An organic solar cell using a composite anode modification layer and a preparation method thereof

Abstract

The present invention relates to an organic solar cell using a composite anode modification layer and a preparation method thereof. The composition of the solar cell from bottom to top is successively a glass substrate, a cathode layer, a cathode modification layer, an active layer, an anode modification layer, an n-type doping layer, and an anode layer; the n-type doping layer is one of the following two-component thin films: BCP-Yb, Bphen-Yb, TPBi-Yb; in the preparation method, a solution method and a vacuum evaporation method are combined, wherein: the cathode modification layer and the active layer are prepared by the solution method, and the anode modification layer, the n-type doping layer, and the anode are prepared by the vacuum evaporation method. The present invention improves the cost advantage of the organic solar cell, not only overcomes the bottleneck factors of the existing preparation process of the reverse organic solar cell, but also exhibits enhanced device performance.

Description

Technical Field

[0001] The technical solution of the present invention relates to solid devices specifically adapted to convert light energy into electrical energy, and more particularly to an organic solar cell using a composite anode modification layer and a preparation method thereof. Background Art

[0002] The energy issue is related to national security and is of great significance. Actively developing renewable clean energy technologies is an important means to solve the current energy shortage problem. Due to its flexibility, low cost, semi-transparency, etc., organic solar cells have become one of the forefront hotspots in current renewable energy technologies. Currently, the highest efficiency of organic photovoltaic devices has reached 20%, entering the threshold of commercialization.

[0003] To promote the industrialization process of organic solar cells, it is necessary to develop simple and efficient organic solar cell structures and preparation methods with cost advantages. In a normal organic solar cell, indium tin oxide conductive thin film is often used as the anode layer, and a blend film of poly(3,4-ethylenedioxythiophene) and poly(styrenesulfonic acid) is often used as the anode modification layer. Since the acidity of poly(styrenesulfonic acid) is highly corrosive to the indium tin oxide thin film, the device stability is reduced. For an inverted organic solar cell, the mainstream composition from bottom to top is a glass substrate, a cathode layer, a cathode modification layer, an active layer, an anode modification layer, and an anode layer. Among them, indium tin oxide thin film is often used as the cathode, and low work function transition metal oxide thin film is often used as the cathode modification layer. Since the low work function transition metal oxide thin film has no obvious destructive effect on the indium tin oxide thin film, higher device stability can be achieved. However, an inverted organic solar cell often uses MoO3 as the anode modification layer. Due to its very low conductivity and poor hole conduction and extraction ability, the device performance is inhibited.

[0004] Currently, the mainstream preparation technology of organic solar cells in the laboratory is the all-solution processing method, that is, from the anode to each functional layer to the cathode, all are prepared into films from solutions. However, the all-solution method is not fully suitable for industrial production because: 1. To prepare a large-area, uniform and pinhole-free organic functional thin film by the solution method, the film thickness needs to be at least above 0.5 microns; while the optimal thickness of the solution-processed anode modification layer commonly used in inverted organic photovoltaic devices is much less than 0.5 microns. 2. Preparing a water / alcohol-soluble anode modification layer on the surface of the active layer by the solution method will cause a certain degree of damage to the active layer and reduce the device stability. Therefore, it can be considered that the all-solution method is not a truly cost-effective method. Summary of the Invention

[0005] The object of the present invention is to provide an organic solar cell using a composite anode modification layer and a preparation method thereof in view of the deficiencies existing in the current technology. This solar cell is an organic solar cell using a composite anode modification layer composed of an anode modification layer and an n-type doping layer; in the preparation method, a solution method and a vacuum evaporation method are combined, wherein: the cathode modification layer and the active layer are prepared by the solution method, and the anode modification layer, the n-type doping layer and the anode are prepared by the vacuum evaporation method. The present invention improves the cost advantage of the organic solar cell, not only overcomes the bottleneck factors of the existing preparation process of the inverted organic solar cell, but also exhibits enhanced device performance.

[0006] The technical solution adopted by the present invention to solve this technical problem is:

[0007] An organic solar cell using a composite anode modification layer is an organic solar cell using a composite anode modification layer composed of an anode modification layer and an n-type doping layer; the components of this solar cell from bottom to top are a glass substrate, a cathode layer, a cathode modification layer, an active layer, an anode modification layer, an n-type doping layer and an anode layer;

[0008] The material of the cathode layer is a conductive indium tin oxide thin film;

[0009] The material of the cathode modification layer is nano zinc oxide;

[0010] The material of the active layer is any one of the following two-component thin films: I. A two-component thin film composed of poly(3-hexylthiophene) and [6,6]-phenyl-C 61 -butyric acid methyl ester, and the mass ratio thereof is poly(3-hexylthiophene):[6,6]-phenyl-C 61 -butyric acid methyl ester = 12:6 to 12:24; II. A two-component thin film composed of poly(4,8-bis(5-(2-ethylhexyl)thienyl)benzo[1,2-b;4,5-b']dithienyl-alt-(4-(2-ethylhexyl-3-fluorothieno[3,4-b]thiophene)-2-carboxylate)) and [6,6]-phenyl-C 71 -butyric acid methyl ester, and the mass ratio thereof is poly(4,8-bis(5-(2-ethylhexyl)thienyl)benzo[1,2-b;4,5-b']dithienyl-alt-(4-(2-ethylhexyl-3-fluorothieno[3,4-b]thiophene)-2-carboxylate)):[6,6]-phenyl-C 71- Methyl butyrate = 10:5 to 10:20; III. A two-component thin film composed of poly([4,8-bis-((2-ethylhexyl)-4-fluoro-2-thienyl)benzo[1,2-b;3,3-b]dithiophene]-alt-[1,3-bis-(thien-5-yl)-5,7-bis-(2-ethylhexyl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione]) and 12,13-bis(2-ethylhexyl)-3,9-undecylene-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2”,3”:4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-bis(5,6-difluoro-3-(dicyanomethylene)indene-1-one]), and the mass ratio thereof is poly([4,8-bis-((2-ethylhexyl)-4-fluoro-2-thienyl)benzo[1,2-b;3,3-b]dithiophene]-alt-[1,3-bis-(thien-5-yl)-5,7-bis-(2-ethylhexyl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione]):12,13-bis(2-ethylhexyl)-3,9-undecylene-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2”,3”:4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-bis(5,6-difluoro-3-(dicyanomethylene)indene-1-one) = 7:3.5 to 7:14;

[0011] The material of the anode modification layer is molybdenum trioxide;

[0012] The n-type doping layer deposited on the anode modification layer is one of the following two-component thin films: I. An n-type doping thin film composed of 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline and ytterbium, and the mass ratio thereof is 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline:ytterbium = 100:1 to 100:40; II. An n-type doping thin film composed of 4,7-diphenyl-1,10-phenanthroline and ytterbium, and the mass ratio thereof is 4,7-diphenyl-1,10-phenanthroline:ytterbium = 100:1 to 100:40; III. An n-type doping thin film composed of 1,3,5-tris(1-phenyl-1H-benzoimidazol-2-yl)benzene and ytterbium, and the mass ratio thereof is 1,3,5-tris(1-phenyl-1H-benzoimidazol-2-yl)benzene:ytterbium = 100:1 to 100:40;

[0013] The material of the anode layer deposited on the n-type doping layer is aluminum.

[0014] The above-mentioned organic solar cell using a composite anode modification layer, wherein the thickness of the indium tin oxide conductive thin film is 80 - 300 nm and the sheet resistance is less than 10 ohms per 4×4 cm 2 square.

[0015] The above-mentioned organic solar cell using a composite anode modification layer, wherein the thickness of the cathode modification layer is 20 - 50 nm.

[0016] The above-mentioned organic solar cell using a composite anode modification layer, wherein the thickness of the active layer is 50 - 500 nm.

[0017] The above-mentioned organic solar cell using a composite anode modification layer, wherein the thickness of the anode modification layer is 2 - 10 nm.

[0018] The above-mentioned organic solar cell using a composite anode modification layer, wherein the thickness of the n-type doping layer is 5 - 50 nm.

[0019] The above-mentioned organic solar cell using a composite anode modification layer, wherein the thickness of the anode layer is 50 - 200 nm.

[0020] The above-mentioned organic solar cell using a composite anode modification layer, and all the materials can be obtained through commercial purchase.

[0021] To save space, the English abbreviations, molecular formulas or element symbols of the following compounds are listed, and the corresponding compounds are represented by the English abbreviations, molecular formulas or element symbols in the following text.

[0022] The English abbreviation of poly(3-hexylthiophene) is P3HT; [6.6]-phenyl-C 61 -methyl butyrate is abbreviated as PC 61 BM; the English abbreviation of poly(4,8-bis(5-(2-ethylhexyl)thienyl)benzo[1,2-b;4,5-b']dithienyl-alt-(4-(2-ethylhexyl-3-fluorothieno[3,4-b]thiophene)-2-carboxylate)) is PTB7-Th; [6.6]-phenyl-C 71 -methyl butyrate is abbreviated as PC 71The English abbreviation of BM; poly([4,8-bis-((2-ethylhexyl)-4-fluoro-2-thienyl)benzo[1,2-b;3,3-b]dithiophene]-alt-[1,3-bis-(thiophen-5-yl)-5,7-bis-(2-ethylhexyl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione]) is PM6; the English abbreviation of 12,13-bis(2-ethylhexyl)-3,9-undecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2”,3”:4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-bis(5,6-difluoro-3-(dicyanomethylene)indene-1-one) is Y6; the English abbreviation of 4,7-diphenyl-1,10-phenanthroline is Bphen; the English abbreviation of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline is BCP; the English abbreviation of 1,3,5-tris(1-phenyl-1H-benzoimidazol-2-yl)benzene is TPBi; the molecular formula of zinc oxide is ZnO; the molecular formula of molybdenum trioxide is MoO3; the element symbol of aluminum is Al.

[0023] The preparation method of an organic solar cell using a composite anode modification layer is as follows:

[0024] First step, treatment of the cathode layer on the substrate

[0025] After cutting the glass substrate covered with the cathode layer, ultrasonically clean it in acetone, ethanol, and deionized water in sequence;

[0026] Second step, deposition of the cathode modification layer on the cathode layer

[0027] Spin-coat the nano-ZnO solution onto the cathode layer treated in the first step at a speed of 1000 - 3000 revolutions per minute for 50 - 70 seconds to form a cathode modification layer film;

[0028] Among them, the solvent of the nano-ZnO solution is ethanol, the concentration is 10 - 30 mg / mL, and the particle size of the nano-ZnO particles is 1 - 3 nm;

[0029] Third step, deposition of the active layer on the cathode modification layer

[0030] Select any one of the following processes:

[0031] Ⅰ. According to the mass ratio of the two-component film as P3HT:PC 61 BM = 12:6 - 24, add P3HT and PC 61 BM to 1,2-o-dichlorobenzene to form a mixed solution. Among them, PC 61The concentration of BM is 6 - 24 mg / mL; then it is spin-coated onto the cathode modification layer deposited in the second step at a speed of 800 - 2000 revolutions per minute, and then placed in the atmosphere for 200 - 1200 seconds to form a two-component thin film;

[0032] II. According to the mass ratio of the two-component thin film PTB7-Th:PC 71 BM = 10:5 - 20, PTB7-Th and PC 71 BM are added to 1,2-dichlorobenzene to form a mixed solution, where the concentration of PC 71 BM is 5 - 20 mg / ml; then it is spin-coated onto the cathode modification layer deposited in the second step at a speed of 800 - 2000 revolutions per minute to form a two-component thin film;

[0033] III. According to the mass ratio of the two-component thin film PM6:Y6 = 7:3.5 - 14, PM6 and Y6 are added to chloroform to obtain a mixed solution, where the concentration of Y6 is 3.5 - 14 mg / mL; then it is spin-coated onto the cathode modification layer deposited in the second step at a speed of 2000 - 5000 revolutions per minute, and then annealed in a nitrogen atmosphere for 2 - 8 minutes at an annealing temperature of 90 - 110 °C to form a two-component thin film.

[0034] The fourth step is to deposit an anode modification layer on the active layer

[0035] The intermediate product with the active layer deposited in the third step is placed in a vacuum coating machine; the vacuum coating machine is pumped to a background vacuum of 4×10 -4 Pa, and MoO3 is deposited on the active layer deposited in the third step as the anode modification layer by thermal evaporation;

[0036] The fifth step is to deposit an n-type doping layer on the anode modification layer

[0037] Any one of the following processes is selected:

[0038] I. The vacuum coating machine is pumped to a background vacuum of 4×10 -4 Pa, and BCP doped with Yb is deposited on the anode modification layer deposited in the fourth step as the n-type doping layer by thermal evaporation, with a thickness of 5 - 50 nm and a mass ratio of BCP:Yb = 100:1 - 100:40;

[0039] II. The vacuum coating machine is pumped to a background vacuum of 4×10 -4 Pa, and Bphen doped with Yb is deposited on the anode modification layer deposited in the fourth step as the n-type doping layer by thermal evaporation, with a thickness of 5 - 50 nm and a mass ratio of Bphen:Yb = 100:1 - 100:40;

[0040] Ⅲ. The background vacuum degree of the vacuum coating machine is pumped to 4×10 -4 Pa. By using the thermal evaporation method, Yb-doped TPBi is deposited on the anode modification layer deposited in the fourth step as the n-type doping layer, with a thickness of 5 - 50 nm, and the mass ratio is TPBi:Yb = 100:1 - 100:40;

[0041] Step 6, deposit the anode layer on the n-type doping layer

[0042] In the vacuum coating machine, the background vacuum degree of the vacuum coating machine is pumped to 4×10 -4 Pa. By using the thermal evaporation method, an Al thin film is deposited on the n-type doping layer deposited in the fifth step as the anode layer, and the deposition rate is Take out this final product from the vacuum coating machine.

[0043] Thus, the above-mentioned organic solar cell using a composite anode modification layer is finally prepared, which is an organic solar cell using a composite anode modification layer composed of an anode modification layer and an n-type doping layer.

[0044] In the preparation method of the above-mentioned organic solar cell using a composite anode modification layer, the equipment and processes involved are well-known to those skilled in the art, and the materials involved are commercially available.

[0045] The substantial features of the present invention are:

[0046] In the current technology, in the organic solar cell technology, the n-type doping layer is used to assist electron collection and conduction, which utilizes the principle that the n-type doping layer has high conductivity, large electron mobility, and its own work function matches the lowest unoccupied molecular orbital energy level of the active layer electron acceptor material. However, due to the mismatch between the work function of the n-type doping layer itself and the highest occupied molecular orbital energy level of the active layer electron donor material, it cannot be used as an anode modification layer. MoO3 is an anode modification layer often used in the current organic photovoltaic technology. It is a high-work-function n-type material that matches the highest occupied molecular orbital energy level of the active layer electron donor material, thereby forming a carrier recombination-type ohmic contact to achieve hole collection and conduction. Although the work function of the n-type doping layer is much smaller than that of MoO3, through the Fermi level flattening principle, the n-type doping layer forms an ohmic contact with MoO3. Since the conductivity of the n-type doping layer is higher than that of MoO3, hole collection and conduction are promoted.

[0047] In the present invention, an n-type doping layer is prepared between the anode modification layer and the anode, or the anode modification layer and the n-type doping layer together form a composite anode modification layer. Through the theory of Fermi level flattening, the synergistic effect of the high work function of MoO3 (to achieve ohmic contact with the electron acceptor material of the active layer) and the high conductivity of the n-type doping layer (to reduce the ohmic loss in the hole transport process) is utilized to achieve efficient hole collection and conduction.

[0048] The beneficial effects of the present invention are as follows:

[0049] The organic solar cell using a composite anode modification layer proposed by the present invention uses an n-type doped thin film to improve the hole transport and extraction efficiency, overcoming the disadvantage of the low conductivity of the traditional anode modification layer MoO3. Different from the conventional MoO3 used as the anode modification layer (which is recognized as the best anode modification layer), in Example 1, a composite anode modification layer composed of MoO3 and an n-type doping layer is used. The photovoltaic device efficiency in Example 1 is approximately 20% higher than that in Comparative Example 1, and the improvement effect of the photovoltaic performance is significant. Brief Description of the Drawings

[0050] The present invention will be further described below in conjunction with the drawings and embodiments.

[0051] Figure 1 It is a schematic structural diagram of the organic solar cell using a composite anode modification layer of the present invention.

[0052] Figure 2 It is a comparison diagram of the photocurrent curves of the organic solar cell using a composite anode modification layer prepared in Example 1 of the present invention and the reverse organic solar cell using 10 nm MoO3 in the prior art. Detailed Embodiments

[0053] Figure 1 The shown embodiments show that an organic solar cell using a composite anode modification layer of the present invention is composed of a cathode layer i on a glass substrate, a cathode modification layer ii deposited on the cathode layer i, an active layer iii deposited on the cathode modification layer ii, an anode modification layer iv deposited on the active layer iii, an n-type doping layer v deposited on the anode modification layer iv, and an anode layer vi deposited on the n-type doping layer v.

[0054] Example 1

[0055] Prepare an organic solar cell using a composite anode modification layer with a structure of ITO with a thickness of 100 nm / nano-ZnO thin film with a thickness of 30 nm / P3HT:PC 61 BM = 12:10 / MoO3 with a thickness of 5 nm / BCP:Yb with a thickness of 5 nm / Al with a thickness of 100 nm.

[0056] The organic solar cell using a composite anode modification layer is composed of an ITO cathode layer with a thickness of 100 nm on a glass substrate, a nano-ZnO thin film cathode modification layer with a thickness of 30 nm deposited on the ITO cathode layer, and a P3HT:PC 61 BM thin film active layer, a MoO3 thin film cathode modification layer with a thickness of 5 nm deposited on the P3HT:PC 61 BM thin film active layer, a BCP:Yb thin film n-type doping layer with a thickness of 5 nm deposited on the MoO3 thin film cathode modification layer, and an Al anode layer with a thickness of 100 nm deposited on the BCP:Yb thin film n-type doping layer, forming an organic solar cell using a composite anode modification layer.

[0057] The above ITO is the abbreviation of indium tin oxide thin film. The ITO cathode layer is attached to the glass substrate, simply referred to as the ITO cathode substrate. The thickness of the indium tin oxide conductive thin film is 100 nm, and the sheet resistance is less than 10 ohms per 4×4 cm 2 square. The ITO cathode substrate of this embodiment is produced by CSG Holding Co., Ltd. and obtained through commercial purchase.

[0058] The preparation method of the above organic solar cell using a composite anode modification layer is as follows:

[0059] First step, treatment of the ITO cathode layer on the substrate

[0060] An ITO cathode substrate square with a thickness of 100 nm, a size of 4×4 cm 2 and a sheet resistance less than 10 ohms per 4×4 cm 2 square is first cleaned twice in an ultrasonic cleaner filled with acetone, then twice in an ultrasonic cleaner filled with ethanol, and finally twice in an ultrasonic cleaner filled with deionized water, each time for 10 minutes;

[0061] Second step, deposition of the cathode modification layer on the cathode layer

[0062] Prepare a solution of ZnO nanoparticles (particle size of 2 nm) with a mass concentration of 20 mg / mL in ethanol as the solvent. Spin-coat it onto the cathode layer treated in the first step at a speed of 2000 revolutions per minute for 60 seconds. After drying, the formed film has a thickness of 30 nm.

[0063] Third step, deposition of the active layer on the cathode modification layer

[0064] According to the mass ratio of the binary component film as P3HT:PC 61BM = 12:10, preparing P3HT at 12 mg / ml and PC at 10 mg / ml 61 The solvent of BM is a mixed solution of 1,2-dichlorobenzene. It is spin-coated onto the cathode modification layer deposited in the second step at a speed of 1000 revolutions per minute for 30 seconds. The thickness of the formed two-component thin film is 80 nm, and then it is placed in the air for 200 - 1200 seconds;

[0065] Fourth step, depositing an anode modification layer on the active layer

[0066] Put the intermediate product with the active layer deposited in the third step into a vacuum coating machine. The vacuum coating machine is pumped to a background vacuum of 4×10 -4 Pa, and Mo3 is deposited as the anode modification layer on the active layer deposited in the third step by thermal evaporation with a thickness of 5 nm.

[0067] Fifth step, depositing an n-type doping layer on the anode modification layer

[0068] The vacuum coating machine is pumped to a background vacuum of 4×10 -4 Pa, and the BCP crucible is heated by thermal evaporation until the evaporation rate of BCP is The Yb crucible is heated until the evaporation rate of Yb is Then the shutter is opened, and BCP doped with Yb is deposited as the n-type doping layer on the anode modification layer deposited in the fourth step with a thickness of 5 nm, and its mass ratio is BCP:Yb = 100:4;

[0069] Sixth step, depositing an anode layer on the n-type doping layer

[0070] In the vacuum coating machine, the vacuum coating machine is pumped to a background vacuum of 4×10 -4 Pa, and an Al thin film is deposited as the anode layer on the n-type doping layer deposited in the fifth step by thermal evaporation with a thickness of 100 nm and a deposition rate of Take out this final product from the vacuum coating machine.

[0071] Thus, the above-mentioned organic solar cell using a composite anode modification layer is finally prepared, which is an organic solar cell using a composite anode modification layer composed of an anode modification layer and an n-type doping layer.

[0072] Comparative Example 1

[0073] Prepare a reverse organic solar cell with a structure of ITO with a thickness of 100 nm / nano ZnO thin film with a thickness of 30 nm / P3HT:PC with a thickness of 80 nm 61 BM = 12:10 / MoO3 with a thickness of 10 nm / Al with a thickness of 100 nm.

[0074] The inverted organic solar cell is composed of an ITO cathode layer with a thickness of 100 nm on a glass substrate, a nano-ZnO thin film cathode modification layer with a thickness of 30 nm deposited on the ITO cathode layer, a P3HT:PC 61 BM thin film active layer with a thickness of 80 nm deposited on the nano-ZnO thin film cathode modification layer, a MoO3 thin film cathode modification layer with a thickness of 10 nm deposited on the P3HT:PC 61 BM thin film active layer, and an Al anode layer with a thickness of 100 nm deposited on the MoO3 thin film cathode modification layer.

[0075] The preparation method of the inverted solar cell is as follows:

[0076] Except for not requiring the "fifth step", the other process steps are the same as those in Example 1.

[0077] Thus, the above-mentioned inverted organic solar cell is finally prepared, which is an inverted organic solar cell with a single anode modification layer.

[0078] Assume that the organic solar cell using the composite anode modification layer of the present invention prepared in Example 1 is Device A, and the existing inverted organic solar cell prepared in Comparative Example 1 is Device B.

[0079] Under the irradiation of AM 1.5G simulated sunlight with an optical intensity of 100 mW / cm 2 , the photocurrent curves of Device A and Device B are tested. Figure 2 Among them, the hollow circle dot curve is the photocurrent curve of Device A, and the solid square dot curve is the photocurrent curve of Device B.

[0080] From Figure 2 The photovoltaic performance parameters of Device A can be obtained: the open-circuit voltage is 0.56 V, the short-circuit current is 8.15 mA / cm², the energy conversion efficiency is 2.45%, and the fill factor is 53.7%; the photovoltaic performance parameters of Device B: the open-circuit voltage is 0.55 V, the short-circuit current is 8.22 mA / cm², the energy conversion efficiency is 2.09%, and the fill factor is 47.1%. It can be seen that the device efficiency of the composite anode modification layer of the present invention is about 20% higher than that of the existing single anode modification layer, and the fill factor is also about 10% higher.

[0081] Example 2

[0082] Prepare a structure of ITO with a thickness of 100 nm / nano-ZnO thin film with a thickness of 30 nm / PTB7-Th:PC with a thickness of 120 nm 71An organic solar cell using a composite anode modification layer with BM = 10:15 / MoO3 with a thickness of 5 nm / Bphen:Yb with a thickness of 5 nm / Al with a thickness of 100 nm.

[0083] The organic solar cell using the composite anode modification layer consists of an ITO cathode layer with a thickness of 100 nm on a glass substrate, a nano-ZnO thin film cathode modification layer with a thickness of 30 nm deposited on the ITO cathode layer, and a PTB7-Th:PC with a thickness of 120 nm deposited on the nano-ZnO thin film cathode modification layer 71 BM thin film active layer, and a MoO3 thin film cathode modification layer with a thickness of 5 nm deposited on the PTB7-Th:PC 71 BM thin film active layer, a Bphen:Yb thin film n-type doping layer with a thickness of 5 nm deposited on the MoO3 thin film cathode modification layer, and an Al anode layer with a thickness of 100 nm deposited on the Bphen:Yb thin film n-type doping layer, forming an organic solar cell using a composite anode modification layer.

[0084] The preparation method of the above-mentioned organic solar cell using a composite anode modification layer is as follows:

[0085] First step, treatment of the ITO cathode layer on the substrate

[0086] Same as Example 1;

[0087] Second step, deposition of the cathode modification layer on the cathode layer

[0088] Same as Example 1.

[0089] Third step, deposition of the active layer on the cathode modification layer

[0090] According to the mass ratio of the two-component thin film of PTB7-Th:PC 71 BM = 10:15, prepare a mixed solution of 10 mg / ml of PTB7-Th and 15 mg / ml of PC 71 BM with 1,2-dichlorobenzene as the solvent, spin-coat it on the cathode modification layer deposited in the second step at a speed of 1000 revolutions per minute for 30 seconds, and the thickness of the formed two-component thin film is 120 nm;

[0091] Fourth step, deposition of the anode modification layer on the active layer

[0092] Same as Example 1.

[0093] Fifth step, deposition of the n-type doping layer on the anode modification layer

[0094] The vacuum coating machine is pumped to a background vacuum of 4×10 -4Pa, by thermal evaporation, heat the Bphen crucible until the evaporation rate of Bphen is Heat the Yb crucible until the evaporation rate of Yb is Then open the baffle and deposit Yb-doped Bphen as the n-type doping layer on the anode modification layer deposited in the fourth step, with a thickness of 5 nm and a mass ratio of Bphen:Yb = 100:4;

[0095] Sixth step, deposit the anode layer on the n-type doping layer

[0096] Same as Example 1.

[0097] Thus, the above-mentioned organic solar cell using a composite anode modification layer is obtained, which is an organic solar cell using a composite anode modification layer composed of an anode modification layer and an n-type doping layer.

[0098] Example 3

[0099] Prepare an organic solar cell using a composite anode modification layer with a structure of ITO with a thickness of 100 nm / nano-ZnO thin film with a thickness of 30 nm / PM6:Y6 = 7:8.4 with a thickness of 120 nm / MoO3 with a thickness of 5 nm / TPBi:Yb with a thickness of 5 nm / Al with a thickness of 100 nm.

[0100] The organic solar cell using a composite anode modification layer is composed of a 100-nm-thick ITO cathode layer on a glass substrate, a 30-nm-thick nano-ZnO thin film cathode modification layer deposited on the ITO cathode layer, a 120-nm-thick PM6:Y6 thin film active layer deposited on the nano-ZnO thin film cathode modification layer, a 5-nm-thick MoO3 thin film cathode modification layer deposited on the PM6:Y6 thin film active layer, a 5-nm-thick TPBi:Yb thin film n-type doping layer deposited on the MoO3 thin film cathode modification layer, and a 100-nm-thick Al anode layer deposited on the TPBi:Yb thin film n-type doping layer, which is an organic solar cell using a composite anode modification layer.

[0101] The preparation method of the above-mentioned organic solar cell using a composite anode modification layer is as follows:

[0102] First step, treatment of the ITO cathode layer on the substrate

[0103] Same as Example 1;

[0104] Second step, deposit the cathode modification layer on the cathode layer

[0105] Same as Example 1.

[0106] Third step, deposit the active layer on the cathode modification layer

[0107] According to the mass ratio of the binary component thin film being PM6:Y6 = 7:8.4, a mixed solution of 7 mg / ml of PM6 and 8.4 mg / ml of Y6 with chloroform as the solvent is prepared. At a speed of 3000 revolutions per minute, it is spin-coated onto the cathode modification layer deposited in the second step. The spin-coating time is 50 seconds, and then it is annealed for 5 minutes in a nitrogen atmosphere at an annealing temperature of 100 °C. The thickness of the formed binary component thin film is 120 nm.

[0108] Step 4, deposit an anode modification layer on the active layer

[0109] Same as Example 1.

[0110] Step 5, deposit an n-type doping layer on the anode modification layer

[0111] The vacuum coating machine is pumped to a background vacuum of 4×10 -4 Pa. Using the thermal evaporation method, heat the TPBi crucible until the evaporation rate of TPBi is Heat the Yb crucible until the evaporation rate of Yb is Then open the shutter and deposit Yb-doped TPBi on the anode modification layer deposited in Step 4 as the n-type doping layer with a thickness of 5 nm, and its mass ratio is TPBi:Yb = 100:4;

[0112] Step 6, deposit an anode layer on the n-type doping layer

[0113] Same as Example 1.

[0114] Thus, the above-mentioned organic solar cell using a composite anode modification layer is finally prepared, which is an organic solar cell using a composite anode modification layer composed of an anode modification layer and an n-type doping layer.

[0115] Matters not covered in this invention are well-known technologies.

Claims

1. An organic solar cell using a composite anode modification layer, characterized in that, The components of the solar cell from bottom to top are a glass substrate, a cathode layer, a cathode modification layer, an active layer, an anode modification layer, an n-type doping layer, and an anode layer in sequence; The n-type doping layer deposited on the anode modification layer is one of the following two-component thin films: I. An n-type doped thin film composed of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and ytterbium, with a mass ratio of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline:ytterbium = 100:1 to 100:40; II. An n-type doped thin film composed of 4,7-diphenyl-1,10-phenanthroline and ytterbium, with a mass ratio of 4,7-diphenyl-1,10-phenanthroline:ytterbium = 100:1 to 100:40; III. An n-type doped thin film composed of 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene and ytterbium, with a mass ratio of 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene:ytterbium = 100:1 to 100:40; The material of the cathode layer is a conductive indium tin oxide thin film; The material of the cathode modification layer is nano zinc oxide; The material of the active layer is any one of the following two-component thin films: I. A two-component thin film composed of poly(3-hexylthiophene) and [6,6]-phenyl-C 61 -butyric acid methyl ester, and the mass ratio thereof is poly(3-hexylthiophene):[6,6]-phenyl-C 61 -butyric acid methyl ester = 12:6 to 12:24; II. A two-component thin film composed of poly(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-alt-(4-(2-ethylhexyl-3-fluorothieno[3,4-b]thiophene)-2-carboxylate)) and [6,6]-phenyl-C 71 -butyric acid methyl ester, and the mass ratio thereof is poly(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-alt-(4-(2-ethylhexyl-3-fluorothieno[3,4-b]thiophene)-2-carboxylate)):[6,6]-phenyl-C 71 -butyric acid methyl ester = 10:5 to 10:20; III. A two-component thin film composed of poly([4,8-bis-((2-ethylhexyl)-4-fluoro-2-thienyl)benzo[1,2-b;3,3-b]dithiophene]-alt-[1,3-bis-(thiophen-5-yl)-5,7-bis-(2-ethylhexyl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione]) and 12,13-bis(2-ethylhexyl)-3,9-undeca-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-bis(5,6-difluoro-3-(dicyanomethylene)indene-1-one), and the mass ratio thereof is poly([4,8-bis-((2-ethylhexyl)-4-fluoro-2-thienyl)benzo[1,2-b;3,3-b]dithiophene]-alt-[1,3-bis-(thiophen-5-yl)-5,7-bis-(2-ethylhexyl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione]):12,13-bis(2-ethylhexyl)-3,9-undeca-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-bis(5,6-difluoro-3-(dicyanomethylene)indene-1-one) = 7:3.5 to 7:14; The material of the anode modification layer is molybdenum trioxide; The material of the anode layer deposited on the n-type doping layer is aluminum; The thickness of the described indium tin oxide conductive film is 80~300 nm and the sheet resistance is less than 10 ohms per 4×4 cm 2 Square; The thickness of the cathode modification layer is 20 - 50 nm; the thickness of the active layer is 50 - 500 nm; the thickness of the anode modification layer is 2 - 10 nm; the thickness of the n-type doping layer is 5 - 50 nm; the thickness of the anode layer is 50 - 200 nm; The preparation method of the organic solar cell using a composite anode modification layer, which method comprises the following steps: First step, treatment of the cathode layer on the substrate After cutting the glass substrate covered with the cathode layer, ultrasonically clean it in acetone, ethanol, and deionized water in sequence; Second step, deposition of the cathode modification layer on the cathode layer Spin-coat the nano ZnO solution onto the cathode layer treated in the first step at a speed of 1000 - 3000 revolutions per minute for 50 - 70 seconds to form a cathode modification layer thin film; Among them, the solvent of the nano ZnO solution is ethanol, the concentration is 10 - 30 mg / mL, and the particle size of the nano ZnO particles is 1 - 3 nm; Third step, deposition of the active layer on the cathode modification layer Select any one of the following processes: Ⅰ. According to the mass ratio of the binary component thin film as P3HT:PC 61 BM = 12:6 to 24, P3HT and PC are added to 1,2-dichlorobenzene to form a mixed solution, where the concentration of PC 61 BM is 6 to 24 mg / mL; then it is spin-coated onto the cathode modification layer deposited in the second step at a speed of 800 to 2000 revolutions per minute, and then placed in the atmosphere for 200 to 1200 seconds to form a two-component thin film; 61 ​ Ⅱ. According to the mass ratio of the binary component thin film as PTB7-Th:PC 71 BM = 10:5 to 20, PTB7-Th and PC 71 BM were added to 1,2-dichlorobenzene to form a mixed solution, wherein the concentration of PC 71 BM was 5 to 20 mg / ml; then it was spin-coated onto the cathode modification layer deposited in the second step at a speed of 800 to 2000 revolutions per minute to form a two-component thin film; III. According to the mass ratio of the two-component thin film of PM6:Y6 = 7: 3.5 - 14, add PM6 and Y6 to chloroform to obtain a mixed solution, where the concentration of Y6 is 3.5 - 14 mg / mL; then spin-coat it onto the cathode modification layer deposited in the second step at a speed of 2000 - 5000 revolutions per minute, and then anneal it in a nitrogen atmosphere for 2 - 8 minutes, and the annealing temperature is 90 - 110 °C to form a two-component thin film; Fourth step, deposition of the anode modification layer on the active layer Put the product with the active layer deposited in the third step into a vacuum coating machine; the vacuum coating machine is pumped to a background vacuum of 4×10 -4 Pa, and MoO3 is deposited on the active layer deposited in the third step as an anode modification layer by thermal evaporation; Fifth step, deposition of the n-type doping layer on the anode modification layer Select any one of the following processes: Ⅰ. The vacuum coating machine is pumped to a background vacuum degree of 4×10 -4 Pa. By using the thermal evaporation method, Yb-doped BCP is deposited as an n-type doping layer on the anodic modification layer deposited in the fourth step, with a thickness of 5 - 50 nm and a mass ratio of BCP:Yb = 100:1 - 100:40; Ⅱ. The vacuum coating machine is pumped to a background vacuum of 4×10 -4 Pa. Using the thermal evaporation method, Yb-doped Bphen is further deposited on the anodic modification layer deposited in the fourth step as an n-type doping layer with a thickness of 5-50 nm, and the mass ratio is Bphen:Yb = 100:1-100:40; Ⅲ. The vacuum coating machine is pumped to a background vacuum degree of 4×10 -4 Pa. By using the thermal evaporation method, Yb-doped TPBi is further deposited on the anodic modification layer deposited in the fourth step as the n-type doping layer with a thickness of 5 - 50 nm, and the mass ratio thereof is TPBi:Yb = 100:1 - 100:40; Sixth step, deposition of the anode layer on the n-type doping layer In a vacuum coating machine, the vacuum coating machine is pumped to a background vacuum of 4×10 -4 Pa. Using the thermal evaporation method, an Al film is deposited as an anode layer on the n-type doped layer deposited in the fifth step, with a deposition rate of 10 - 30 Å / s. This final product is taken out of the vacuum coating machine, and the above-mentioned organic solar cell using the composite anode modification layer is finally prepared.

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