer, and the evaporation rate is about Al thickness is 100nm-200nm.

本发明提供了一种双阳极缓冲层的体异质结有机太阳能电池,使得有机太阳能电池的性能,尤其是影响因子及能量转换效率都有很大程度的提高,具有制备工艺简单、成本低、效率高等优点。The invention provides a bulk heterojunction organic solar cell with a double anode buffer layer, which greatly improves the performance of the organic solar cell, especially the impact factor and energy conversion efficiency, and has the advantages of simple preparation process, low cost, High efficiency and other advantages.

与现有的技术相比,本发明的优点在于:Compared with the prior art, the present invention has the advantages of:

一、本发明提供的双阳极缓冲层体异质结有机太阳能电池,以PTFE和MoO3组合成双阳极缓冲层,提高了阳极表面功函数,极好的修饰了阳极ITO与活性层之间的界面能级差,保证了良好的界面性能。1. The double anode buffer layer body heterojunction organic solar cell provided by the present invention is composed of PTFE and MoO3 to form a double anode buffer layer, which improves the surface work function of the anode and excellently modifies the contact between the anode ITO and the active layer. The poor interface energy level ensures good interface performance.

二、本发明提供的双阳极缓冲层体异质结有机太阳能电池,以PTFE和MoO3组合成双阳极缓冲层,相对于单层阳极缓冲层MoO3,提高了对电子的阻挡能力,极大的降低了电子与空穴的复合几率,从而提高了太阳能电池的能量转换效率。2. The double-anode buffer layer body heterojunction organic solar cell provided by the present invention is composed of PTFE and MoO3 to form a double - anode buffer layer. Compared with the single - layer anode buffer layer MoO3, the blocking ability to electrons is greatly improved. It reduces the recombination probability of electrons and holes, thereby improving the energy conversion efficiency of solar cells.

三、本发明提供的双阳极缓冲层体异质结有机太阳能电池,以PTFE和MoO3组合成双阳极缓冲层,相比于传统的阳极缓冲层PEDOT:PSS,PTFE的化学性质和物理性质都很稳定,具有耐湿性,且不会侵蚀阳极ITO,因此器件具有更好的稳定性。3. The double anode buffer layer body heterojunction organic solar cell provided by the present invention is composed of PTFE and MoO3 to form a double anode buffer layer. Compared with the traditional anode buffer layer PEDOT:PSS, the chemical properties and physical properties of PTFE are all the same. It is very stable, has moisture resistance, and will not corrode the anode ITO, so the device has better stability.

四、本发明提供的双阳极缓冲层体异质结有机太阳能电池,以PTFE和MoO3组合成双阳极缓冲层,材料来源广泛,成本低,制备工艺简单。4. The double-anode buffer layer bulk heterojunction organic solar cell provided by the present invention is composed of PTFE and MoO3 to form a double - anode buffer layer, which has a wide range of material sources, low cost and simple preparation process.

附图说明Description of drawings

下面结合附图及具体实施方式对本发明作进一步的说明。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

图1是本发明的双阳极缓冲层体异质结有机太阳能电池的结构示意图;Fig. 1 is the structural representation of double anode buffer layer bulk heterojunction organic solar cell of the present invention;

图2是本发明的双阳极缓冲层体异质结有机太阳能电池的实施例1与对比器件在光照强度为AM1.5G下测得的J-V曲线;Fig. 2 is the J-V curve measured under the light intensity of AM1.5G of embodiment 1 of the double anode buffer layer bulk heterojunction organic solar cell of the present invention and comparative device;

图3是本发明的双阳极缓冲层体异质结有机太阳能电池的性能随PTFE阳极缓冲层的厚度改变而改变的示意图。Fig. 3 is a schematic diagram showing that the performance of the double anode buffer layer bulk heterojunction organic solar cell of the present invention changes with the thickness of the PTFE anode buffer layer.

图4是本发明的双阳极缓冲层体异质结有机太阳能电池的实施例2与对比器件在光照强度为AM1.5G下测得的J-V曲线。Fig. 4 is the J-V curve measured under the illumination intensity of AM1.5G of the embodiment 2 of the double anode buffer layer bulk heterojunction organic solar cell of the present invention and the comparative device.

图5是本发明的双阳极缓冲层体异质结有机太阳能电池的性能与MoO3阳极缓冲层厚度的关系示意图。Fig. 5 is a schematic diagram of the relationship between the performance of the double anode buffer layer bulk heterojunction organic solar cell of the present invention and the thickness of the MoO 3 anode buffer layer.

具体实施方式detailed description

如图1所示,本发明的双阳极缓冲层体异质结有机太阳能电池采用正型结构,自下而上依次为:透明衬底、透明导电阳极、双阳极缓冲层、有机活性层、阴极缓冲层、金属阳极。双阳极缓冲层的第一层为PTFE阳极缓冲层,制备于透明导电阳极上,其厚度范围为0.3~2nm;第二层为MoO3阳极缓冲层,制备于PTFE阳极缓冲层上,其厚度范围为4~10nm;有机活性层由电子给体材料和电子受体材料混合而成,制备于MoO3阳极缓冲层上。As shown in Figure 1, the double-anode buffer layer bulk heterojunction organic solar cell of the present invention adopts a positive structure, and the order from bottom to top is: transparent substrate, transparent conductive anode, double-anode buffer layer, organic active layer, cathode Buffer layer, metal anode. The first layer of the double anode buffer layer is a PTFE anode buffer layer, which is prepared on a transparent conductive anode, and its thickness ranges from 0.3 to 2 nm; the second layer is an MoO 3 anode buffer layer, which is prepared on a PTFE anode buffer layer, and its thickness ranges from 4-10nm; the organic active layer is formed by mixing electron donor materials and electron acceptor materials, and is prepared on the MoO 3 anode buffer layer.

其中实施例1中有机活性层由给体材料PCDTBT与受体材料PC71BM混合制备而成,所述PCDTBT:PC71BM混合溶液的质量百分比为1:4,溶剂为邻二氯苯,溶液浓度为PCDTBT:PC71BM=8mg/ml:32mg/ml,混合后的溶液以60℃加热搅拌12h。实施例5中活性层由给体材料P3HT与受体材料PC61BM混合制备而成,所述的P3HT:PC61BM混合溶液的质量百分比为1:1,溶剂为邻二氯苯,溶液浓度为P3HT:PC61BM=17mg/ml:17mg/ml,混合后的溶液在室温下搅拌14h。Wherein the organic active layer in embodiment 1 is prepared by mixing the donor material PCDTBT and the acceptor material PC 71 BM, the mass percent of the PCDTBT:PC 71 BM mixed solution is 1:4, the solvent is o-dichlorobenzene, the solution The concentration is PCDTBT:PC 71 BM=8mg/ml:32mg/ml, and the mixed solution is heated and stirred at 60°C for 12h. In Example 5, the active layer is prepared by mixing the donor material P3HT and the acceptor material PC 61 BM, the mass percentage of the P3HT:PC 61 BM mixed solution is 1:1, the solvent is o-dichlorobenzene, and the concentration of the solution is P3HT:PC 61 BM=17mg/ml:17mg/ml, the mixed solution was stirred at room temperature for 14h.

实施例1:Example 1:

双阳极缓冲层体异质结有机太阳能电池制备方法如下:首先依次使用甲苯、丙酮、洗涤剂、去离子水、异丙醇对透明衬底及氧化铟锡(ITO)透明导电阳极所组成的基片进行超声清洗,每步各20min。用氮气将清洗后的基片吹干后,移入干燥箱中烘干20min。然后用Plasma清洗机处理基片5min。双阳极缓冲层采用真空蒸镀的方法制备,首先将处理好的基片移入真空镀膜机中在透明导电阳极上蒸镀PTFE阳极缓冲层,PTFE的蒸发速率为然后在PTFE阳极缓冲层上蒸镀MoO3阳极缓冲层,MoO3的蒸发速率为蒸镀完成后,PTFE阳极缓冲层的厚度为1.5nm,MoO3阳极缓冲层的厚度为5nm。将蒸镀了双阳极缓冲层的基片移入Plasma清洗机,处理2min。将电子给体材料PCDTBT与电子受体材料PC71BM按质量百分比为1:4溶于邻二氯苯,得到浓度为PCDTBT:PC71BM=8mg/ml:32mg/ml的混合溶液,混合溶液以60℃加热搅拌12h;然后将基片移入手套箱(氮气氛围)中,采用旋涂法在MoO3阳极缓冲层上制备PCDTBT:PCB71M有机活性层,转速为1500rpm/s,时间为40s,厚度约为90nm。旋涂成膜后,将基片放在加热板上进行热退火(70℃,30min),以便蒸发掉多余的溶剂,使有机活性层形成良好的相分离结构。退火后将基片移入真空镀膜机,在有机活性层上依次蒸镀阴极缓冲层Alq3(厚度为1nm,蒸发速率为)和金属阴极Al(厚度为120nm,蒸发速率为)。金属阴极Al蒸镀完成后,要在手套箱中停留15min,以使基片冷却,防止Al电极在空气中被氧化。制备好的器件有效面积为0.05cm2。器件均在100mw/cm2的AM1.5的模拟光照下进行测试,电流密度-电压(J-V)曲线由Keithley2400数字源表测得,测试过程均在大气环境下进行。本发明器件结构为:透明衬底/ITO/PTFE(厚度1.5nm)/MoO3(厚度5nm)/PCDTBT:PC71BM/Alq3(厚度1nm)/Al(厚度120nm)。本发明的器件与对比器件所测得的J-V曲线如图2所示。对比例1:The preparation method of the double-anode buffer layer bulk heterojunction organic solar cell is as follows: firstly, toluene, acetone, detergent, deionized water, and isopropanol are used in sequence to form a substrate composed of a transparent substrate and an indium tin oxide (ITO) transparent conductive anode. The slices were ultrasonically cleaned, each step was 20 min. After the cleaned substrate was blown dry with nitrogen, it was moved into a drying oven to dry for 20 minutes. The substrate was then treated with a Plasma cleaner for 5 min. The double anode buffer layer is prepared by vacuum evaporation. Firstly, the treated substrate is moved into a vacuum coating machine and the PTFE anode buffer layer is evaporated on the transparent conductive anode. The evaporation rate of PTFE is Then evaporate MoO 3 anode buffer layer on the PTFE anode buffer layer, the evaporation rate of MoO 3 is After the evaporation is completed, the thickness of the PTFE anode buffer layer is 1.5nm, and the thickness of the MoO3 anode buffer layer is 5nm. Move the substrate on which the double anode buffer layer has been evaporated into the Plasma cleaning machine, and process it for 2 minutes. The electron donor material PCDTBT and the electron acceptor material PC 71 BM are dissolved in o-dichlorobenzene at a mass percentage of 1:4 to obtain a mixed solution with a concentration of PCDTBT:PC 71 BM=8mg/ml:32mg/ml, and the mixed solution Heat and stir at 60°C for 12h; then move the substrate into a glove box (nitrogen atmosphere), and prepare a PCDTBT:PCB 71 M organic active layer on the MoO 3 anode buffer layer by spin coating at a speed of 1500rpm/s for 40s , with a thickness of about 90nm. After spin-coating to form a film, put the substrate on a heating plate for thermal annealing (70°C, 30min), so as to evaporate excess solvent and form a good phase-separated structure in the organic active layer. After annealing, the substrate is moved into a vacuum coating machine, and the cathode buffer layer Alq3 (thickness is 1 nm, evaporation rate is ) and metal cathode Al (thickness is 120nm, evaporation rate is ). After the metal cathode Al evaporation is completed, stay in the glove box for 15 minutes to cool the substrate and prevent the Al electrode from being oxidized in the air. The prepared device has an effective area of 0.05 cm 2 . The devices were tested under 100mw/cm 2 AM1.5 simulated light, the current density-voltage (JV) curve was measured by Keithley2400 digital source meter, and the test process was carried out in the atmospheric environment. The device structure of the present invention is: transparent substrate/ITO/PTFE (thickness 1.5nm)/MoO 3 (thickness 5nm)/PCDTBT:PC 71 BM/Alq3 (thickness 1nm)/Al (thickness 120nm). The JV curves measured by the device of the present invention and the comparative device are shown in FIG. 2 . Comparative example 1:

将清洗好的透明衬底及ITO透明导电阳极所组成的基片用氮气吹干,烘干20min并用Plasma清洗机处理基片5min后,移入真空镀膜机中蒸镀阳极缓冲层MoO3(厚度为5nm,蒸发速率为)。将蒸镀了阳极缓冲层MoO3的基片移入Plasma清洗机,处理2min。然后将基片移入手套箱(氮气氛围)中,采用旋涂法在阳极缓冲层上制备有机活性层。有机活性层由电子给体材料PCDTBT与电子受体材料PC71BM混合制备而成,PCDTBT:PC71BM混合溶液的质量百分比为1:4,溶剂为邻二氯苯,有机活性层PCDTBT:PC71BM采用旋涂法制备,转速为1500rpm/s,时间为40s,厚度约为90nm。然后进行热退火(70℃,30min)。在有机活性层上依次蒸镀阴极缓冲层Alq3(厚度为1nm,蒸发速率为)及金属阴极Al(厚度为120nm,蒸发速率为)。制备完成的器件在标准条件下(AM1.5,100mw/cm2)进行测量,使用Keithley2400数字源表收集J-V曲线数据。对比器件结构为:透明衬底/ITO/MoO3(厚度5nm)/PCDTBT:PC71BM/Alq3(厚度1nm)/Al(厚度120nm)。The substrate composed of the cleaned transparent substrate and the ITO transparent conductive anode was blown dry with nitrogen, dried for 20 minutes and processed with a Plasma cleaning machine for 5 minutes, then moved into a vacuum coating machine to evaporate the anode buffer layer MoO 3 (thickness: 5nm, the evaporation rate is ). Move the substrate on which the anode buffer layer MoO 3 is evaporated into the Plasma cleaning machine, and process it for 2 minutes. Then the substrate was moved into a glove box (nitrogen atmosphere), and an organic active layer was prepared on the anode buffer layer by spin coating. The organic active layer is prepared by mixing the electron donor material PCDTBT and the electron acceptor material PC 71 BM, the mass percentage of PCDTBT:PC 71 BM mixed solution is 1:4, the solvent is o-dichlorobenzene, the organic active layer PCDTBT:PC 71 BM was prepared by spin-coating method, the rotating speed was 1500rpm/s, the time was 40s, and the thickness was about 90nm. Then thermal annealing (70°C, 30min) was performed. On the organic active layer, the cathode buffer layer Alq3 (thickness is 1nm, evaporation rate is ) and metal cathode Al (thickness is 120nm, evaporation rate is ). The fabricated device was measured under standard conditions (AM1.5, 100mw/cm 2 ), and the JV curve data was collected using a Keithley2400 digital source meter. The comparative device structure is: transparent substrate/ITO/MoO 3 (thickness 5nm)/PCDTBT:PC 71 BM/Alq3 (thickness 1nm)/Al (thickness 120nm).

对比例2:Comparative example 2:

将清洗好的透明衬底及ITO透明导电阳极所组成的基片用氮气吹干,烘干20min并用Plasma清洗机处理基片5min后,在阳极上旋涂阳极缓冲层聚乙撑二氧噻吩(PEDOT:PSS)(转速为3000rpm/s,时间为60s),在120℃的条件下加热10min。然后将基片移入手套箱(氮气氛围)中,采用旋涂法在阳极缓冲层上制备有机活性层;有机活性层由电子给体材料PCDTBT与电子受体材料PC71BM混合制备而成,PCDTBT:PC71BM混合溶液的质量百分比为1:4,溶剂为邻二氯苯,有机活性层PCDTBT:PC71BM采用旋涂法制备,转速为1500rpm/s,时间为40s,厚度约为90nm;然后进行热退火(70℃,30min)。在活性层上依次蒸镀阴极缓冲层Alq3(厚度为1nm,蒸发速率为)及金属阴极Al(厚度为120nm,蒸发速率为)。制备完成的器件在标准条件下(AM1.5,100mw/cm2)进行测量,使用Keithley2400数字源表收集J-V曲线数据。对比器件结构为:透明衬底/ITO/PEDOT:PSS/PCDTBT:PC71BM/Alq3(厚度1nm)/Al(厚度120nm)。The substrate composed of the cleaned transparent substrate and the ITO transparent conductive anode was blown dry with nitrogen, dried for 20 minutes and treated with a Plasma cleaning machine for 5 minutes, and then spin-coated the anode buffer layer polyethylenedioxythiophene ( PEDOT:PSS) (rotating speed is 3000rpm/s, time is 60s), heated at 120°C for 10min. Then the substrate was moved into the glove box (nitrogen atmosphere), and the organic active layer was prepared on the anode buffer layer by spin coating; the organic active layer was prepared by mixing the electron donor material PCDTBT and the electron acceptor material PC 71 BM, PCDTBT : The mass percentage of the PC 71 BM mixed solution is 1:4, the solvent is o-dichlorobenzene, and the organic active layer PCDTBT:PC 71 BM is prepared by spin coating, the rotating speed is 1500rpm/s, the time is 40s, and the thickness is about 90nm; Then thermal annealing (70°C, 30min) was performed. On the active layer, the cathode buffer layer Alq3 (thickness is 1nm, evaporation rate is ) and metal cathode Al (thickness is 120nm, evaporation rate is ). The fabricated device was measured under standard conditions (AM1.5, 100mw/cm 2 ), and the JV curve data was collected using a Keithley2400 digital source meter. The comparative device structure is: transparent substrate/ITO/PEDOT:PSS/PCDTBT:PC 71 BM/Alq3 (thickness 1nm)/Al (thickness 120nm).

表1为实施例1与对比例1和对比例2的数据结果对比,结果显示,以PTFE阳极缓冲层和MoO3阳极缓冲层组合成双阳极缓冲层,相对于单层阳极缓冲层MoO3,器件的短路电流提高9.3%,填充因子提高9.8%,能量转换效率提高25%;对比于传统的阳极缓冲层PEDOT:PSS,短路电流提高14.3%,填充因子提高8.83%,能量转换效率提高26.3%。Table 1 is a comparison of the data results of Example 1 and Comparative Example 1 and Comparative Example 2. The results show that the dual anode buffer layer is combined with PTFE anode buffer layer and MoO3 anode buffer layer. Compared with the single - layer anode buffer layer MoO3, The short-circuit current of the device is increased by 9.3%, the fill factor is increased by 9.8%, and the energy conversion efficiency is increased by 25%. Compared with the traditional anode buffer layer PEDOT:PSS, the short-circuit current is increased by 14.3%, the fill factor is increased by 8.83%, and the energy conversion efficiency is increased by 26.3%. .

表1为实施例1的发明结构器件与对比器件性能测试的结果对比Table 1 is the result comparison of the inventive structure device of embodiment 1 and the comparison device performance test

Jsc(mA/cm2)Jsc(mA/cm 2 ) Voc(V)Voc(V) FF(%)FF(%) PCE(%)PCE(%) 实施例1器件Embodiment 1 device 12.92612.926 0.8960.896 63.1263.12 7.3117.311 对比例1器件Device of Comparative Example 1 11.82311.823 0.8610.861 57.4857.48 5.8505.850 对比例2器件Device of Comparative Example 2 11.31011.310 0.8820.882 58.0058.00 5.7875.787

实施例2Example 2

双阳极缓冲层体异质结有机太阳能电池制备方法如下:首先依次使用甲苯、丙酮、洗涤剂、去离子水、异丙醇对透明衬底及氧化铟锡(ITO)透明导电阳极所组成的基片进行超声清洗,每步各20min。将清洗好的透明衬底及ITO透明导电阳极所组成的基片用氮气吹干,烘干20min并用Plasma清洗机处理基片5min后,移入真空镀膜机中依次蒸镀PTFE阳极缓冲层(厚度为0.3nm,蒸发速率为)及MoO3阳极缓冲层(厚度为5nm),蒸发速率为)。将基片移入Plasma清洗机,处理2min后,采用与实施例1相同的方法在MoO3阳极缓冲层上制备有机活性层PCDTBT:PCB71M。之后将基片移入真空镀膜机,在有机活性层上依次蒸镀阴极缓冲层Alq3(厚度为1nm,蒸发速率为)及金属阴极Al(厚度为120nm,蒸发速率为)。制备完成的器件在标准条件下(AM1.5,100mw/cm2)进行测量,使用Keithley2400数字源表收集J-V曲线数据。器件结构为:透明衬底/ITO/PTFE(厚度0.3nm)/MoO3(厚度5nm)/PCDTBT:PC71BM/Alq3(厚度1nm)/Al(厚度120nm)。实施例2的器件所测得的J-V曲线如图3所示。The preparation method of the double-anode buffer layer bulk heterojunction organic solar cell is as follows: firstly, toluene, acetone, detergent, deionized water, and isopropanol are used in sequence to form a substrate composed of a transparent substrate and an indium tin oxide (ITO) transparent conductive anode. The slices were ultrasonically cleaned, each step was 20 min. The substrate composed of the cleaned transparent substrate and the ITO transparent conductive anode was blown dry with nitrogen, dried for 20 minutes and treated with a Plasma cleaning machine for 5 minutes, and then moved into a vacuum coating machine to evaporate and deposit a PTFE anode buffer layer (thickness: 0.3nm, the evaporation rate is ) and MoO 3 anode buffer layer (thickness is 5nm), the evaporation rate is ). The substrate was moved into a Plasma cleaning machine, and after being treated for 2 minutes, the organic active layer PCDTBT:PCB 71 M was prepared on the MoO 3 anode buffer layer by the same method as in Example 1. Afterwards, the substrate is moved into a vacuum coating machine, and the cathode buffer layer Alq3 (thickness is 1 nm, and the evaporation rate is ) and metal cathode Al (thickness is 120nm, evaporation rate is ). The fabricated device was measured under standard conditions (AM1.5, 100mw/cm 2 ), and the JV curve data was collected using a Keithley2400 digital source meter. The device structure is: transparent substrate/ITO/PTFE (thickness 0.3nm)/MoO 3 (thickness 5nm)/PCDTBT:PC 71 BM/Alq3 (thickness 1nm)/Al (thickness 120nm). The measured JV curve of the device of Example 2 is shown in FIG. 3 .

实施例3Example 3

双阳极缓冲层体异质结有机太阳能电池制备方法如下:首先依次使用甲苯、丙酮、洗涤剂、去离子水、异丙醇对透明衬底及氧化铟锡(ITO)透明导电阳极所组成的基片进行超声清洗,每步各20min。将清洗好的透明衬底及ITO透明导电阳极所组成的基片用氮气吹干,烘干20min并用Plasma清洗机处理基片5min后,移入真空镀膜机中依次蒸镀PTFE阳极缓冲层(厚度为1.0nm,蒸发速率为)及MoO3阳极缓冲层(厚度为5nm,蒸发速率为)。将基片移入Plasma清洗机,处理2min后,采用与实施例1相同的方法在MoO3阳极缓冲层上制备有机活性层PCDTBT:PC71BM。在有机活性层上依次蒸镀阴极缓冲层Alq3(厚度为1nm,蒸发速率为)及金属阴极Al(厚度为120nm,蒸发速率为)。制备完成的器件在标准条件下(AM1.5,100mw/cm2)进行测量,使用Keithley2400数字源表收集J-V曲线数据。器件结构为:透明衬底/ITO/PTFE(厚度1.0nm)/MoO3(厚度5nm)/PCDTBT:PC71BM/Alq3(厚度1nm)/Al(厚度120nm)。实施例3的器件所测得的J-V曲线如图3所示。The preparation method of the double-anode buffer layer bulk heterojunction organic solar cell is as follows: firstly, toluene, acetone, detergent, deionized water, and isopropanol are used in sequence to form a substrate composed of a transparent substrate and an indium tin oxide (ITO) transparent conductive anode. The slices were ultrasonically cleaned, each step was 20 min. The substrate composed of the cleaned transparent substrate and the ITO transparent conductive anode was blown dry with nitrogen, dried for 20 minutes and treated with a Plasma cleaning machine for 5 minutes, and then moved into a vacuum coating machine to evaporate and deposit a PTFE anode buffer layer (thickness: 1.0nm, the evaporation rate is ) and MoO 3 anode buffer layer (thickness is 5nm, evaporation rate is ). The substrate was moved into a Plasma cleaning machine, and after being treated for 2 minutes, the organic active layer PCDTBT:PC 71 BM was prepared on the MoO 3 anode buffer layer by the same method as in Example 1. On the organic active layer, the cathode buffer layer Alq3 (thickness is 1nm, evaporation rate is ) and metal cathode Al (thickness is 120nm, evaporation rate is ). The fabricated device was measured under standard conditions (AM1.5, 100mw/cm 2 ), and the JV curve data was collected using a Keithley2400 digital source meter. The device structure is: transparent substrate/ITO/PTFE (thickness 1.0nm)/MoO 3 (thickness 5nm)/PCDTBT:PC 71 BM/Alq3 (thickness 1nm)/Al (thickness 120nm). The measured JV curve of the device of Example 3 is shown in FIG. 3 .

实施例4Example 4

双阳极缓冲层体异质结有机太阳能电池制备方法如下:首先依次使用甲苯、丙酮、洗涤剂、去离子水、异丙醇对透明衬底及氧化铟锡(ITO)透明导电阳极所组成的基片进行超声清洗,每步各20min。将清洗好的透明衬底及ITO透明导电阳极所组成的基片用氮气吹干,烘干20min并用Plasma清洗机处理基片5min后,移入真空镀膜机中依次蒸镀PTFE阳极缓冲层(厚度为2.0nm,蒸发速率为)及MoO3阳极缓冲层(厚度5nm,蒸发速率为)。将基片移入Plasma清洗机,处理2min后,采用与实施例1相同的方法在MoO3阳极缓冲层上制备有机活性层PCDTBT:PC71BM。在有机活性层上依次蒸镀阴极缓冲层Alq3(厚度为1nm,蒸发速率为)及金属阴极Al(厚度为120nm,蒸发速率为)。制备完成的器件在标准条件下(AM1.5,100mw/cm2)进行测量,使用Keithley2400数字源表收集J-V曲线数据。器件结构为:透明衬底/ITO/PTFE(厚度2.0nm)/MoO3(厚度5nm)/PCDTBT:PC71BM/Alq3(厚度1nm)/Al(厚度120nm)。实施例4的器件所测得的J-V曲线如图3所示。The preparation method of the double-anode buffer layer bulk heterojunction organic solar cell is as follows: firstly, toluene, acetone, detergent, deionized water, and isopropanol are used in sequence to form a substrate composed of a transparent substrate and an indium tin oxide (ITO) transparent conductive anode. The slices were ultrasonically cleaned, each step was 20 min. The substrate composed of the cleaned transparent substrate and the ITO transparent conductive anode was blown dry with nitrogen, dried for 20 minutes and treated with a Plasma cleaning machine for 5 minutes, and then moved into a vacuum coating machine to evaporate and deposit a PTFE anode buffer layer (thickness: 2.0nm, the evaporation rate is ) and MoO 3 anode buffer layer (thickness 5nm, evaporation rate is ). The substrate was moved into a Plasma cleaning machine, and after being treated for 2 minutes, the organic active layer PCDTBT:PC 71 BM was prepared on the MoO 3 anode buffer layer by the same method as in Example 1. On the organic active layer, the cathode buffer layer Alq3 (thickness is 1nm, evaporation rate is ) and metal cathode Al (thickness is 120nm, evaporation rate is ). The fabricated device was measured under standard conditions (AM1.5, 100mw/cm 2 ), and the JV curve data was collected using a Keithley2400 digital source meter. The device structure is: transparent substrate/ITO/PTFE (thickness 2.0nm)/MoO 3 (thickness 5nm)/PCDTBT:PC 71 BM/Alq3 (thickness 1nm)/Al (thickness 120nm). The measured JV curve of the device of Example 4 is shown in FIG. 3 .

表2为实施例1~4的发明结构器件性能测试的结果对比Table 2 is the result comparison of the invention structure device performance test of embodiments 1-4

Jsc(mA/cm2)Jsc(mA/cm 2 ) Voc(V)Voc(V) FF(%)FF(%) PCE(%)PCE(%) 实施例1器件Embodiment 1 device 12.92612.926 0.8960.896 63.1263.12 7.3117.311 实施例2器件Embodiment 2 device 11.93511.935 0.8670.867 60.5660.56 6.2686.268 实施例3器件Embodiment 3 device 12.30412.304 0.8860.886 63.8963.89 6.9676.967 实施例4器件Embodiment 4 device 11.64911.649 0.8820.882 61.2661.26 6.2946.294

实施例5Example 5

双阳极缓冲层体异质结有机太阳能电池制备方法如下:首先依次使用甲苯、丙酮、洗涤剂、去离子水、异丙醇对透明衬底及氧化铟锡(ITO)透明导电阳极所组成的基片进行超声清洗,每步各20min。将清洗好的透明衬底及ITO透明导电阳极所组成的基片用氮气吹干,烘干20min,用Plasma清洗机处理基片5min后,移入真空镀膜机中依次蒸镀PTFE阳极缓冲层(厚度为1.5nm,蒸发速率为)及MoO3阳极缓冲层(厚度为5nm,蒸发速率为)。将蒸镀了双阳极缓冲层的基片移入Plasma清洗机,处理2min。将电子给体材料P3HT与电子受体材料PC61BM按质量百分比为1:1溶于邻二氯苯,得到浓度为P3HT:PC61BM=17mg/ml:17mg/ml的混合溶液,混合溶液室温搅拌14h;然后将基片移入手套箱(氮气氛围)中,采用旋涂法在MoO3阳极缓冲层上制备P3HT:PC61BM有机活性层,转速为700rpm/s,时间为36s,厚度约为230nm;旋涂成膜后,在手套箱中放置3h以使溶剂挥发。在有机活性层上依次蒸镀阴极缓冲层Alq3(厚度为1nm,蒸发速率为)及金属阴极Al(厚度为120nm,蒸发速率为)。制备完成的器件在标准条件(AM1.5,100mw/cm2)下进行测量,使用Keithley2400数字源表收集J-V曲线数据。本发明器件结构为:透明衬底/ITO/PTFE(厚度1.5nm)/MoO3(厚度5nm)/P3HT:PC61BM/Alq3(厚度1nm)/Al(厚度120nm)。本发明的器件与对比器件所测得的J-V曲线如图4所示。The preparation method of the double-anode buffer layer bulk heterojunction organic solar cell is as follows: firstly, toluene, acetone, detergent, deionized water, and isopropanol are used in sequence to form a substrate composed of a transparent substrate and an indium tin oxide (ITO) transparent conductive anode. The slices were ultrasonically cleaned, each step was 20 min. The substrate composed of the cleaned transparent substrate and the ITO transparent conductive anode was blown dry with nitrogen, and dried for 20 minutes. After the substrate was processed with a Plasma cleaning machine for 5 minutes, it was moved into a vacuum coating machine to evaporate and deposit a PTFE anode buffer layer (thickness is 1.5nm, the evaporation rate is ) and MoO 3 anode buffer layer (thickness is 5nm, evaporation rate is ). Move the substrate on which the double anode buffer layer has been evaporated into the Plasma cleaning machine, and process it for 2 minutes. The electron donor material P3HT and the electron acceptor material PC 61 BM are dissolved in o-dichlorobenzene at a mass percentage of 1:1 to obtain a mixed solution with a concentration of P3HT:PC 61 BM=17mg/ml:17mg/ml, and the mixed solution Stir at room temperature for 14 h; then move the substrate into a glove box (nitrogen atmosphere), and prepare a P3HT:PC 61 BM organic active layer on the MoO 3 anode buffer layer by spin coating at a speed of 700 rpm/s for 36 s with a thickness of about 230nm; after spin-coating to form a film, place it in a glove box for 3h to evaporate the solvent. On the organic active layer, the cathode buffer layer Alq3 (thickness is 1nm, evaporation rate is ) and metal cathode Al (thickness is 120nm, evaporation rate is ). The fabricated device was measured under standard conditions (AM1.5, 100mw/cm 2 ), and the JV curve data was collected using a Keithley2400 digital source meter. The device structure of the present invention is: transparent substrate/ITO/PTFE (thickness 1.5nm)/MoO 3 (thickness 5nm)/P3HT:PC 61 BM/Alq3 (thickness 1nm)/Al (thickness 120nm). The JV curves measured by the device of the present invention and the comparative device are shown in FIG. 4 .

对比例3Comparative example 3

将清洗好的透明衬底及透明导电阳极ITO所组成的基片用氮气吹干,烘干20min并用Plasma清洗机处理基片5min后,移入真空镀膜机中蒸镀阳极缓冲层MoO3(厚度为5nm,蒸发速率为)。将蒸镀了阳极缓冲层MoO3的基片移入Plasma清洗机,处理2min。将电子给体材料P3HT与电子受体材料PC61BM按质量百分比为1:1溶于邻二氯苯,得到浓度为P3HT:PC61BM=17mg/ml:17mg/ml的混合溶液,混合溶液室温搅拌14h;然后将基片移入手套箱(氮气氛围)中,采用旋涂法在MoO3阳极缓冲层上制备P3HT:PC61BM有机活性层,转速为700rpm/s,时间为36s,厚度约为230nm;然后在手套箱中放置3h以使溶剂挥发。在有机活性层上依次蒸镀阴极缓冲层Alq3(厚度为1nm,蒸发速率为)及金属阴极Al(厚度为120nm,蒸发速率为)。制备完成的器件在标准条件(AM1.5,100mw/cm2)下进行测量,使用Keithley2400数字源表收集J-V曲线数据。对比器件结构为:透明衬底/ITO/MoO3(厚度5nm)/P3HT:PC61BM/Alq3(厚度1nm)/Al(厚度120nm)。The substrate composed of the cleaned transparent substrate and the transparent conductive anode ITO was blown dry with nitrogen, dried for 20 minutes and processed with a Plasma cleaning machine for 5 minutes, and then moved into a vacuum coating machine to evaporate the anode buffer layer MoO 3 (thickness: 5nm, the evaporation rate is ). Move the substrate on which the anode buffer layer MoO 3 is evaporated into the Plasma cleaning machine, and process it for 2 minutes. The electron donor material P3HT and the electron acceptor material PC 61 BM are dissolved in o-dichlorobenzene at a mass percentage of 1:1 to obtain a mixed solution with a concentration of P3HT:PC 61 BM=17mg/ml:17mg/ml, and the mixed solution Stir at room temperature for 14 h; then move the substrate into a glove box (nitrogen atmosphere), and prepare a P3HT:PC 61 BM organic active layer on the MoO 3 anode buffer layer by spin coating at a speed of 700 rpm/s for 36 s with a thickness of about 230nm; then placed in the glove box for 3h to evaporate the solvent. On the organic active layer, the cathode buffer layer Alq3 (thickness is 1nm, evaporation rate is ) and metal cathode Al (thickness is 120nm, evaporation rate is ). The fabricated device was measured under standard conditions (AM1.5, 100mw/cm 2 ), and the JV curve data was collected using a Keithley2400 digital source meter. The comparative device structure is: transparent substrate/ITO/MoO 3 (thickness 5nm)/P3HT:PC 61 BM/Alq3 (thickness 1nm)/Al (thickness 120nm).

表3为实施例5与对比例3的数据结果对比,结果显示,对于有机活性层材料P3HT:PC61BM,以PTFE阳极缓冲层和MoO3阳极缓冲层组合成双阳极缓冲层,相比于单层阳极缓冲层,器件的短路电流提高17.6%,填充因子提高6.47%,能量转换效率提高26.6%。Table 3 is the data result comparison of embodiment 5 and comparative example 3, and the result shows, for organic active layer material P3HT:PC 61 BM, with PTFE anode buffer layer and MoO The anode buffer layer is combined into double anode buffer layer, compared to With a single-layer anode buffer layer, the short-circuit current of the device is increased by 17.6%, the fill factor is increased by 6.47%, and the energy conversion efficiency is increased by 26.6%.

表3为实施例5的发明结构器件与对比器件性能测试的结果对比Table 3 is the result comparison of the inventive structure device of embodiment 5 and the comparative device performance test

实施例6Example 6

双阳极缓冲层体异质结有机太阳能电池制备方法如下:将清洗好的透明衬底及ITO透明导电阳极所组成的基片用氮气吹干,烘干20min并用Plasma清洗机处理基片5min后,移入真空镀膜机中依次蒸镀PTFE阳极缓冲层(厚度为0.8nm,蒸发速率为)及MoO3阳极缓冲层(厚度为4nm,蒸发速率为)。与实施例1相同的方法在MoO3阳极缓冲层上制备有机活性层PCDTBT:PC71BM。在有机活性层上依次蒸镀阴极缓冲层Alq3(厚度为1nm,蒸发速率为)及金属阴极Al(厚度为120nm,蒸发速率为)。制备完成的器件在标准条件下(AM1.5,100mw/cm2)进行测量,使用Keithley2400数字源表收集J-V曲线数据。器件结构为:透明衬底/ITO/PTFE(厚度0.8nm)/MoO3(厚度4nm)/PCDTBT:PC71BM/Alq3(厚度1nm)/Al(厚度120nm)。实施例6的器件所测得的J-V曲线如图5所示。The preparation method of the double anode buffer layer bulk heterojunction organic solar cell is as follows: dry the substrate composed of the cleaned transparent substrate and the ITO transparent conductive anode with nitrogen, dry it for 20 minutes, and treat the substrate with a Plasma cleaning machine for 5 minutes. Move into the vacuum coating machine and vapor-deposit PTFE anode buffer layer (thickness is 0.8nm, evaporation rate is ) and MoO 3 anode buffer layer (thickness is 4nm, evaporation rate is ). The same method as in Example 1 was used to prepare the organic active layer PCDTBT:PC 71 BM on the MoO 3 anode buffer layer. On the organic active layer, the cathode buffer layer Alq3 (thickness is 1nm, evaporation rate is ) and metal cathode Al (thickness is 120nm, evaporation rate is ). The fabricated device was measured under standard conditions (AM1.5, 100mw/cm 2 ), and the JV curve data was collected using a Keithley2400 digital source meter. The device structure is: transparent substrate/ITO/PTFE (thickness 0.8nm)/MoO 3 (thickness 4nm)/PCDTBT:PC 71 BM/Alq3 (thickness 1nm)/Al (thickness 120nm). The measured JV curve of the device of Example 6 is shown in FIG. 5 .

实施例7Example 7

双阳极缓冲层体异质结有机太阳能电池制备方法如下:将清洗好的透明衬底及ITO透明导电阳极所组成的基片用氮气吹干,烘干20min并用Plasma清洗机处理基片5min后,移入真空镀膜机中依次蒸镀PTFE阳极缓冲层(厚度为0.8nm,蒸发速率为)及MoO3阳极缓冲层(厚度为5nm,蒸发速率为)。与实施例1相同的方法在MoO3阳极缓冲层上制备有机活性层PCDTBT:PC71BM。在有机活性层上依次蒸镀阴极缓冲层Alq3(厚度为1nm,蒸发速率为)及金属阴极Al(厚度为120nm,蒸发速率为)。制备完成的器件在标准条件下(AM1.5,100mw/cm2)进行测量,使用Keithley2400数字源表收集J-V曲线数据。器件结构为:透明衬底/ITO/PTFE(厚度0.8m)/MoO3(厚度5nm)/PCDTBT:PC71BM/Alq3(厚度1nm)/Al(厚度120nm)。实施例7的器件所测得的J-V曲线如图5所示。The preparation method of the double anode buffer layer bulk heterojunction organic solar cell is as follows: dry the substrate composed of the cleaned transparent substrate and the ITO transparent conductive anode with nitrogen, dry it for 20 minutes, and treat the substrate with a Plasma cleaning machine for 5 minutes. Move into the vacuum coating machine and vapor-deposit PTFE anode buffer layer (thickness is 0.8nm, evaporation rate is ) and MoO 3 anode buffer layer (thickness is 5nm, evaporation rate is ). The same method as in Example 1 was used to prepare the organic active layer PCDTBT:PC 71 BM on the MoO 3 anode buffer layer. On the organic active layer, the cathode buffer layer Alq3 (thickness is 1nm, evaporation rate is ) and metal cathode Al (thickness is 120nm, evaporation rate is ). The fabricated device was measured under standard conditions (AM1.5, 100mw/cm 2 ), and the JV curve data was collected using a Keithley2400 digital source meter. The device structure is: transparent substrate/ITO/PTFE (thickness 0.8m)/MoO 3 (thickness 5nm)/PCDTBT:PC 71 BM/Alq3 (thickness 1nm)/Al (thickness 120nm). The measured JV curve of the device of Example 7 is shown in FIG. 5 .

实施例8Example 8

双阳极缓冲层体异质结有机太阳能电池制备方法如下:将清洗好的透明衬底及ITO透明导电阳极所组成的基片用氮气吹干,烘干20min并用Plasma清洗机处理基片5min后,移入真空镀膜机中依次蒸镀PTFE阳极缓冲层(厚度为0.8nm,蒸发速率为)及MoO3阳极缓冲层(厚度为10nm,蒸发速率为)。与实施例1相同的方法在MoO3阳极缓冲层上制备有机活性层PCDTBT:PC71BM。在有机活性层上依次蒸镀阴极缓冲层Alq3(厚度为1nm,蒸发速率为)及金属阴极Al(厚度为120nm,蒸发速率为)。制备完成的器件在标准条件下(AM1.5,100mw/cm2)进行测量,使用Keithley2400数字源表收集J-V曲线数据。器件结构为:透明衬底/ITO/PTFE(厚度0.8m)/MoO3(厚度10nm)/PCDTBT:PC71BM/Alq3(厚度1nm)/Al(厚度120nm)。实施例8的器件所测得的J-V曲线如图5所示。The preparation method of the double anode buffer layer bulk heterojunction organic solar cell is as follows: dry the substrate composed of the cleaned transparent substrate and the ITO transparent conductive anode with nitrogen, dry it for 20 minutes, and treat the substrate with a Plasma cleaning machine for 5 minutes. Move into the vacuum coating machine and vapor-deposit PTFE anode buffer layer (thickness is 0.8nm, evaporation rate is ) and MoO 3 anode buffer layer (thickness is 10nm, evaporation rate is ). The same method as in Example 1 was used to prepare the organic active layer PCDTBT:PC 71 BM on the MoO 3 anode buffer layer. On the organic active layer, the cathode buffer layer Alq3 (thickness is 1nm, evaporation rate is ) and metal cathode Al (thickness is 120nm, evaporation rate is ). The fabricated device was measured under standard conditions (AM1.5, 100mw/cm 2 ), and the JV curve data was collected using a Keithley2400 digital source meter. The device structure is: transparent substrate/ITO/PTFE (thickness 0.8m)/MoO 3 (thickness 10nm)/PCDTBT:PC 71 BM/Alq3 (thickness 1nm)/Al (thickness 120nm). The measured JV curve of the device of Example 8 is shown in FIG. 5 .

实施例6~8的结果显示,在允许范围内改变MoO3阳极缓冲层的厚度,对器件的性能影响不是很大。The results of Examples 6-8 show that changing the thickness of the MoO 3 anode buffer layer within the allowable range does not have a great impact on the performance of the device.

表4为实施例6~8的发明结构器件性能测试的结果对比Table 4 is the result comparison of the invention structure device performance test of embodiment 6~8

Jsc(mA/cm2)Jsc(mA/cm 2 ) Voc(V)Voc(V) FF(%)FF(%) PCE(%)PCE(%) 实施例6器件Embodiment 6 device 11.75011.750 0.8770.877 63.6963.69 6.5666.566 实施例7器件Embodiment 7 device 11.64311.643 0.8710.871 65.8965.89 6.6816.681 实施例8器件Embodiment 8 device 11.89911.899 0.8790.879 63.5063.50 6.6406.640

本发明不限于上述实施例,所述的阴极缓冲层材料还可以为LiF、卟啉小分子、Bphen、BCP中的一种,或由其中两种以上材料按顺序一层层制备而成。所述的金属阴极材料还可以为Al、Ca、Ag、Au中的一种,或由其中两种以上材料按顺序一层层制备而成。所述的透明衬底还可以为透明柔性聚合物衬底,透明柔性聚合物材料包括聚乙烯、聚对苯二甲酸乙二脂、聚甲基丙烯酸甲酯、聚碳酸酯、聚氨基甲酸酯、聚酰亚胺或聚丙烯酸中的一种,或由其中两种以上材料混合制成,或由其中两种以上材料按顺序一层层制备而成。The present invention is not limited to the above examples, and the cathode buffer layer material can also be one of LiF, porphyrin small molecule, Bphen, BCP, or two or more of them can be prepared layer by layer sequentially. The metal cathode material can also be one of Al, Ca, Ag, Au, or prepared layer by layer from two or more of these materials in sequence. The transparent substrate can also be a transparent flexible polymer substrate, and the transparent flexible polymer material includes polyethylene, polyethylene terephthalate, polymethyl methacrylate, polycarbonate, polyurethane , polyimide or polyacrylic acid, or by mixing two or more of them, or by layer by layer of two or more of them in sequence.

本发明已通过上述实施例对本发明进行了说明。值得注意的是,实施例只是用于对本发明的举例及说明,并不局限于上述实例。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The Invention The invention has been illustrated by the above examples. It should be noted that the embodiments are only used to illustrate and describe the present invention, and are not limited to the above examples. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1.一种双阳极缓冲层体异质结有机太阳能电池,采用正型结构,自下而上依次为:透明衬底、透明导电阳极、阳极缓冲层、有机活性层、阴极缓冲层、金属阴极;其特征在于所述阳极缓冲层为PTFE阳极缓冲层和MoO3阳极缓冲层构成的双阳极缓冲层;PTFE阳极缓冲层制备于透明导电阳极上;MoO3阳极缓冲层制备于PTFE阳极缓冲层与有机活性层之间;PTFE阳极缓冲层厚度为0.3~2nm,MoO3阳极缓冲层厚度为4~10nm。1. A double-anode buffer layer bulk heterojunction organic solar cell, which adopts a positive-type structure, from bottom to top: transparent substrate, transparent conductive anode, anode buffer layer, organic active layer, cathode buffer layer, metal cathode ; It is characterized in that the anode buffer layer is a double anode buffer layer composed of PTFE anode buffer layer and MoO3 anode buffer layer; PTFE anode buffer layer is prepared on a transparent conductive anode; MoO3 anode buffer layer is prepared on PTFE anode buffer layer and Between the organic active layers; the thickness of the PTFE anode buffer layer is 0.3-2nm, and the thickness of the MoO 3 anode buffer layer is 4-10nm. 2.根据权利要求1所述的双阳极缓冲层体异质结有机太阳能电池,其特征在于所述PTFE阳极缓冲层厚度优选1.5nm。2. The double anode buffer layer bulk heterojunction organic solar cell according to claim 1, characterized in that the thickness of the PTFE anode buffer layer is preferably 1.5 nm. 3.根据权利要求1所述的双阳极缓冲层体异质结有机太阳能电池,其特征在于所述的透明衬底为透明玻璃或者透明柔性聚合物。3. The double anode buffer layer body heterojunction organic solar cell according to claim 1, characterized in that the transparent substrate is transparent glass or transparent flexible polymer. 4.根据权利要求3所述的双阳极缓冲层体异质结有机太阳能电池,其特征在于透明柔性聚合物为聚乙烯、聚对苯二甲酸乙二脂、聚甲基丙烯酸甲酯、聚碳酸酯、聚氨基甲酸酯、聚酰亚胺或聚丙烯酸中的一种,或由其中两种以上材料混合制成,或由其中两种以上材料按顺序一层层制备而成。4. The double anode buffer layer body heterojunction organic solar cell according to claim 3, characterized in that the transparent flexible polymer is polyethylene, polyethylene terephthalate, polymethyl methacrylate, polycarbonate One of ester, polyurethane, polyimide or polyacrylic acid, or two or more of them are mixed, or two or more of them are prepared layer by layer in sequence. 5.根据权利要求1所述的双阳极缓冲层体异质结有机太阳能电池,其特征在于所述透明导电阳极,其材料为氧化铟锡,沉积于透明衬底上。5. The double anode buffer layer bulk heterojunction organic solar cell according to claim 1, characterized in that the transparent conductive anode is made of indium tin oxide and deposited on a transparent substrate. 6.根据权利要求1所述的双阳极缓冲层体异质结有机太阳能电池,其特征在于所述的有机活性层是由电子给体材料PCDTBT和电子受体材料PC71BM按1:4的质量比配置的混合物,或者是由电子给体材料P3HT和电子受体材料PC61BM按1:1的质量比配置的混合物。6. The dual anode buffer layer bulk heterojunction organic solar cell according to claim 1, wherein the organic active layer is composed of electron donor material PCDTBT and electron acceptor material PC 71 BM according to 1:4 The mixture configured by mass ratio, or the mixture configured by electron donor material P3HT and electron acceptor material PC 61 BM according to a mass ratio of 1:1. 7.根据权利要求1所述的双阳极缓冲层体异质结有机太阳能电池,其特征在于所述的阴极缓冲层,其材料为Alq3、LiF、卟啉小分子、Bphen或BCP中的一种,或由其中两种以上材料按顺序一层层制备而成,厚度为1~10nm;所述的金属阴极,其材料为Al、Ca、Ag或Au中的一种,或由其中两种以上材料按顺序一层层制备而成,厚度为100nm~200nm。7. double anode buffer layer bulk heterojunction organic solar cell according to claim 1, is characterized in that described cathode buffer layer, its material is a kind of in Alq3, LiF, porphyrin small molecule, Bphen or BCP , or prepared layer by layer from two or more materials in sequence, with a thickness of 1-10 nm; the metal cathode is made of one of Al, Ca, Ag or Au, or two or more of them The material is prepared layer by layer in sequence, and the thickness is 100nm-200nm. 8.一种如权利要求1所述双阳极缓冲层体异质结有机太阳能电池的制备方法,包括以下步骤:8. A method for preparing a double anode buffer layer body heterojunction organic solar cell as claimed in claim 1, comprising the following steps: ①依次使用甲苯、丙酮、洗涤剂、去离子水、异丙醇对透明导电阳极与透明衬底构成的基片进行超声清洗,清洗过后的基片保存在异丙醇中备用;① Use toluene, acetone, detergent, deionized water, and isopropanol in sequence to ultrasonically clean the substrate composed of the transparent conductive anode and the transparent substrate, and store the cleaned substrate in isopropanol for later use; ②清洗后的基片用氮气吹干,移入干燥箱中烘干,然后用Plasma清洗机进行等离子体处理;②The cleaned substrate is blown dry with nitrogen, moved into a drying oven for drying, and then plasma treated with a Plasma cleaning machine; ③将处理好的基片移入真空镀膜机里,在透明导电阳极上蒸镀PTFE阳极缓冲层,然后在PTFE阳极缓冲层上蒸镀MoO3阳极缓冲层;其中PTFE的蒸发速率为厚度为0.3~2nm,MoO3的蒸发速率为厚度为4~10nm;③ Move the treated substrate into the vacuum coating machine, evaporate the PTFE anode buffer layer on the transparent conductive anode, and then evaporate the MoO3 anode buffer layer on the PTFE anode buffer layer; wherein the evaporation rate of PTFE is The thickness is 0.3~2nm, the evaporation rate of MoO 3 is The thickness is 4~10nm; ④将上述蒸镀了双阳极缓冲层的基片移入Plasma清洗机,进行等离子体处理;④ Move the above-mentioned substrate on which the double anode buffer layer has been vapor-deposited into the Plasma cleaning machine for plasma treatment; ⑤在MoO3阳极缓冲层上制备有机活性层;⑤ Prepare an organic active layer on the MoO 3 anode buffer layer; ⑥将步骤⑤获得的基片移入真空镀膜机里,依次在有机活性层上蒸镀阴极缓冲层和金属阴极。⑥ Move the substrate obtained in step ⑤ into a vacuum coating machine, and sequentially vapor-deposit a cathode buffer layer and a metal cathode on the organic active layer. 9.根据权利要求8所述的双阳极缓冲层体异质结有机太阳能电池的制备方法,其特征在于所述步骤⑤中采用旋涂的方法在氮气氛围中将电子给体材料PCDTBT和电子受体材料PC71BM按1:4的质量比配置的混合溶液旋涂在MoO3阳极缓冲层上,匀胶机转速为1500rpm/s,旋涂时间为40s;所述混合溶液的溶剂为邻二氯苯,溶液的浓度为PCDTBT:PC71BM=8mg/ml:32mg/ml;然后在70℃的条件下退火30min蒸发掉溶剂,得到有机活性层。9. the preparation method of double anode buffer layer body heterojunction organic solar cell according to claim 8, it is characterized in that in described step 5. adopt the method for spin-coating electron donor material PCDTBT and electron acceptor material in nitrogen atmosphere The bulk material PC 71 BM is spin-coated on the MoO 3 anode buffer layer with a mass ratio of 1:4, the speed of the homogenizer is 1500rpm/s, and the spin-coating time is 40s; the solvent of the mixed solution is Chlorobenzene, the concentration of the solution is PCDTBT:PC 71 BM=8mg/ml:32mg/ml; then annealing at 70°C for 30min to evaporate the solvent to obtain an organic active layer. 10.根据权利要求8所述的双阳极缓冲层体异质结有机太阳能电池的制备方法,其特征在于所述步骤⑤中,采用旋涂的方法在氮气氛围中将电子给体材料P3HT和电子受体材料PC61BM按1:1的质量比配置的混合溶液旋涂在MoO3阳极缓冲层上,匀胶机转速为700rpm/s,旋涂时间为36s;所述混合溶液的溶剂为邻二氯苯,溶液的浓度为P3HT:PC61BM=17mg/ml:17mg/ml;然后室温退火3h蒸发掉溶剂,得到有机活性层。10. The method for preparing a double anode buffer layer bulk heterojunction organic solar cell according to claim 8, characterized in that in the step 5, the electron donor material P3HT and electron Acceptor material PC 61 BM is spin-coated on the MoO 3 anode buffer layer according to the mass ratio configuration of 1:1, the speed of homogenizer is 700rpm/s, and the spin-coating time is 36s; The solvent of described mixed solution is o Dichlorobenzene, the concentration of the solution is P3HT:PC 61 BM=17mg/ml:17mg/ml; then anneal at room temperature for 3 hours to evaporate the solvent to obtain an organic active layer.
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