Composite hole transport layer ink, organic photovoltaic device and manufacturing method and application thereof

Abstract

The invention discloses composite hole transport layer ink, an organic photovoltaic device and a manufacturing method and application of the organic photovoltaic device. The composite hole transport layer ink comprises inorganic carrier transport material particles, a small molecule additive with sulfonyl and a solvent. The composite hole transport layer ink is low in cost, large-area film formation of a solution-method hole transport layer material can be effectively promoted by adding the small molecule additive, meanwhile, the interface interaction between a solution-method hole transport layer and a metal electrode is obviously improved, and the hole transport efficiency is improved. The charge transfer between the metal electrode and the hole transport layer can be greatly improved, and the performance such as the device efficiency of the large-area organic solar cell can be remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of organic semiconductors, and particularly to a composite hole transport layer ink, an organic photovoltaic device, a manufacturing method thereof, and an application thereof. Background Art

[0002] Due to many advantages such as flexibility, light weight, rich colors, and suitability for roll-to-roll processes, organic solar cells have received extensive attention in the field of new-generation photovoltaic cells. With the continuous development of organic semiconductor optoelectronic materials and the continuous development of interface engineering, the photoelectric conversion efficiency of single-junction organic solar cells has exceeded 19%, showing good application prospects.

[0003] A typical organic solar cell is mainly prepared by sandwiching a photoactive layer composed of a blended donor and acceptor between two electrodes (a cathode and an anode) and corresponding interface buffer layers. During the preparation process, each functional layer is deposited layer by layer. Among them, the bottom electrode usually uses a pre-prepared patterned electrode such as ITO or FTO, the electron transport layer is generally formed by metal oxides such as ZnO and TiO2, the photoactive layer is deposited by blending donor and acceptor materials, and finally a hole transport layer made of materials such as MoO3 and nickel oxide and a top electrode made of metal Al are evaporated. In the existing organic solar cell manufacturing process, each of the above functional layers can be processed by solution methods. Based on this, constructing different composite inks can effectively regulate device performance.

[0004] There are a wide variety of hole transport layer inks suitable for solution processing. According to different material types, they can usually be divided into three categories, including: organic hole transport layer materials, such as PEDOT:PSS, CPE-K, etc.; inorganic hole transport layer materials, such as: HMoO x , NiO x etc.; organic / inorganic composite hole transport layer materials, such as PEDOT:PSS / WS2, PANI / Ag, etc. Based on the above different hole transport layer inks, solution preparation of the hole transport layer of organic solar cells can be realized.

[0005] In practical applications, there are certain problems with the above-mentioned solution-processed hole transport layer materials. For example, PEDOT:PSS is costly, and its inherent acidity and hygroscopic properties can reduce the stability of the corresponding organic batteries. Additionally, in the preparation of large-area hole transport layers, the film-forming properties of these solution-processed hole transport layer materials are relatively poor. Moreover, existing hole transport layer materials mainly focus on their own hole transport performance. In organic solar cells, in addition to the properties of each functional layer itself, there are also obvious interfacial effects between the functional layers. For example, in inverted-structure organic solar cells, anode materials such as Al, Ag, and Au are deposited on the hole transport layer, and the interaction between the formed metal / hole transport layer interfaces can also affect the photoelectric conversion efficiency of the battery, but there is currently no effective solution to such problems. Summary of the Invention

[0006] In view of this, the purpose of the present invention is to provide a composite hole transport layer ink, an organic photovoltaic device, its manufacturing method and application, so as to overcome the deficiencies of the prior art.

[0007] To achieve the above purpose, the technical solutions provided by the present invention are as follows:

[0008] The first aspect of the present invention provides a composite hole transport layer ink, which includes inorganic carrier transport material particles, small molecule additives with sulfonyl groups, and a solvent.

[0009] The second aspect of the present invention provides a composite carrier transport layer, which is made from the composite hole transport layer ink.

[0010] The third aspect of the present invention provides a composite carrier transport layer, which includes an inorganic carrier transport material and small molecule additives with sulfonyl groups.

[0011] The fourth aspect of the present invention provides a preparation method for a composite carrier transport layer, which includes: applying the composite hole transport layer ink onto the surface of a substrate to form a film layer, and then removing at least part of the solvent in the film layer, thereby obtaining the composite carrier transport layer.

[0012] The fifth aspect of the present invention provides the use of the composite hole transport layer ink or the composite carrier transport layer in the preparation of organic optoelectronic devices, organic light-emitting semiconductors, or organic photodetectors.

[0013] The sixth aspect of the present invention provides an organic optoelectronic device, which includes a first electrode, a first carrier transport layer, a photoactive layer, a second carrier transport layer, and a second electrode arranged in sequence along a specified direction; wherein, the first carrier transport layer or the second carrier transport layer includes the composite carrier transport layer.

[0014] The seventh aspect of the present invention provides a method for fabricating an organic optoelectronic device, comprising the steps of fabricating a first electrode, a first charge transport layer, a photoactive layer, a second charge transport layer, and a second electrode; wherein, the step of fabricating the first charge transport layer or the second charge transport layer comprises: fabricating the composite charge transport layer by using the preparation method of the composite charge transport layer.

[0015] Compared with the prior art, the present invention introduces a small molecule additive with a sulfonyl group into the inorganic hole transport layer ink system to construct a composite hole transport layer ink. This composite hole transport layer ink has a low cost, and by adding the aforementioned small molecule additive, it can effectively promote the large-area film formation of the solution-processed hole transport layer material. At the same time, the sulfonyl group in the small molecule additive provides nucleation sites for the initial deposition of the evaporated metal electrode, improves the interfacial interaction between the solution-processed hole transport layer and the metal electrode, enhances the charge transport between the electrode and the hole transport layer, and improves the performance of large-area organic solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0017] Figure 1(a) shows the diiodomethane (DIM) contact angle of the composite hole transport layer film in Comparative Example 1;

[0018] Figure 1(b) shows the water contact angle of the composite hole transport layer film in Comparative Example 1;

[0019] Figure 1(c) shows the diiodomethane (DIM) contact angle of the composite hole transport layer film in Example 1;

[0020] Figure 1(d) shows the water contact angle of the composite hole transport layer film in Example 1;

[0021] Figure 1(e) shows the diiodomethane (DIM) contact angle of the composite hole transport layer film in Example 2;

[0022] Figure 1(f) shows the water contact angle of the composite hole transport layer film in Example 2;

[0023] Figure 1(g) shows the diiodomethane (DIM) contact angle of the composite hole transport layer film in Example 3;

[0024] Figure 1(h) shows the water contact angle of the composite hole transport layer film in Example 3;

[0025] Figure 2(a) is the topographical map of the ultra-thin metal Al (1 nm) on the composite hole transport layer in Comparative Example 1;

[0026] Figure 2(b) is the topographical map of the ultra-thin metal A1 (1 nm) on the composite hole transport layer in Example 3;

[0027] Figure 3 are the J-V curves of the composite hole transport layer films in Comparative Example 1 and Comparative Example 2;

[0028] Figure 4 are the J-V curves of the 1 cm 2 organic solar cells in Comparative Example 1 and Comparative Example 2; Detailed implementation manners

[0029] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

[0030] In each diagram of the present invention, for the convenience of illustration, the dimensions of some structures or parts are enlarged relative to other structures or parts. Therefore, it is only used to illustrate the basic structure of the subject matter of the present invention.

[0031] Spatial relative position terms such as "upper", "lower", "left", "right", etc. used herein are for the purpose of facilitating description of the relationship between one unit or feature and another unit or feature as shown in the accompanying drawings. The spatial relative position terms may be intended to include different orientations of the device in use or operation other than the orientation shown in the figures. For example, if the device in the figure is flipped, the unit described as being "above" other units or features will be located "below" other units or features. Therefore, the exemplary term "above" can encompass both the upper and lower orientations. The device may be oriented in other ways (rotated 90° or other orientations), and the spatially related descriptive terms used herein are interpreted accordingly.

[0032] A composite hole transport layer ink provided by some embodiments of the present invention includes inorganic carrier transport material particles, small molecule additives having sulfonyl groups, and a solvent.

[0033] In one embodiment, the small molecule additive further has at least one or more functional groups among carboxyl group, amino group, hydroxyl group, and halogen atom.

[0034] In one embodiment, the relative molecular weight of the small molecule additive is less than 500.

[0035] In one embodiment, the structural formula of the small molecule additive is R1-R2, where R1 is at least selected from substituted or unsubstituted aryl or substituted or unsubstituted alkyl, and R2 includes a sulfonyl group or a sulfonyl group and one or more of the functional groups.

[0036] In one embodiment, the small molecule additive includes a combination of one or more of the following compounds;

[0037]

[0038] In one embodiment, the sulfonyl group is a fluorosulfonyl group. Compared with the chlorosulfonyl group, the fluorine atom has a stronger electronegativity, the electron cloud on the fluorine atom is more dense, the electron cloud is biased towards the fluorine atom, and the coordination ability between the negatively charged fluorine atom and the metal atom is stronger.

[0039] In one embodiment, the inorganic carrier transport material particles include at least one of metal oxide particles and polyoxometalate particles.

[0040] In one embodiment, the metal oxide particles include nickel oxide (NiO x ), molybdenum oxide (MoO 3-x ), copper oxide (CuO x ), tungsten oxide (WO 3-x ), vanadium oxide (V2O 5-x ) or a combination of one or more of them, and is not limited thereto.

[0041] In one embodiment, the polyoxometalate particles include a combination of one or more of molybdic acid and vanadic acid, and is not limited thereto.

[0042] In one embodiment, the particle size of the inorganic carrier transport material particles is 3 nm to 20 nm. Preferably 3 nm to 10 nm. If the particle size of the inorganic carrier transport material particles is greater than this range, it will result in a low film density, thereby affecting the device performance.

[0043] In one embodiment, the mass ratio of the small molecule additive to the inorganic carrier transport material particles is (1% to 10%)∶1. Preferably 5%∶1. If the content of the small molecule additive is lower than this range, the effect of promoting film formation is not significant, and the number of nucleation sites provided for the initial deposition of the evaporated metal electrode is small; if the content of the small molecule additive is too high, the device performance will be reduced.

[0044] In one embodiment, the composite hole transport layer ink contains 3 to 20 g / L of inorganic carrier transport material particles.

[0045] In one embodiment, the solvent includes one or a combination of more of water, methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether, and is not limited thereto.

[0046] A method for preparing the composite hole transport layer ink provided by some embodiments of the present invention includes: uniformly mixing inorganic carrier transport material particles, small molecule additives having a sulfonyl group, and a solvent.

[0047] Exemplarily, the inorganic carrier transport material particles can be first uniformly dispersed in the solvent to form an inorganic hole transport layer ink, and then the small molecule additives are added to the inorganic hole transport layer ink, and after uniform mixing, the composite hole transport layer ink is obtained.

[0048] The composite hole transport layer ink provided by the above embodiments of the present invention has simple components, low cost, is easy to fabricate, and does not require complex post-treatment processes. Among them, by introducing small molecule additives having a sulfonyl group, the film-forming property of the solution-processed hole transport layer can be significantly improved, the quality of the large-area hole transport layer film can be improved, and at the same time, sites can be provided for the deposition of metal electrodes, promoting charge transport at the hole transport layer / metal electrode interface.

[0049] A composite carrier transport layer provided by some embodiments of the present invention is made of the composite hole transport layer ink.

[0050] Furthermore, the composite carrier transport layer includes an inorganic carrier transport material and a small molecule additive having a sulfonyl group.

[0051] The inorganic carrier transport material and the small molecule additive having a sulfonyl group coexist in a chemical bonding or physical blending manner.

[0052] Among them, the type and specific molecular structure of the small molecule additive are as described above, and will not be elaborated here.

[0053] In one embodiment, the inorganic carrier transport material includes metal oxides, such as NiO x , MoO 3-x , CuO x , WO 3-x , V2O 5-x or a combination of one or more of them.

[0054] In one embodiment, the inorganic carrier transport material includes polyoxometalate particles, such as a combination of one or more of hydrogen molybdate and hydrogen vanadate, and is not limited thereto.

[0055] In one embodiment, the mass ratio of the small molecule additive to the inorganic carrier transport material is (1% - 10%) : 1. Preferably, it is 5% : 1. If the content of the small molecule additive is lower than this range, the effect of promoting film formation is not significant, and fewer nucleation sites are provided for the initial deposition of the evaporated metal electrode; if the content of the small molecule additive is too high, it will lead to a decrease in device performance.

[0056] In one embodiment, the small molecule additive is uniformly distributed on the surface and inside of the composite carrier transport layer.

[0057] Exemplarily, the composite carrier transport layer has a layered structure formed by the aggregation of a plurality of inorganic carrier transport material particles, and the small molecule additive is uniformly distributed on the surface and inside of the layered structure.

[0058] A method for preparing a composite carrier transport layer provided by some embodiments of the present invention includes: applying the composite hole transport layer ink on the surface of a substrate to form a film layer, and then removing at least part of the solvent in the film layer, thereby obtaining the composite carrier transport layer.

[0059] In one embodiment, the preparation method further includes: annealing the film layer at 50 - 100 °C for 1 - 10 min to obtain the composite carrier transport layer. The annealing treatment is carried out, for example, in a glove box. The annealing treatment is carried out, for example, in an air atmosphere.

[0060] Some embodiments of the present invention provide the use of the composite hole transport layer ink or the composite carrier transport layer in the preparation of organic optoelectronic devices. The organic optoelectronic devices include, but are not limited to, organic photovoltaic devices, organic light-emitting devices (such as OLEDs), organic photodetectors, etc.

[0061] Some embodiments of the present invention provide an organic optoelectronic device, including a first electrode, a first carrier transport layer, a photoactive layer, a second carrier transport layer, and a second electrode sequentially arranged along a specified direction; the first carrier transport layer or the second carrier transport layer includes the composite carrier transport layer.

[0062] In one embodiment, the organic optoelectronic device is an organic photovoltaic device, and the first carrier transport layer is a hole transport layer, and the hole transport layer includes the composite carrier transport layer.

[0063] In one embodiment, the second electrode is a metal electrode, and the second electrode is directly electrically combined with the composite carrier transport layer.

[0064] Some embodiments of the present invention provide a method for fabricating an organic optoelectronic device, including the steps of fabricating a first electrode, a first charge carrier transport layer, a photoactive layer, a second charge carrier transport layer, and a second electrode; wherein, the step of fabricating the first charge carrier transport layer or the second charge carrier transport layer includes: fabricating the composite charge carrier transport layer by using the preparation method of the composite charge carrier transport layer.

[0065] In one embodiment, the first charge carrier transport layer and the second charge carrier transport layer are an electron transport layer and a hole transport layer respectively, and the hole transport layer includes the composite charge carrier transport layer; and, the fabrication method specifically includes:

[0066] First, perform the step of fabricating the second charge carrier transport layer,

[0067] After that, perform the step of fabricating the second electrode, including: forming the second electrode on the composite charge carrier transport layer by using a metal evaporation method.

[0068] Furthermore, the organic optoelectronic device is an organic solar cell.

[0069] Generally, according to the different structures of organic solar cells, they are divided into: normal structure and inverted structure organic solar cells. In these two structures, the bottom electrode usually uses a pre-prepared patterned electrode such as ITO or FTO, the electron transport layer usually uses materials such as ZnO and PFN-Br, the photoactive layer is co-deposited by donor-acceptor materials, the hole transport layer is deposited by materials such as MoO3 and PEDOT∶PSS, and finally the top electrode made of materials such as metal Al and Ag is deposited. In the commercialization process of organic solar cells, the large-area fabrication of the cells is a basic requirement. Compared with small-area organic solar cells, due to the area amplification effect of large-area organic solar cells, the defects in each functional layer increase, and the interfaces between each functional layer also increase, and the loss of charge transport at the interfaces of each functional layer also increases, thereby resulting in a low fill factor FF of the organic solar cell and a reduction in the efficiency of the device.

[0070] In the organic solar cell provided by the above embodiments of the present invention, by using the composite hole transport layer ink to form the hole transport layer, not only can the large-area film formation of the hole transport layer be realized, but also the interface performance between the hole transport layer and the metal electrode can be regulated, effectively improving the charge transport property at the interface between the hole transport layer and the metal electrode, greatly increasing the fill factor FF of the large-area organic solar cell, and thus significantly improving the device efficiency.

[0071] The technical solution of the present invention will be further described below in conjunction with several embodiments. Unless otherwise specified, the raw materials, detection reagents, production equipment, detection equipment, etc. used in the following embodiments can be purchased from the market, and the corresponding detection methods, etc. are also commonly used in the art.

[0072] Example 1

[0073] A composite hole transport layer ink provided in this embodiment contains approximately 10 mg of molybdenum oxide particles, approximately 0.5 mg of benzenesulfonyl fluoride, and approximately 1 mL of ethanol solvent. The molybdenum oxide particles have a particle size of approximately 5 nm, and the structural formula of benzenesulfonyl fluoride is as follows:

[0074]

[0075] This composite hole transport layer ink can be prepared by the following method, including: at room temperature, first uniformly disperse the molybdenum oxide particles in the ethanol solvent to form an inorganic hole transport layer ink, and then add benzenesulfonyl fluoride into the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0076] A method for preparing an organic solar cell using this composite hole transport layer ink includes the following steps:

[0077] First, successively use detergent, deionized water, acetone, and isopropanol to ultrasonically clean the substrate composed of a transparent substrate and an indium tin oxide (ITO) transparent conductive bottom electrode. The cleaning time for each time is 30 min. After drying the substrate with nitrogen, then treat the substrate with a UVO ozone cleaner for 30 min;

[0078] Preparation of the electron transport layer on the bottom electrode: Spin-coat an ethanol dispersion of ZnO nanoparticles on the bottom electrode to form a zinc oxide thin film with a thickness of 30 nm. The spin-coating speed is 3000 rpm, and it is dried at a temperature of 130 °C for 15 min;

[0079] Preparation of the organic active layer: Dissolve the electron donor PM6 and the electron acceptor L8-BO in chloroform according to a mass percentage of 1:1.2, stir for 1 h to form a uniform mixed solution with a solute concentration of 15.4 mg / L. Then add DIO with a volume fraction of 0.25% of the volume of chloroform to the uniform mixed solution, stir for 0.5 h, and then spin-coat the mixed solution on the surface of the electron transport layer to obtain an organic active layer with a thickness of approximately 120 nm. Then, it is annealed at 100 °C for 10 min;

[0080] Preparation of hole transport layer: The hole transport layer was prepared using the above-mentioned composite hole transport layer ink. Among them, the concentration of molybdenum oxide ink was 10 mg / mL. The composite ink was spin-coated on the organic active layer at a rotation speed of 3000 rpm, and then annealed at 120 °C for 10 min to obtain a hole transport layer with a thickness of 10 nm;

[0081] Preparation of top electrode: By means of vacuum evaporation, a 200-nm-thick aluminum layer was evaporated on the hole transport layer; thus, the PM6:L8-BO organic solar cell was obtained.

[0082] The area of the finally prepared organic solar cell in this example was 1 cm 2 , named Product 1. The device performance is shown in Table 2.

[0083] The diiodomethane (DIM) contact angle and water contact angle of the composite hole transport layer film prepared in this example are shown in Figure 1(c) and Figure 1(d) respectively. The surface energy of the composite hole transport layer film is shown in Table 1. It can be seen that the introduction of the sulfonyl small molecule additive increases the surface energy of the composite hole transport layer film. This result is beneficial to the deposition of the metal electrode.

[0084] Example 2

[0085] A composite hole transport layer ink provided in this example contains about 10 mg of molybdenum oxide particles, about 0.5 mg of benzenesulfonyl chloride and 1 mL of solvent ethanol. Among them, the molybdenum oxide is the same as that in Example 1, and the structural formula of benzenesulfonyl chloride is:

[0086]

[0087] This composite hole transport layer ink can be prepared by the following method, including: under room temperature conditions, first uniformly disperse the molybdenum oxide particles in the solvent ethanol to form an inorganic hole transport layer ink, and then add benzenesulfonyl chloride to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0088] The difference between the preparation method of the organic solar cell using this composite hole transport layer ink provided in this example and that in Example 1 is only that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this example, and the others are the same as those in Example 1.

[0089] The area of the finally prepared organic solar cell in this example was 1 cm 2 , named Product 2. The device performance is shown in Table 2.

[0090] The diiodomethane (DIM) contact angle and water contact angle of the composite hole transport layer film prepared in this example are shown in Figures 1(e) and 1(f) respectively. The surface energy of the composite hole transport layer film is shown in Table 1. It can be seen that the introduction of the sulfonyl small molecule additive increases the surface energy of the composite hole transport layer film. This result is beneficial to the deposition of the metal electrode.

[0091] Example 3

[0092] A composite hole transport layer ink provided in this example contains about 10 mg of molybdenum oxide particles, about 0.5 mg by weight of m-benzenedisulfonyl chloride, and 1 mL of isopropyl alcohol solvent. Among them, the molybdenum oxide particles are the same as those in Example 1, and the structural formula of m-benzenedisulfonyl chloride is as follows:

[0093]

[0094] This composite hole transport layer ink can be prepared by the following method, including: at room temperature, first uniformly disperse the molybdenum oxide particles in the isopropyl alcohol solvent to form an inorganic hole transport layer ink, and then add benzenesulfonyl fluoride to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0095] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this example, and the others are the same as those in Example 1.

[0096] The area of the organic solar cell finally prepared in this example is 1 cm 2 , named Product 3. The device performance is shown in Table 2

[0097] The diiodomethane (DIM) contact angle and water contact angle of the composite hole transport layer film prepared in this example are shown in Figures 1(g) and 1(h) respectively. The surface energy of the composite hole transport layer film is shown in Table 1. It can be seen that the introduction of the sulfonyl small molecule additive increases the surface energy of the composite hole transport layer film. This result is beneficial to the deposition of the metal electrode.

[0098] Figure 2(b) is the topographic map of the ultra-thin metal Al (1 nm) on the composite hole transport layer in this example. Compared with Figure 2(a), the metal Al is more likely to form continuous growth on the composite hole transport layer in this example, that is, MoO x : The m-benzenedisulfonyl fluoride composite hole transport layer is beneficial to the growth of the metal.

[0099] Example 4

[0100] A composite hole transport layer ink provided in this embodiment contains 10 mg of molybdenum oxide particles, approximately 0.5 mg of triphenylsulfonyl fluoride, and 1 mL of ethanol solvent. The molybdenum oxide particles are the same as those in Example 1; the structural formula of triphenylsulfonyl fluoride is as follows:

[0101]

[0102] This composite hole transport layer ink can be prepared by the following method, including: under room temperature conditions, first uniformly disperse the vanadium oxide particles in the ethanol solvent to form an inorganic hole transport layer ink, and then add triphenylsulfonyl fluoride to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0103] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this embodiment, and the others are implemented in the same way as in Example 1.

[0104] The area of the organic solar cell finally prepared in this embodiment is 1 cm 2 , named Product 4. The device performance is shown in Table 2.

[0105] Example 5

[0106] A composite hole transport layer ink provided in this embodiment contains approximately 10 mg of nickel oxide particles, 0.25 mg of p-bromosulfonylbenzoic acid, and 1 mL of ethanol solvent. The nickel oxide particles are purchased from Sigma and have a particle size of approximately 10 nm; the structural formula of p-bromosulfonylbenzoic acid is as follows:

[0107]

[0108] This composite hole transport layer ink can be prepared by the following method, including: under room temperature conditions, first uniformly disperse the molybdenum oxide particles in the ethanol solvent to form an inorganic hole transport layer ink, and then add benzenesulfonyl bromide to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0109] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this embodiment, and the others are implemented in the same way as in Example 1.

[0110] The area of the organic solar cell finally prepared in this embodiment is 1 cm 2 , named Product 5. The device performance is shown in Table 2.

[0111] Example 6

[0112] A composite hole transport layer ink provided in this embodiment contains approximately 10 mg of molybdenum oxide particles, 0.5 mg of p-fluorosulfonylbenzoic acid, and 1 mL of ethanol solvent. The molybdenum oxide particles are the same as those in Example 1, with a particle size of approximately 5 nm; the structural formula of p-fluorosulfonylbenzoic acid is as follows:

[0113]

[0114] This composite hole transport layer ink can be prepared by the following method, including: at room temperature, first uniformly disperse the molybdenum oxide particles in the ethanol solvent to form an inorganic hole transport layer ink, and then add fluorosulfonylbenzoic acid to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0115] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this embodiment, and the others are the same as those in Example 1.

[0116] The area of the organic solar cell finally prepared in this embodiment is 1 cm 2 , named Product 6. The device performance is shown in Table 2.

[0117] Example 7

[0118] A composite hole transport layer ink provided in this embodiment contains approximately 10 mg of molybdenum oxide particles, 0.5 mg of fluorosulfonylpropane, and 1 mL of n-butanol solvent. The molybdenum oxide particles are the same as those in Example 1, with a particle size of approximately 5 nm; the structural formula of fluorosulfonylpropane is as follows:

[0119]

[0120] The composite hole transport layer ink can be prepared by the following method, including: at room temperature, first uniformly disperse the molybdenum oxide particles in the n-butanol solvent to form an inorganic hole transport layer ink, and then add fluorosulfonylpropane to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0121] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this embodiment, and the others are the same as those in Example 1.

[0122] The area of the organic solar cell finally prepared in this embodiment is 1 cm 2 , named Product 7. The device performance is shown in Table 2.

[0123] Example 8

[0124] A composite hole transport layer ink provided in this example contains approximately 10 mg of molybdenum oxide particles, 0.5 mg of bromosulfonyl propane, and 1 mL of n-butanol solvent. The molybdenum oxide particles are the same as those in Example 1, and the particle size is approximately 5 nm; the structural formula of bromosulfonyl propane is as follows:

[0125]

[0126] This composite hole transport layer ink can be prepared by the following method, including: at room temperature, first uniformly disperse the molybdenum oxide particles in the n-butanol solvent to form an inorganic hole transport layer ink, and then add bromosulfonyl propane to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0127] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this example, and the others are the same as those in Example 1.

[0128] The area of the organic solar cell finally prepared in this example is 1 cm 2 , named Product 8. The device performance is shown in Table 2.

[0129] Example 9

[0130] A composite hole transport layer ink provided in this example contains approximately 10 mg of molybdenum oxide particles, 0.5 mg of benzenesulfonamide, and 1 mL of n-butanol solvent. The molybdenum oxide particles are the same as those in Example 1, and the particle size is approximately 5 nm; the structural formula of benzenesulfonamide is:

[0131]

[0132] This composite hole transport layer ink can be prepared by the following method, including: at room temperature, first uniformly disperse the molybdenum oxide particles in the n-butanol solvent to form an inorganic hole transport layer ink, and then add benzenesulfonamide to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0133] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this example, and the others are the same as those in Example 1.

[0134] The area of the organic solar cell finally prepared in this example is 1 cm 2 , named Product 9. The device performance is shown in Table 2.

[0135] Example 10

[0136] A composite hole transport layer ink provided in this example contains approximately 10 mg of molybdenum oxide particles, 0.5 mg of methanesulfonyl benzene, and 1 mL of n-butanol solvent. The molybdenum oxide particles are the same as those in Example 1, and the particle size is approximately 5 nm; the structural formula of methanesulfonyl benzene is as follows:

[0137]

[0138] This composite hole transport layer ink can be prepared by the following method, including: at room temperature, first uniformly disperse the molybdenum oxide particles in the n-butanol solvent to form an inorganic hole transport layer ink, and then add methanesulfonyl benzene to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0139] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this example, and the others are the same as those in Example 1.

[0140] The area of the finally prepared organic solar cell in this example is 1 cm 2 , named Product 10. The device performance is shown in Table 2.

[0141] Example 11

[0142] A composite hole transport layer ink provided in this example contains approximately 10 mg of molybdenum oxide particles, 0.5 mg of propylsulfonamide, and 1 mL of n-butanol solvent. The molybdenum oxide particles are the same as those in Example 1, and the particle size is approximately 5 nm; the structural formula of propylsulfonamide is as follows:

[0143]

[0144] This composite hole transport layer ink can be prepared by the following method, including: at room temperature, first uniformly disperse the molybdenum oxide particles in the n-butanol solvent to form an inorganic hole transport layer ink, and then add propylsulfonamide to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0145] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this example, and the others are the same as those in Example 1.

[0146] The area of the finally prepared organic solar cell in this example is 1 cm 2, named Product 11. The device performance is shown in Table 2.

[0147] Example 12

[0148] A composite hole transport layer ink provided in this example contains approximately 10 mg of molybdenum oxide particles, 0.5 mg of 2-fluorosulfonylnaphthalene, and 1 mL of n-butanol solvent. Among them, the molybdenum oxide particles are the same as those in Example 1, with a particle size of approximately 5 nm. The structural formula of 2-fluorosulfonylnaphthalene is as follows:

[0149]

[0150] This composite hole transport layer ink can be prepared by the following method, including: at room temperature, first uniformly disperse the molybdenum oxide particles in the n-butanol solvent to form an inorganic hole transport layer ink, and then add 2-fluorosulfonylnaphthalene to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0151] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this example, and the others are implemented in the same way as in Example 1.

[0152] The area of the organic solar cell finally prepared in this example is 1 cm 2 , named Product 12. The device performance is shown in Table 2.

[0153] Example 13

[0154] A composite hole transport layer ink provided in this example contains approximately 10 mg of molybdenum oxide particles, 0.5 mg of 2,7-bis(fluorosulfonyl)naphthalene, and 1 mL of n-butanol solvent. Among them, the molybdenum oxide particles are the same as those in Example 1, with a particle size of approximately 5 nm; the structural formula of 2,7-bis(fluorosulfonyl)naphthalene is as follows:

[0155]

[0156] This composite hole transport layer ink can be prepared by the following method, including: at room temperature, first uniformly disperse the molybdenum oxide particles in the n-butanol solvent to form an inorganic hole transport layer ink, and then add 2,7-bis(fluorosulfonyl)naphthalene to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0157] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this example, and the others are implemented in the same way as in Example 1.

[0158] The area of the organic solar cell finally obtained in this example is 1 cm 2 , named Product 13. The device performance is shown in Table 2.

[0159] Example 14

[0160] A composite hole transport layer ink provided in this example contains about 10 mg of molybdenum oxide particles, 0.5 mg of fluorosulfonylpropionic acid, and 1 mL of n-butanol solvent. The molybdenum oxide particles are the same as those in Example 1, with a particle size of about 5 nm. The structural formula of fluorosulfonylpropionic acid is as follows:

[0161]

[0162] This composite hole transport layer ink can be prepared by the following method, including: at room temperature, first uniformly disperse the molybdenum oxide particles in the n-butanol solvent to form an inorganic hole transport layer ink, and then add the fluorosulfonylpropionic acid to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0163] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this example, and the others are the same as those in Example 1.

[0164] The area of the organic solar cell finally obtained in this example is 1 cm 2 , named Product 14. The device performance is shown in Table 2.

[0165] Example 15

[0166] A composite hole transport layer ink provided in this example contains about 10 mg of molybdenum oxide particles, 0.5 mg of chlorosulfonylpropionic acid, and 1 mL of n-butanol solvent. The molybdenum oxide particles are the same as those in Example 1, with a particle size of about 5 nm; the structural formula of sulfonylpropionic acid is as follows:

[0167]

[0168] This composite hole transport layer ink can be prepared by the following method, including: at room temperature, first uniformly disperse the molybdenum oxide particles in the n-butanol solvent to form an inorganic hole transport layer ink, and then add the chlorosulfonylpropionic acid to the inorganic hole transport layer ink. After uniform mixing, the composite hole transport layer ink is obtained.

[0169] A method for preparing an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced with the composite hole transport layer ink in this example, and the others are the same as those in Example 1.

[0170] The area of the finally obtained organic solar cell in this embodiment is 1 cm 2 , named Product 15. The device performance is shown in Table 2.

[0171] Example 16

[0172] The difference between this embodiment and Example 1 is only that the composite hole transport layer ink contains about 10 mg of copper oxide particles, about 0.1 mg of benzenesulfonyl fluoride, and about 1 mL of ethanol solvent. The rest is the same as in Example 1, and the device performance obtained is shown in Table 2.

[0173] Example 17

[0174] The difference between this embodiment and Example 1 is only that the composite hole transport layer ink contains about 10 mg of tungsten oxide particles, about 1 mg of benzenesulfonyl fluoride, and about 1 mL of ethanol solvent. The rest is the same as in Example 1, and the obtained device performance is good.

[0175] Example 18

[0176] The difference between this embodiment and Example 1 is only that the composite hole transport layer ink contains about 3 mg of vanadium oxide particles, about 0.3 mg of benzenesulfonyl fluoride, and about 1 mL of ethanol solvent. The rest is the same as in Example 1, and the obtained device performance is good.

[0177] Example 19

[0178] The difference between this embodiment and Example 1 is only that the composite hole transport layer ink contains about 20 mg of nickel oxide particles, about 0.2 mg of benzenesulfonyl fluoride, and about 1 mL of ethanol solvent. The rest is the same as in Example 1, and the obtained device performance is good.

[0179] Comparative Example 1

[0180] A hole transport layer ink provided in this comparative example contains 10 mg of molybdenum oxide particles and 1 mL of ethanol solvent. The molybdenum oxide particles are the same as those in Example 1, and the particle size is about 5 nm.

[0181] This hole transport layer ink can be prepared by the following method, including: dispersing molybdenum oxide particles uniformly in ethanol solvent at room temperature to form an inorganic hole transport layer ink.

[0182] The difference between the preparation method of the organic solar cell prepared using this inorganic hole transport layer ink and that of Example 1 is only that the composite hole transport layer ink in Example 1 is replaced with the inorganic hole transport layer ink in this comparative example, and the others are the same as in Example 1.

[0183] The area of the finally obtained organic solar cell in this comparative example is 1 cm 2, named as Control Product 1. The device performance is shown in Table 2.

[0184] The diiodomethane (DIM) contact angle and water contact angle of the composite hole transport layer thin film prepared in this comparative example are shown in Fig. 1(a) and Fig. 1(b) respectively. The surface energy of the composite hole transport layer thin film is shown in Table 2. It can be seen that the introduction of the sulfonyl small molecule additive increases the surface energy of the composite hole transport layer thin film. This result is beneficial to the deposition of the metal electrode.

[0185] Fig. 2(a) is the topographic image of the ultra-thin metal Al (1 nm) on the composite hole transport layer in Comparative Example 1. Figure 4 is the 1 cm prepared in this comparative example 2 J-V curve of the organic solar cell.

[0186] Comparative Example 2

[0187] A hole transport layer ink provided in this comparative example contains 10 mg of molybdenum oxide particles, 0.5 mg of fluorosulfonyl polyethylene glycol with an average molecular weight of 20,000, and 1 mL of ethanol solvent. The molybdenum oxide particles are the same as those in Example 1, and the particle size is about 5 nm.

[0188] This hole transport layer ink can be prepared by the following method, including: at room temperature, uniformly dispersing the molybdenum oxide particles in the ethanol solvent to form an inorganic hole transport layer ink. Then, adding the fluorosulfonyl polyethylene glycol to the inorganic hole transport layer ink and uniformly mixing to obtain the composite hole transport layer ink.

[0189] A preparation method of an organic solar cell using this composite hole transport layer ink is only different from that in Example 1 in that the composite hole transport layer ink in Example 1 is replaced by the composite hole transport layer ink in this example, and the others are the same as those in Example 1.

[0190] The area of the finally prepared organic solar cell in this comparative example is about 1 cm 2 , named as Control Product 2. The device performance is as described in Table 2.

[0191] Figure 3 are the J-V curves of the composite hole transport layer thin films in Comparative Example 1 and Comparative Example 2. It can be clearly seen from this that the conductivity of the composite hole transport layer thin film in Comparative Example 2 is significantly lower than that of the composite hole transport layer thin film in Example 1, that is, the use of the polymer additive containing sulfonyl will cause the conductivity of the corresponding composite hole transport layer thin film to decrease. Figure 4 is the J-V curve of the 1 cm organic solar cell in this comparative example. This result is consistent with the above conclusion that the use of the polymer additive containing sulfonyl will cause the conductivity of the corresponding 1 cm 2 organic solar cell to decrease. 2Device performance degradation.

[0192] Comparative Example 3

[0193] A hole transport layer treatment method provided in this comparative example, wherein molybdenum oxide particles are first deposited and then treated with p-fluorosulfonylbenzoic acid solution. Among them, the molybdenum oxide particles are the same as those in Example 1 and have a particle size of about 5 nm.

[0194] This comparative example provides a molybdenum oxide hole transport layer ink, and its preparation method includes: at room temperature, uniformly dispersing molybdenum oxide particles in an ethanol solvent to form a molybdenum oxide inorganic hole transport layer ink, and depositing to obtain a hole transport layer thin film. Then, the molybdenum oxide thin film is treated with p-fluorosulfonylbenzoic acid solution.

[0195] A method for preparing an organic solar cell by treating a hole transport layer with p-fluorosulfonylbenzoic acid provided in this comparative example includes the following steps:

[0196] First, sequentially use a detergent, deionized water, acetone, and isopropanol to ultrasonically clean the substrate composed of a transparent substrate and an indium tin oxide (ITO) transparent conductive bottom electrode. The cleaning time for each time is 30 min. After that, the substrate is dried with nitrogen and then treated with a UVO ozone cleaner for 30 min;

[0197] Preparation of the electron transport layer on the bottom electrode: Spin-coat an ethanol dispersion of ZnO nanoparticles on the bottom electrode to form a zinc oxide thin film with a thickness of 30 nm. The spin-coating speed is 3000 rpm, and it is dried at 130 °C for 15 min;

[0198] Preparation of the organic active layer: The organic active layer is composed of an electron donor PM6 and an electron acceptor L8-BO dissolved in chloroform according to a mass percentage of 1:1.2, stirred for 1 h to form a uniform mixed solution with a solute concentration of 15.4 mg / L. Then, 0.25% of the volume fraction of the chloroform volume of DIO is added to the uniform mixed solution, stirred for 0.5 h, and then the mixed solution is spin-coated on the surface of the electron transport layer to obtain an organic active layer with a thickness of about 120 nm, and then annealed at 100 °C for 10 min;

[0199] Preparation of the hole transport layer: Using the above molybdenum oxide hole transport layer ink (the concentration of the molybdenum oxide ink is 10 mg / mL), spin-coat the composite ink on the organic active layer. The spin-coating speed is 3000 rpm, and then annealed at 120 °C for 10 min to obtain a hole transport layer with a thickness of 10 nm; then spin-coat p-fluorosulfonylbenzoic acid on the above hole transport layer, and the spin-coating speed is 3000 rpm to obtain a p-fluorosulfonylbenzoic acid-treated molybdenum oxide hole transport layer;

[0200] Preparation of the top electrode: By means of vacuum evaporation, a layer of aluminum with a thickness of 200 nm was evaporated on the hole transport layer; thus, the PM6:L8-BO organic solar cell was obtained.

[0201] The area of the finally prepared organic solar cell in this comparative example was about 1 cm 2 , named as control product 3. The device performance is shown in Table 2.

[0202] The surface energy of the composite hole transport layer films in Examples 1 to 3 and Comparative Example 1 of the present invention was tested, and the results are shown in Table 1. The device performance in Examples 1 to 15 and Comparative Examples 1 to 3 of the present invention was tested, and the results are shown in Table 2.

[0203] Table 1 Surface energy of different composite hole transport layer films in Examples 1 to 3 and Comparative Example 1

[0204]

[0205]

[0206] Table 2 Photoelectric performance table of 1 cm 2 Composite hole transport layer device

[0207] Group Voc (V) <![CDATA[Jsc (mA / cm 2 )]]> FF (%) PCE (%) Example 1 0.888 23.70 79.23 16.68 Example 2 0.884 24.01 78.81 16.72 Example 3 0.884 23.80 78.10 16.43 Example 4 0.887 23.75 78.29 16.49 Example 5 0.883 23.50 76.91 15.96 Example 6 0.877 23.84 77.48 16.20 Example 7 0.882 23.31 78.29 16.10 Example 8 0.877 23.35 77.92 15.96 Example 9 0.872 22.95 77.60 15.53 Example 10 0.873 23.72 76.94 15.93 Example 11 0.878 23.58 77.00 15.94 Example 12 0.879 23.33 78.53 16.10 Example 13 0.875 23.59 77.56 16.01 Example 14 0.867 24.39 79.09 16.72 Example 15 0.856 23.27 80.00 15.94 Example 16 0.833 21.22 68.33 12.08 Comparative Example 1 0.851 23.99 73.98 15.10 Comparative Example 2 0.852 21.42 71.76 13.09 Comparative Example 3 0.827 20.31 66.37 11.15

[0208] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above-described exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be regarded as limiting the claimed rights.

[0209] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A composite hole transport layer ink, comprising inorganic carrier transport material particles and a solvent; characterized in that: The ink further comprises a small molecule additive having a sulfonyl group.

2. The composite hole transport layer ink according to claim 1, characterized in that: The relative molecular weight of the small molecule additive having a sulfonyl group is less than 500; and / or, the small molecule additive further has at least one or more functional groups selected from carboxyl group, amino group, hydroxyl group, and halogen atom.

3. The composite hole transport layer ink according to claim 2, wherein: The structural formula of the small molecule additive is R1-R2, wherein R1 is at least selected from substituted or unsubstituted aryl or substituted or unsubstituted alkyl, and R2 includes a sulfonyl group or a sulfonyl group and one or more of the functional groups.

4. The composite hole transport layer ink according to claim 3, characterized in that: The small molecule additive comprises one or more combinations of the following compounds; 5. The composite hole transport layer ink according to claim 1 or 3, characterized in that: The sulfonyl group is a fluorosulfonyl group.

6. The composite hole transport layer ink according to claim 1, characterized in that: The inorganic carrier transport material particles include at least one of metal oxide particles and polyoxometalate particles; and / or, the particle size of the inorganic carrier transport material particles is 3 nm to 20 nm; and / or, the mass ratio of the small molecule additive to the inorganic carrier transport material particles is (1% - 10%) : 1; and / or, the composite hole transport layer ink contains 3 - 20 g / L of inorganic carrier transport material particles; and / or, the solvent includes one or more combinations of water, methanol, ethanol, isopropanol, ethylene glycol, and ethylene glycol monomethyl ether.

7. The composite hole transport layer ink according to claim 6, characterized in that: The material of the metal oxide particles includes one or more combinations of nickel oxide, molybdenum oxide, copper oxide, tungsten oxide, and vanadium oxide; and / or, the polyoxometalate particles include one or more combinations of hydrogen molybdate and hydrogen vanadate.

8. A composite carrier transport layer comprising an inorganic carrier transport material, characterized in that: The composite carrier transport layer further comprises a small molecule additive having a sulfonyl group.

9. The composite carrier transport layer according to claim 8, wherein: The structural formula of the small molecule additive is R1-R2, wherein R1 is at least selected from substituted or unsubstituted aryl or substituted or unsubstituted alkyl, R2 includes a sulfonyl group or a sulfonyl group and one or more functional groups, and the functional groups include one or more of carboxyl group, amino group, hydroxyl group, and halogen atom; and / or, the relative molecular weight of the small molecule additive having a sulfonyl group is less than 500.

10. The composite carrier transport layer according to claim 9, wherein: The small molecule additive comprises one or more combinations of the following compounds; 11. The composite carrier transport layer according to any one of claims 8-9, characterized in that: The sulfonyl group is a fluorosulfonyl group; and / or, the inorganic carrier transport material includes at least one of metal oxide and polyoxometalate particles; and / or, the mass ratio of the small molecule additive to the inorganic carrier transport material is (1% - 10%) : 1; and / or, the small molecule additive is uniformly distributed on the surface and inside of the composite carrier transport layer.

12. The composite carrier transport layer according to claim 11, wherein: The metal oxide includes one or more combinations of nickel oxide, molybdenum oxide, copper oxide, tungsten oxide, and vanadium oxide; and / or, the polyoxometalate particles include one or more combinations of hydrogen molybdate and hydrogen vanadate.

13. A preparation method of a composite carrier transport layer, characterized in that, Comprising: Applying the composite hole transport layer ink according to any one of claims 1 - 7 to the surface of a substrate to form a film layer, and then removing at least part of the solvent in the film layer, thereby obtaining a composite carrier transport layer.

14. The preparation method according to claim 13, characterized in that: Annealing the film layer at 50 - 100 °C for 1 - 10 min to obtain the composite carrier transport layer. Use of the composite hole transport layer ink according to any one of claims 1-7 or the composite charge transport layer according to any one of claims 8-12 in the preparation of an organic optoelectronic device.

16. An organic optoelectronic device, comprising a first electrode, a first charge transport layer, a photoactive layer, a second charge transport layer, and a second electrode sequentially arranged in a specified direction; characterized in that: The first charge transport layer or the second charge transport layer comprises the composite charge transport layer according to any one of claims 8-12.

17. The organic optoelectronic device according to claim 16, characterized in that: The organic optoelectronic device is an organic photovoltaic device, and the first charge transport layer is a hole transport layer, and the hole transport layer comprises the composite charge transport layer.

18. The organic optoelectronic device according to claim 17, wherein: The second electrode is a metal electrode, and the second electrode is directly electrically combined with the composite charge transport layer.

19. A method for fabricating an organic optoelectronic device, comprising the steps of fabricating a first electrode, a first charge transport layer, a photoactive layer, a second charge transport layer, and a second electrode, characterized in that, The step of fabricating the first charge transport layer or the second charge transport layer comprises: fabricating the composite charge transport layer by the method according to any one of claims 13-14.

20. The manufacturing method according to claim 19, wherein The first charge transport layer and the second charge transport layer are an electron transport layer and a hole transport layer respectively, and the hole transport layer comprises the composite charge transport layer; And, the fabrication method specifically comprises: first performing the step of fabricating the second charge transport layer, and then performing the step of fabricating the second electrode, comprising: forming the second electrode on the composite charge transport layer by a metal evaporation method.

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