CN117050303A - Cathode interface layer materials, cathode interface layer coating fluids and organic photovoltaic modules - Google Patents
Cathode interface layer materials, cathode interface layer coating fluids and organic photovoltaic modules Download PDFInfo
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Abstract
本发明公开了一种阴极界面层材料、阴极界面层涂布液及有机光伏组件，本发明是提供一种由萘四甲酸二酐或苝四甲酸二酐改质成的化合物或聚合物以作为阴极界面层材料，该阴极接口层材料的化学通式上具有哌嗪(piperazine)基团，以使得阴极界面层材料可以用水、甲醇、乙醇、异丙醇或其组合溶解而形成阴极界面层涂布液，并且使得利用该阴极接口层材料所制作的有机光伏组件其具有优良的能量转换效率(PCE)及热稳定性。
The invention discloses a cathode interface layer material, a cathode interface layer coating liquid and an organic photovoltaic module. The invention provides a compound or polymer modified by naphthalene tetracarboxylic dianhydride or perylene tetracarboxylic dianhydride as a Cathode interface layer material, the cathode interface layer material has a piperazine (piperazine) group in its general chemical formula, so that the cathode interface layer material can be dissolved in water, methanol, ethanol, isopropyl alcohol or a combination thereof to form a cathode interface layer coating The liquid is distributed, and the organic photovoltaic module produced using the cathode interface layer material has excellent power conversion efficiency (PCE) and thermal stability.
Description
Technical Field
The invention provides a compound or polymer modified by naphthalene tetracarboxylic dianhydride (naphthalenetetracarboxylic dianhydride, NTCDA) or perylene tetracarboxylic dianhydride (perylenetetracarboxylic dianhydride, PTCDA) as a cathode interface layer material, wherein piperazine (piperazine) groups are arranged on the chemical general formula of the cathode interface layer material, so that the cathode interface layer material can be dissolved with water, methanol, ethanol, isopropanol or a combination thereof to form a cathode interface layer coating solution, and an organic photovoltaic module manufactured by using the cathode interface layer material has excellent energy conversion efficiency (PCE) and thermal stability.
Background
With the evolution of the age, the consumption of energy resources such as coal, petroleum, natural gas and nuclear energy is increasing, and the energy crisis also relatively emerging, so that the solar power generation is developed. Solar power generation is a renewable environment-friendly power generation mode and can reduce environmental pollution. The first generation of solar cells was based on silicon-based (silicon-based) solar cells, which have high photoelectric conversion rates. The second generation solar cell is a thin-film cadmium telluride (CdTe) solar cell, but the toxicity of raw materials and the manufacturing process of the solar cell have great pollution to the environment. Accordingly, the third generation organic solar cells have grown with the implications that include dye sensitized cells (dye-sensitized solar cell, DSSC), nanocrystalline cells or organic photovoltaic modules (organic photovoltaic, OPV). Compared with inorganic materials which are required to be manufactured by vacuum Cheng Dumo, the organic photovoltaic module can be manufactured by dip coating, spin coating, slit coating, screen printing, ink-jet printing and the like, so that the economic benefits of low cost and mass production are easier to realize.
Currently, organic photovoltaic modules are produced in the industry by adopting a trans-structure, and the cathode interface layer material is usually a metal oxide such as zinc oxide (ZnO), however, the use of metal oxide requires high-temperature sintering (> 150 ℃) to prepare the organic photovoltaic modules, which is disadvantageous for manufacturing large-area flexible substrates. Thus, for example, chinese patent publication No. CN 113582991a (document one) and CN 113666927a (document two) propose, as a cathode interface layer material, naphthalene tetracarboxylic dianhydride (naphthalenetetracarboxylic dianhydride, NTCDA) or a derivative modified from perylene tetracarboxylic dianhydride. However, the derivatives mentioned in the first document have linear terminal groups, and therefore, the organic photovoltaic modules formed therefrom have poor thermal stability; the derivative disclosed in the second literature may have higher thermal stability by introducing imidazole groups at the tail end, but has poor solubility, cannot be dissolved in common methanol, ethanol or isopropanol, and has limited applicability in organic photovoltaic modules because trifluoroethanol is required.
Disclosure of Invention
Therefore, the cathode interfacial layer material is developed and the organic photovoltaic module has excellent performance
P CE and thermal stability, and being soluble in water, methanol, ethanol, isopropanol, or combinations thereof, are the subjects of the present invention.
Accordingly, a first object of the present invention is to provide a cathode interfacial layer material comprising at least one compound represented by the following formula (I) or (II):
wherein,
is->
R 1 Is H or C 1 ～C 12 Linear, branched or cyclic alkyl;
R 2 is C 1 ～C 12 Linear, branched or cyclic alkyl;
x is C l, B r or I;
m is an integer between 1 and 6; the method comprises the steps of,
n is an integer between 2 and 6.
In one embodiment, the cathode interfacial layer material further comprises a polyethyleneimine.
The second object of the present invention is to provide a cathode interfacial layer material, which at least comprises a polymer, wherein the repeating units of the polymer have piperazine (piperazine) groups.
In one embodiment, the polymer comprises at least a structure or repeating unit of formula (III) or formula (IV) below:
in one embodiment, the polymer is formed by copolymerizing the compound with a modifying agent having at least two ethylene oxide groups. Preferably, the method comprises the steps of,is->R 1 Is H; and m is an integer between 1 and 6.
In one embodiment, the polymer is formed by copolymerizing the compound with a polyethyleneimine and a modifier having at least two ethylene oxide groups. Preferably, the method comprises the steps of,is->R 1 Is H; and m is an integer between 1 and 6.
In one embodiment, the polymer is prepared by copolymerizing the compound with polyethyleneimine and the modifying agent, and then reacting with sultone, wherein the modifying agent has at least two ethylene oxide groups. Preferably, the method comprises the steps of,is->R 1 Is H; and m is an integer between 1 and 6.
Accordingly, a third object of the present invention is to provide a cathode interface layer coating liquid containing the aforementioned cathode interface layer material, wherein the solvent of the cathode interface layer coating liquid is water, methanol, ethanol, isopropanol or a combination thereof.
Accordingly, a fourth object of the present invention is to provide an organic photovoltaic module comprising the aforementioned cathode interfacial layer material.
Preferably, the organic photovoltaic module comprises a substrate, a first electrode laminated on the substrate, an electron transport layer laminated on the first electrode, an active layer laminated on the electron transport layer, a hole transport layer laminated on the active layer, and a second electrode laminated on the hole transport layer, wherein the electron transport layer comprises the cathode interface layer material.
Preferably, the organic photovoltaic module comprises a substrate, a first electrode laminated on the substrate, a hole transport layer laminated on the first electrode, an active layer laminated on the hole transport layer, an electron transport layer laminated on the active layer, and a second electrode laminated on the electron transport layer, wherein the electron transport layer comprises the cathode interface layer material.
The invention has the following effects: the compound or polymer modified by naphthalene tetracarboxylic dianhydride or perylene tetracarboxylic dianhydride is used as a cathode interface layer material, piperazine groups in the chemical general formula of the cathode interface layer material are utilized to enable the cathode interface layer material to be dissolved by water, methanol, ethanol, isopropanol or a combination thereof to form a cathode interface layer coating liquid, and an organic photovoltaic module manufactured by utilizing the cathode interface layer material has excellent energy conversion efficiency (PCE) and thermal stability.
Drawings
Other features and advantages of the present invention will become apparent from the following description of the embodiments with reference to the drawings, in which:
FIG. 1 is a schematic cross-sectional view illustrating a first structure of an organic photovoltaic module according to the present invention;
FIG. 2 is a schematic cross-sectional view illustrating a second structure of the organic photovoltaic module according to the present invention; and
Fig. 3 is a graph of energy conversion efficiency, illustrating thermal stability of the organic photovoltaic modules of application comparative example 2 and application example 4, respectively.
Detailed Description
Examples 1 to 11 below are cathode interfacial layer materials of the present invention.
< preparation examples 1 to 10 and coating liquids, examples 1 to 5 and 10 were compounds >.
Preparation example 1 and coating liquid:
compound 1:3,4,9, 10-perylene tetracarboxylic dianhydride (1.0 g) and N-aminoethylpiperazine (1.3 g) were placed in reaction bottles, respectively, and dimethylformamide (30 mL) was added thereto and stirred under a nitrogen system, followed by continuous heating at 90℃for 16 to 18 hours. Cooling after the reaction is finished, pouring the mixture into acetone for precipitation, filtering and purifying, and repeating until filtrate is clear, thus obtaining a dark green solid, namely the example 1. Further, when example 1 was diluted with pure water or methanol, and then the pH was adjusted to 6 to 7 with acetic acid, a diluted solution having a concentration of 0.05wt% was obtained as the coating solution of example 1, and was used for producing a cathode interface layer (electron transport layer) to be described later.
Preparation example 2 and coating liquid:
a reaction flask was charged with the dark green solid example 1 (0.5 g) and 1, 4-butane sultone (0.67 g), methanol (10 mL) was added and stirred under nitrogen, and heating was continued at 70℃for 16-18 hr. And (3) after the reaction is cooled, carrying out suction filtration and purification on the toluene precipitation solid, and finally washing the solid with acetone, carrying out suction filtration and drying to obtain the black solid example 2. Further, when example 2 was diluted with pure water or methanol, and then the pH was adjusted to 6 to 7 with acetic acid, a diluted solution having a concentration of 0.05wt% was obtained as the coating solution of example 2, and was used for producing a cathode interface layer (electron transport layer) to be described later.
Preparation examples 3 and 4 and coating liquid:
the dark green solid obtained in example 1, example 1 (2 g), was placed in a reaction flask, anhydrous dimethylformamide (40 mL) was added and stirred under a nitrogen system, 60% sodium hydride (0.252 g) was added after cooling to 0 ℃, stirring was performed for 0.5 hours at low temperature, bromoethane (0.744 g) was further added, stirring was performed for 0.5 hours at room temperature, and after completion of the reaction, the solid was precipitated with acetone, filtered and purified, and dried to obtain 1g of black solid, example 3. Example 3 (1 g) was placed in a reaction flask, dimethylformamide (20 mL) was added and stirred under a nitrogen system, and finally bromoethane (1.77 g) was added, and the mixture was stirred at 90 ℃ for 18 hours, and after the reaction was completed and the temperature was lowered, acetone was used to precipitate a solid, which was purified by suction filtration, and dried to obtain 1.6g of black solid example 4. In addition, when example 3 and example 4 were diluted with pure water or methanol, respectively, and then the pH was adjusted to 6 to 7 with acetic acid, the diluted solutions having a concentration of 0.05wt% were obtained as the coating solutions of example 3 and example 4, respectively, and were used for producing a cathode interface layer (electron transport layer) to be described later.
Preparation example 5 and coating liquid:
the solid example 3 (0.5 g) was placed in a reaction flask, and 50% hydrogen peroxide (0.46 g) was added thereto and stirred under a nitrogen system, heated to 100℃and stirred for 16 to 18 hours. And (5) after the reaction is over and cooled, filtering and purifying by using acetone precipitation solids, and drying to obtain black solid example 5. Further, when example 5 was diluted with pure water or methanol, and then the pH was adjusted to 6 to 7 with acetic acid, a diluted solution having a concentration of 0.05wt% was obtained as the coating solution of example 5, and was used for producing a cathode interface layer (electron transport layer) to be described later.
< preparation example 6 and coating liquid, example 6 was a mixture of compound types >.
Preparation example 6 and coating liquid:
example 6 is a mixture comprising dark green solid example 1 and polyethylenimine, example 1 does not react chemically with polyethylenimine, branched polyethylenimine (branched polyethylenimine, b-PEI) is employed, and the branched polyethylenimine is prepared from 33% of primary, secondary and tertiary amines: 41%:26% of amine groups, for example, has a weight average molecular weight of about 25000 g/mol.S. igma-Aldrich, product number: 408727,CA S Numb er:9002-98-6. Firstly, adding 0.01g of polyethyleneimine into 20g of 2-butanol, stirring and dissolving, and preparing 0.05wt% of polyethyleneimine diluent by using water or methanol; next, the foregoing 0.05% by weight of the polyethylene imine diluent and 0.05% by weight of the coating liquid of example 1 were mixed with stirring at a volume ratio of 1:1 to obtain a coating liquid of example 6.
Preparation example 10 and coating liquid:
compound 2:1,4,5, 8-naphthalene tetracarboxylic dianhydride (1.0 g) and N-aminoethylpiperazine (1.9 g) were placed in reaction bottles, respectively, and dimethylformamide (30 mL) was added thereto and stirred under a nitrogen system, followed by heating at 90℃for 16 to 18 hours. Cooling after the reaction is finished, pouring the mixture into acetone for precipitation, filtering and purifying, and repeating until filtrate is clear, thus obtaining a dark green solid, namely the example 10. Further, when example 10 was diluted with pure water or methanol, and then the pH was adjusted to 6 to 7 with acetic acid, a diluted solution having a concentration of 0.05wt% was obtained as the coating solution of example 10, and was used for producing a cathode interface layer (electron transport layer) to be described later.
< preparation examples 7 to 9 and 11 coating liquids, examples 7 to 9 and 11 were polymers >.
Preparation example 7 and coating liquid:
glycerol diglycidyl ether (0.25 g; modifier) and example 1 (0.20 g) were placed in reaction bottles, respectively, and dimethyl sulfoxide (20 mL) was added thereto and stirred for dissolution. Heating at 80 deg.c for 12-16 hr under nitrogen system. After cooling, example 7 was obtained in the form of a polymer as a brown liquid product. The diluted solution of example 7 was diluted with pure water or methanol, and the pH was adjusted to 6 to 7 with acetic acid to obtain a diluted solution having a concentration of 0.05wt% as the coating solution of example 7, and was used for producing a cathode interface layer (electron transport layer) to be described later.
Preparation example 8 and coating liquid:
polyethyleneimine (1.0 g), glycerol diglycidyl ether (0.25 g; modifier, crosslinker) and example 1 (0.20 g) were placed in reaction bottles, and dimethyl sulfoxide (20 mL) was added thereto and stirred for dissolution. Heating at 80 deg.c for 12-16 hr under nitrogen system. After cooling, brown liquid product example 8 was obtained, and the secondary amine group of example 1 reacted with the primary amine group of polyethyleneimine and the epoxy group on glycerol diglycidyl ether to ring-open polymerize to give polymer type example 8, wherein the polymerization reaction mechanism can be referred to example 7 and taiwan patent No. I740188. The diluted solution of example 8 was diluted with pure water or methanol, and the pH was adjusted to 6 to 7 with acetic acid to obtain a diluted solution having a concentration of 0.05wt% as the coating solution of example 8, which was used for the production of a cathode interface layer (electron transport layer) to be described later.
Preparation example 9 and coating liquid:
the brown liquid, example 8 (23.53 g) and 1, 4-butane sultone (0.15 g; modifier, crosslinker) were placed in a reaction flask and heated at 70℃for 16-18 hr. After cooling, example 9 in which the brown liquid was polymer was obtained, and example 8 in which the two-and three-stage amines were reacted with sultone to form zwitterionic polymer example 9 (see taiwan patent No. I740188). The diluted solution of example 9 was diluted with pure water or methanol, and the pH was adjusted to 6 to 7 with acetic acid to obtain a diluted solution having a concentration of 0.05wt% as the coating solution of example 9, and was used for the production of a cathode interface layer (electron transport layer) to be described later.
Preparation example 11 and coating liquid:
glycerol diglycidyl ether (0.25 g; modifier) and example 10 (0.20 g) were placed in reaction bottles, respectively, and dimethyl sulfoxide (20 mL) was added thereto and dissolved under stirring. Heating at 80 deg.c for 12-16 hr under nitrogen system. After cooling, example 11 was obtained in the form of a polymer as a brown liquid product. The diluted solution of example 11 was diluted with pure water or methanol and then adjusted to pH 6 to 7 with acetic acid to obtain a diluted solution having a concentration of 0.05wt% which was used as a coating solution of example 11 for the production of a cathode interface layer (electron transport layer) to be described later.
The coating liquids of examples 1 to 11 are the cathode interface layer coating liquids of the present invention.
< preparation of comparative examples 1 to 2 and coating liquid, comparative example 1 was a compound, and comparative example 2 was a polymer >.
Comparative example 1 and coating liquid:
the structure of comparative example 1 (PDINO) is illustrated below:
comparative example 1 is a perylene tetracarboxylic dianhydride modified derivative whose terminal group is linear as described in literature. The diluted solution of comparative example 1 was diluted with methanol and then adjusted to pH 6 to 7 with acetic acid, and the diluted solution was used as a coating solution of comparative example 1 for the production of a cathode interface layer (electron transport layer) described later.
Comparative example 2 and coating liquid were prepared:
polyethyleneimine (1.0 g) and glycerol diglycidyl ether (0.25 g; modifier) were placed in reaction bottles, and dimethyl sulfoxide (20 mL) was added thereto and stirred for dissolution. Heating at 80 deg.c for 12-16 hr under nitrogen system. After cooling, comparative example 2, which is a colorless liquid product, was obtained, and comparative example 2 is polyethyleneimine having a zwitterionic group of taiwan patent I740188. The diluted solution of comparative example 2, in which pure water or methanol was added to dilute the solution, and then acetic acid was used to adjust the pH to 6 to 7, was used as a coating solution of comparative example 2, and was used for producing a cathode interface layer (electron transport layer) described later.
< organic photovoltaic Module Structure >
FIG. 1 is a cross-sectional view of a first structure of an organic photovoltaic module used in the present invention. The organic photovoltaic device comprises a substrate 70, a first electrode 80 laminated on the substrate 70, an organic photovoltaic layer 90 laminated on the first electrode 80, and a second electrode 100 laminated on the organic photovoltaic layer 90. The organic photovoltaic layer 90 includes an electron transport layer (cathode interfacial layer) 91 laminated over the first electrode 80, a photoactive layer 92 laminated over the electron transport layer 91, and a hole transport layer (anode interfacial layer) 93 laminated over the photoactive layer 92.
FIG. 2 is a cross-sectional view of a second structure of an organic photovoltaic module used in the present invention. The organic photovoltaic device comprises a substrate 70, a first electrode 80 laminated on the substrate 70, an organic photovoltaic layer 90 laminated on the first electrode 80, and a second electrode 100 laminated on the organic photovoltaic layer 90. The organic photovoltaic layer 90 includes a hole transport layer (anode interfacial layer) 93 laminated over the first electrode 80, a photoactive layer 92 laminated over the hole transport layer 93, and an electron transport layer (cathode interfacial layer) 91 laminated over the photoactive layer 92.
< preparation of photoactive layer solution >
The P-type donor material, the non-fullerene acceptor material and the fullerene acceptor material are mixed according to the weight ratio of 1:1.2:0.2, and then xylene is used as a solvent to prepare a photoactive layer solution. Wherein the P-type donor material has a repeating unit structure represented by the following formula:
the non-fullerene acceptor materials are:
the fullerene acceptor material is as follows:
< preparation of organic photovoltaic Module (OPV, O rganic p ho tovoltai c) >)
Comparative examples 1 to 2 and examples 1, 2, 3, 5, 6, 8 and 9, which are used in table 1 below, were used to prepare the organic photovoltaic modules of the application comparative examples and application examples, wherein the application comparative example 1 was an electron transport layer-free organic photovoltaic module, and the other preparation methods were the same.
Before preparing the organic photovoltaic component, a patterned ITO (indium tin oxide) glass substrate [ having a resistance value of 12 Ω/≡ (omm/square) ] is sequentially cleaned in an ultrasonic vibration tank for 10 minutes by using a cleaning agent, deionized water, acetone and isopropanol, respectively. After the ITO glass substrate is cleaned by ultrasonic vibration, surface treatment is carried out for 30 minutes in an ultraviolet ozone (UV-ozone) cleaner. Wherein the glass substrate is the substrate 70, the ITO is the first electrode 80, and the cathode is the structure of FIG. 1.
The coating solutions of comparative examples 1 to 2 and the coating solutions of examples 1, 2, 3, 5, 6, 8 and 9 were spin-coated on an IT O glass substrate, respectively, and baked at 100 ℃ for 5 minutes under nitrogen to complete the corresponding electron transport layer 91.
The photoactive layer solution was spin-coated on the electron transport layer 91 and baked at 100 ℃ for 10 minutes under nitrogen to form the photoactive layer 92 on the electron transport layer 91.
Then, the mixture is sent into a vacuum cavity to deposit molybdenum trioxide (Mo O) 3 ) About 10nm, so that the hole transport layer 93 is formed on the photoactive layer 92. Next, ag metal (about 100 nm) is deposited as the second electrode 100, i.e., the anode, in the structure of FIG. 1.
< Electrical analysis of organic photovoltaic Module >
The measurement area of the organic photovoltaic module was defined as 0.04cm via the metal shield 2 . Keithley 2400 was used as the power supply and was programmed with Lab-View at an illuminance of 100mW/cm 2 The AM 1.5G simulated sunlight (SAN-EI XE S-40S 3) is used for measuring the electrical property of the organic photovoltaic module under the irradiation of the simulated sunlight and is recorded by a computer program.
< analysis of energy conversion efficiency (PCE) of organic photovoltaic Module >
The following table 1 shows that the electrical properties of the organic photovoltaic modules according to the application examples and the application examples were also different after the electrical property analysis. In table 1, voc represents an open voltage (open voltage), jsc represents a short-circuit current (short-circuit current), FF represents a fill factor (fill factor), and PCE represents energy conversion efficiency (energy conversion efficiency). The open circuit voltage and the short circuit current are the intercept of the voltage-current density curve in the X-axis and the Y-axis, respectively, and when the two values are increased, the efficiency of the organic photovoltaic component is better improved. The fill factor is a value obtained by dividing the area which can be plotted in the curve by the product of the short-circuit current and the open-circuit voltage. When three values of open circuit voltage, short circuit current and fill factor are divided by the irradiated light, energy conversion efficiency is obtained, and the energy conversion efficiency is preferably higher. The thermal stability test shows that the above components are packaged (initial efficiency value is PCE 0 ) Heating at 120deg.C for 10 min, and heating at 140deg.C for 10 min to obtain PCE 1 Thermal stability=pce 1 /PCE 0 。
TABLE 1
From the results of table 1, it can be found that the electrons generated by absorption of the photoactive layer cannot be successfully collected to the cathode without assistance of the electron transport layer (cathode interface layer material) in comparative example 1, so PCE is only 4.6%, which is far lower than those of the other comparative examples and application examples, and thus comparative example 1 is a defective organic photovoltaic module.
Table 1 is prepared as tables 2 and 3, respectively, according to the electron transport layer used in the organic photovoltaic module, in which the cathode interfacial layer material is a compound or a polymer.
Table 2 (cathode interfacial layer material is a compound)
Comparative example 2 an organic photovoltaic module having a PCE of 11.5% was prepared using comparative example 1 as the cathode interfacial layer material, and comparative example 1 was as in the case of the derivatives modified with perylene tetracarboxylic dianhydride as proposed in the literature, the terminal groups of which were linear. Application example 1 the application example 1 was used as a cathode interface layer material, electrons were transferred to the cathode through a suitable energy level to make the organic photovoltaic module PCE reach 14.1%, example 1 was a compound modified with perylene tetracarboxylic dianhydride as a cathode interface layer material, and the cathode interface layer material had piperazine groups in the chemical formula. Next, based on modification of example 1 to example 2 and example 3 by chemical structure so that the energy levels of application example 2 (using example 2) and application example 3 (using example 3) are more in line with electron transfer, the voltage is increased from 0.780V of application example 1 to 0.800V of application example 2 and 0.810V of application example 3, and the pce is optimally increased to 14.6%. In addition, example 6 used in application example 5 was a mixture of example 1 and polyethyleneimine, and the interfacial energy transfer loss was reduced by assisting example 1 with the characteristic of better film forming property of polyethyleneimine polymer, the voltage was increased from 0.780V in application example 1 to 0.810V in application example 5, and the pce was increased from 14.1% to 14.8%.
In addition, comparative example 1 was used as a cathode interface layer material in comparative example 2, and the terminal group of the derivative modified with perylene tetracarboxylic dianhydride as described in literature 1 was linear; however, examples 1 to 3 and 5 to 6 used in application examples 1 to 5 were compounds modified with perylene tetracarboxylic dianhydride as cathode interface layer materials, and piperazine groups having chemical formulas on the cathode interface layer materials were more stable than those of comparative example 1, so that the thermal stability of application examples 1 to 5 was 96.61% to 99.03% higher than that of application example 2, and also refer to the thermal stability test result chart of fig. 3, which illustrates the thermal stability of the organic photovoltaic modules of application examples 2 and 4.
TABLE 3 (cathode interfacial layer material is a polymer)
By using comparative example 3 and comparative example 2 as cathode interfacial layer materials, an organic photovoltaic module having PCE of 14.5% was prepared, and comparative example 2 was polyethyleneimine having zwitterionic groups of taiwan patent No. I740188. Example 8, which is different from comparative example 2, was used in example 6 in that example 8 was modified by polymerization reaction in accordance with example 1, so that the performance of the organic photovoltaic device was greatly improved by example 6, the energy level was more suitable for matching indium tin oxide with the photoactive layer, and the PCE was increased to 15.9%. Example 9, which is used in example 7, differs from example 8 in that example 9 further zwitterionic it through sultone, enhancing electron transfer effect and PCE boosting to 16.7%.
Therefore, as can be seen from the above results, the compounds or polymers modified by perylene tetracarboxylic dianhydride are used as the cathode interface layer material, and the piperazine groups in the chemical formula of the cathode interface layer material are utilized to make the organic photovoltaic module manufactured by the cathode interface layer material have excellent energy conversion efficiency (PCE) and thermal stability.
However, the foregoing is merely illustrative of the present invention and, therefore, it is not intended to limit the scope of the invention, but it is intended to cover modifications and variations within the scope of the invention as defined by the appended claims and their equivalents.
[ symbolic description ]
70: substrate board
80: first electrode
90: organic photovoltaic layer
91: electron transport layer
92: active layer
93: hole transport layer
100: second electrode
Claims (10)
1. A cathode interfacial layer material comprising at least one compound represented by the following formula (I) or (II):
wherein,
is->
R 1 Is H or C 1 ～C 12 Linear, branched or cyclic alkyl;
R 2 is C 1 ～C 12 Linear, branched or cyclic alkyl;
x is Cl, br or I;
m is an integer between 1 and 6; the method comprises the steps of,
n is an integer between 2 and 6.
2. The cathode interface layer material of claim 1, wherein the cathode interface layer material further comprises polyethylenimine.
3. A cathode interfacial layer material comprising at least one polymer comprising at least one structure or repeating unit of formula (III):
4. the cathode interfacial layer material of claim 3, wherein the polymer is formed by copolymerizing a compound with a modifier, the modifier having at least two ethylene oxide groups, the compound being represented by the following formula (I) or (II):
wherein,
is->
R 1 Is H; the method comprises the steps of,
m is an integer between 1 and 6.
5. The cathode interfacial layer material of claim 3, wherein the polymer is formed by copolymerizing a compound, polyethyleneimine, and a modifier, the modifier having at least two ethylene oxide groups, the compound being represented by the following formula (I) or (II):
wherein,
is->
R 1 Is H; the method comprises the steps of,
m is an integer between 1 and 6.
6. The cathode interfacial layer material of claim 3, wherein said polymer is formed by copolymerizing a compound, polyethyleneimine and a modifier, and then reacting with sultone, said modifier having at least two ethylene oxide groups, said compound having the following formula (I) or (II):
wherein,
is->
R 1 Is H; the method comprises the steps of,
m is an integer between 1 and 6.
7. A cathode interface layer coating liquid comprising the cathode interface layer material according to any one of claims 1 to 7, wherein the solvent of the cathode interface layer coating liquid is water, methanol, ethanol, isopropanol or a combination thereof.
8. An organic photovoltaic module comprising the cathode interfacial layer material of any one of claims 1 to 7.
9. The organic photovoltaic device of claim 8, wherein the organic photovoltaic device comprises a substrate, a first electrode layered over the substrate, an electron transport layer layered over the first electrode, an active layer layered over the electron transport layer, a hole transport layer layered over the active layer, and a second electrode layered over the hole transport layer, and the electron transport layer comprises the cathode interfacial layer material.
10. The organic photovoltaic device of claim 8, wherein the organic photovoltaic device comprises a substrate, a first electrode layered over the substrate, a hole transport layer layered over the first electrode, an active layer layered over the hole transport layer, an electron transport layer layered over the active layer, and a second electrode layered over the electron transport layer, and the electron transport layer comprises the cathode interfacial layer material.
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