Organic solar cell containing primary amine group and pyrene structure, preparation method and application thereof

Abstract

The invention relates to an organic solar cell containing a primary amine group and a pyrene structure, a preparation method and an application thereof. The organic solar cell containing the primary amine group and the pyrene structure comprises a substrate, an anode, a hole transport layer, an active layer, a first electron transport layer and a cathode in sequence from bottom to top, wherein the material of the first electron transport layer is selected from an organic compound containing a primary amine group and a pyrene structure; an organic compound containing a primary amine group and a pyrene structure is introduced as an electron transport layer, so that the efficiency of the cell is improved, and the energy conversion efficiency of the organic solar cell is improved to more than 15%.

Description

Technical Field

[0001] The present invention belongs to the field of organic optoelectronic devices, and particularly relates to an organic solar cell containing a primary amine group and a pyrene structure, a preparation method thereof, and an application thereof. Background Art

[0002] In today's world, with the rapid development of the economy, energy issues have attracted more and more attention. The energy crisis caused by the depletion of fossil fuels and the greenhouse effect caused by burning fossil fuels have posed major challenges to the earth's environment. Solar energy, which accounts for more than 90% of the total energy on the earth, has gradually come into people's view. The characteristics of solar energy, such as wide distribution, green pollution-free, and sustainable, have been favored by many scientists. Solar energy plays a key role in solving serious environmental problems and the energy challenges faced by the world today, and has promoted the rapid development of photovoltaic technology. Organic polymer bulk heterojunction photovoltaic devices are a new type of semiconductor device that has emerged only recently. It combines many excellent characteristics, such as being able to be prepared into flexible, lightweight, and cheaper optoelectronic devices through a simple solution processing method.

[0003] In recent years, non-fullerene-based organic photovoltaic cells have developed rapidly. Organic photovoltaic cells have reached a crossroads towards commercialization. However, organic solar cells still face problems such as too short battery life and not high enough battery energy conversion efficiency. In order to further improve the efficiency and life of organic solar cells, the cathode interface layer can be started with, thereby improving the efficiency and life of organic solar cells. Summary of the Invention

[0004] Therefore, the purpose of the present invention is to provide an organic solar cell containing a primary amine group and a pyrene structure, introducing an organic compound containing a primary amine group and a pyrene structure as an electron transport layer, thereby improving the efficiency of the battery.

[0005] The present invention discloses an organic solar cell containing a primary amine group and a pyrene structure. The organic solar cell containing a primary amine group and a pyrene structure sequentially includes from bottom to top: a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode;

[0006] Wherein, the electron transport layer includes a first electron transport layer, and the material of the first electron transport layer is selected from organic compounds containing a primary amine group and a pyrene structure;

[0007] The organic compound containing a primary amine group and a pyrene structure specifically has the following structure:

[0008]

[0009] R1, R2, R3, and R4 do not exist, or are independently selected from alkyl derivatives and aryl derivatives with a primary amino group as an end group;

[0010] And at least one of R1, R2, R3, and R4 exists;

[0011] All carbon atoms on the alkyl derivative are unsubstituted, or one or more carbon atoms are substituted by one or more of an oxygen atom, an amino group, a sulfone group, a carbonyl group, an aryl group, an alkenyl group, an alkynyl group, an ester group, a cyano group, and a nitro group;

[0012] Or

[0013] All hydrogen atoms on the alkyl derivative are unsubstituted, or one or more hydrogen atoms are substituted by one or more of a halogen, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a nitro group, an aryl group, an alkenyl group, and an alkynyl group;

[0014] The aryl derivative is selected from groups containing one or more benzene ring structures, where all hydrogen atoms on the benzene rings are unsubstituted,

[0015] Or

[0016] One or more hydrogen atoms at any position on one or more benzene rings are substituted by one or more of a halogen, a hydroxyl group, an amino group, a cyano group, a nitro group, an aryl group, an alkenyl group, an alkynyl group, a carboxyl group, an ester group, a cyano group, or a nitro group.

[0017] Furthermore, a second electron transport layer is further included;

[0018] The second electron transport layer is disposed between the first electron transport layer and the cathode;

[0019] Or

[0020] The second electron transport layer is disposed between the active layer and the first electron transport layer.

[0021] Furthermore, the thickness of the second electron transport layer is 2 nm - 50 nm.

[0022] Furthermore, the thickness of the first electron transport layer is 2 nm - 50 nm.

[0023] Furthermore, the material of the second electron transport layer is selected from one or more of PDIN and PDIN derivatives.

[0024] Furthermore, the organic compound containing a primary amine group and a pyrene structure is selected from one of the following structures:

[0025]

[0026] Furthermore, the material of the substrate is selected from one or more of transparent glass, a polyimide (PI) substrate, and a polyester (PET) substrate.

[0027] Furthermore, the material of the anode is selected from ITO (indium tin oxide), and the thickness is 30 - 200 nm.

[0028] Furthermore, the material of the hole transport layer is selected from one or more of PEDOT:PSS, NiOx, and carbazole phosphate-based SAM hole transport materials.

[0029] Furthermore, the material of the active layer is selected from one or more of PBDB-T-F:L8-BO, PBDB-T-F:BTP-eC9, and D18-CI:L8-BO.

[0030] Furthermore, the thickness of the cathode is 80 - 120 nm.

[0031] Furthermore, the material of the cathode is selected from one or more of Ag, Al, and Au.

[0032] The present invention also provides a method for preparing the organic solar cell containing a primary amine group and a pyrene structure, comprising the following steps:

[0033] S1. Coat the anode on the upper surface of the substrate;

[0034] S2. Spin-coat the hole transport layer on the upper surface of the anode and perform annealing treatment;

[0035] S3. Spin-coat the active layer on the upper surface of the hole transport layer by solution method and perform annealing treatment;

[0036] S4. Spin-coat the electron transport layer on the upper surface of the active layer by solution method;

[0037] S5. Prepare the cathode by vacuum evaporation to obtain an organic solar cell containing a primary amine group and a pyrene structure.

[0038] Furthermore, step S4 further includes the following steps:

[0039] Spin-coat a first electron transport layer on the upper surface of the active layer;

[0040] Or

[0041] Spin-coat a second electron transport layer on the upper surface of the active layer, and then spin-coat a first electron transport layer;

[0042] Or

[0043] Spin-coat a first electron transport layer on the upper surface of the active layer, and then spin-coat a second electron transport layer.

[0044] Furthermore, in step S2, the temperature of the annealing treatment is 100 - 150 °C;

[0045] In step S3, the temperature of the annealing treatment is 90 - 120 °C.

[0046] The present invention also provides an application of the organic solar cell containing a primary amine group and a pyrene structure in semiconductors.

[0047] Compared with the prior art, the main advantages of the present invention are as follows:

[0048] By introducing an organic compound containing a primary amine group and a pyrene structure as the electron transport layer, the present invention can effectively extract charges, reduce the energy level difference between interfaces, and improve the efficiency of the battery. In addition, by using the organic compound containing a primary amine group and a pyrene structure and PDIN together as the electron transport layer, not only can the light stability of the solar cell be effectively improved, thus having better beneficial effects in terms of device performance, but also the synergistic effect of using the organic compound containing a primary amine group and a pyrene structure and PDIN together as the electron transport layer can be utilized. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 It is a J-V characteristic curve diagram of the devices of Examples 1 - 3 and Comparative Examples 1 - 2.

[0050] Figure 2 It is a light stability diagram of the devices of Example 1 and Example 3.

[0051] Figure 3 It is a schematic structural diagram of Example 1.

[0052] Figure 4 It is a schematic structural diagram of Example 2.

[0053] Figure 5 It is a schematic structural diagram of Example 3.

[0054] Figure 6 It is a schematic structural diagram of Comparative Example 1.

[0055] Figure 7 It is a schematic structural diagram of Comparative Example 2.

[0056] Figure 8 It is a chemical structure diagram of the polymer donor PM6, the non-fullerene acceptor L8-BO, and TCB.

[0057] Figure 9 It is a chemical structure diagram of PDIN and tetra-(p-aminophenyl)-pyrene (CAS: 1610471-69-6).

[0058] In the figure: 1. Substrate; 2. Anode; 3. Hole transport layer; 4. Active layer; 5. First electron transport layer; 6. Second electron transport layer; 7. Cathode. DETAILED DESCRIPTION OF THE INVENTION

[0059] To more clearly illustrate the technical solutions of the present invention, the following examples are listed. Unless otherwise specified, the raw materials, reactions, and post-treatment means in the examples are common raw materials on the market and technical means well-known to those skilled in the art.

[0060] In the examples of the present invention, unless otherwise mentioned, the preparation steps related to organic solar cells are all carried out by conventional means well-known to those skilled in the art.

[0061] In the examples, the chemical structural diagrams of the polymer donor PM6, non-fullerene acceptor L8-BO, and TCB are as Figure 8 shown; the chemical structural diagrams of PDIN and tetra-(p-aminophenyl)-pyrene (CAS: 1610471-69-6) are as Figure 9 shown.

[0062] Example 1

[0063] An organic solar cell containing a primary amine group and a pyrene structure, with a structure as Figure 3 shown. The organic solar cell containing a primary amine group and a pyrene structure includes, from bottom to top in sequence: a substrate 1 (glass, 2 mm), an anode 2 (ITO, 130 nm), a hole transport layer 3 (PEDOT:PSS, 30 nm), an active layer 4 (PM6:L8-BO, 100 nm), a first electron transport layer 5 (PTAI, 5 nm), and a cathode 7 (Ag, 80 nm);

[0064] The preparation method of the organic solar cell containing a primary amine group and a pyrene structure includes the following steps:

[0065] S1. The glass substrate coated with the ITO anode is successively ultrasonically cleaned with deionized water, isopropanol, deionized water, and isopropanol, dried in an oven, and then placed in a petri dish for standby;

[0066] S2. Using the spin-coating method, PEDOT:PSS is spin-coated on the upper surface of the anode at a speed of 3000 rpm for 30 s, and annealed at 150 °C for 15 min to obtain the hole transport layer;

[0067] S3. The polymer donor material PBDB-T-F (PM6), the acceptor material L8-BO, and the solid additive trichlorobenzene (TCB) are dissolved in a chloroform solvent to obtain a mixed solution, which is then stirred at 50 °C for 6 h and then spin-coated on the upper surface of the hole transport layer and annealed at 100 °C for 10 min to obtain the active layer;

[0068] Among them, in the mixed solution, the total concentration of PM6 and L8-BO is 17 mg / mL, and the concentration of TCB is 10 mg / mL; the mass ratio of PM6 to L8-BO is 1:1.2;

[0069] S4. At a rotational speed of 2000 rpm, the 0.5 mg / mL PTAI solution was spin-coated on the upper surface of the active layer by the solution method to obtain the first electron transport layer;

[0070] Among them, the solvent of the PTAI solution is dimethyl sulfoxide and methanol, and the volume ratio is 1:2;

[0071] S5. Silver was deposited on the upper surface of the first electron transport layer as the cathode by vacuum thermal evaporation deposition method to obtain an organic solar cell containing a primary amine group and a pyrene structure.

[0072] Example 2

[0073] An organic solar cell containing a primary amine group and a pyrene structure, the structure is as Figure 4 shown. The organic solar cell containing a primary amine group and a pyrene structure includes, from bottom to top in sequence: a substrate 1 (glass, 2 mm), an anode 2 (ITO, 130 nm), a hole transport layer 3 (PEDOT:PSS, 30 nm), an active layer 4 (PM6:L8-BO, 100 nm), a first electron transport layer 5 (PTAI, 5 nm), a second electron transport layer 6 (PDIN, 5 nm), and a cathode 7 (Ag, 80 nm);

[0074] The preparation method of the organic solar cell containing a primary amine group and a pyrene structure includes the following steps:

[0075] S1. The glass substrate coated with the ITO anode was ultrasonically cleaned successively with deionized water, isopropanol, deionized water, and isopropanol, dried in an oven, and then placed in a petri dish for standby;

[0076] S2. PEDOT:PSS was spin-coated on the upper surface of the anode at a rotational speed of 3000 rpm by the spin-coating method, spin-coated for 30 s, and annealed at 150 °C for 15 min to obtain the hole transport layer;

[0077] S3. The polymer donor material PBDB-T-F (PM6), the acceptor material L8-BO, and the solid additive trichlorobenzene (TCB) were dissolved in a chloroform solvent to obtain a mixed solution, then stirred at 50 °C for 6 h, and then spin-coated on the upper surface of the hole transport layer and annealed at 100 °C for 10 min to obtain the active layer;

[0078] Among them, in the mixed solution, the total concentration of PM6 and L8-BO is 17 mg / mL, and the concentration of TCB is 10 mg / mL; the mass ratio of PM6 to L8-BO is 1:1.2;

[0079] S4-1. At a rotational speed of 2000 rpm, using the solution method, a 0.5 mg / mL PTAI solution was spin-coated on the upper surface of the active layer to obtain the first electron transport layer;

[0080] Among them, the solvent of the PTAI solution is dimethyl sulfoxide and methanol, and the volume ratio is 1:2;

[0081] S4-2. At a rotational speed of 2000 rpm, a 2 mg / mL PDIN methanol solution was spin-coated on the upper surface of the first electron transport layer to obtain the second electron transport layer;

[0082] S5. Using the vacuum thermal evaporation method, silver was deposited on the upper surface of the second electron transport layer as the cathode to obtain an organic solar cell containing a primary amine group and a pyrene structure.

[0083] Example 3

[0084] An organic solar cell containing a primary amine group and a pyrene structure, the structure is as Figure 5 shown. The organic solar cell containing a primary amine group and a pyrene structure includes, from bottom to top in sequence: a substrate 1 (glass, 2 mm), an anode 2 (ITO, 130 nm), a hole transport layer 3 (PEDOT:PSS, 30 nm), an active layer 4 (PM6:L8-BO, 100 nm), a second electron transport layer 6 (PDIN, 5 nm), a first electron transport layer 5 (PTAI, 5 nm), and a cathode 7 (Ag, 80 nm);

[0085] The preparation method of the organic solar cell containing a primary amine group and a pyrene structure includes the following steps:

[0086] S1. The glass substrate coated with the ITO anode was ultrasonically cleaned successively with deionized water, isopropyl alcohol, deionized water, and isopropyl alcohol, dried in an oven, and then placed in a petri dish for standby;

[0087] S2. Using the spin-coating method, PEDOT:PSS was spin-coated on the upper surface of the anode at a rotational speed of 3000 rpm for 30 s, and annealed at 150 °C for 15 min to obtain the hole transport layer;

[0088] S3. The polymer donor material PBDB-T-F (PM6), the acceptor material L8-BO, and the solid additive trichlorobenzene (TCB) were dissolved in a chloroform solvent to obtain a mixed solution, which was then stirred at 50 °C for 6 h, and then spin-coated on the upper surface of the hole transport layer and annealed at 100 °C for 10 min to obtain the active layer;

[0089] Among them, in the mixed solution, the total concentration of PM6 and L8-BO is 17 mg / mL, and the concentration of TCB is 10 mg / mL; the mass ratio of PM6 to L8-BO is 1:1.2;

[0090] S4-1. Spin-coat a 2 mg / mL PDIN methanol solution on the upper surface of the active layer at a rotational speed of 2000 rpm to obtain the second electron transport layer;

[0091] S4-2. Spin-coat a 0.5 mg / mL PTAI solution on the upper surface of the second electron transport layer by solution method at a rotational speed of 2000 rpm to obtain the first electron transport layer;

[0092] Among them, the solvent of the PTAI solution is dimethyl sulfoxide and methanol, and the volume ratio is 1:2;

[0093] S5. Deposit silver on the upper surface of the second electron transport layer as the cathode by vacuum thermal evaporation to obtain an organic solar cell containing a primary amine group and a pyrene structure.

[0094] Comparative Example 1

[0095] An organic solar cell, the structure of which is as Figure 6 shown. The difference between this comparative example and Example 1 is that the first electron transport layer 5 is removed, and other structures and preparation methods are the same.

[0096] Comparative Example 2

[0097] An organic solar cell, the structure of which is as Figure 7 shown. The difference between this comparative example and Example 1 is that the first electron transport layer 5 (PTAI) is replaced by the second electron transport layer 6 (PDIN), and other structures and preparation methods are the same.

[0098] Comparative Example 3

[0099] An organic solar cell, the structure of which is as Figure 4 shown. The difference between this comparative example and Example 2 is that the material of the first electron transport layer 5 is replaced by sodium 1-pyrenesulfonate (PYS) (CAS: 59323-54-5), and other structures and preparation methods are the same.

[0100] The structural formula of the sodium 1-pyrenesulfonate (PYS) is as shown below.

[0101]

[0102] Test Example 1

[0103] Perform performance tests on the organic solar cells prepared in Examples 1-3 and Comparative Examples 1-3.

[0104] Test method:

[0105] Current-Voltage (I-V) Curve Measurement: Under 1 sun intensity, the forward and reverse current density-voltage (J-V) curves were measured using a computer-controlled Keithley 2400 source meter in the range of -0.2 V to 1.2 V with a scan step of 20 mV and a dwell time of 5 ms at each measurement point.

[0106] Among them, the AM 1.5G spectrum was provided by a solar simulator manufactured by Enlitech Co., Ltd., with a light intensity of 100 mW / cm 2 , and was calibrated by a monocrystalline silicon reference cell (equipped with a KG1 filter, Enlitech) certified by the China General Certification Center.

[0107] External Quantum Efficiency (EQE) Measurement: The external quantum efficiency (EQE) spectrum was measured using a commercial EQE measurement system (model QE-R3011, manufactured by Enlitech Co., Ltd.).

[0108] Table 1 Performance Parameters of the Organic Solar Cells Prepared in Examples 1-3 and Comparative Examples 1-3

[0109]

[0110]

[0111] As can be seen from Table 1, comparing the performance of the organic solar cells prepared with the PTAI electron transport material with that without an electron transport layer, the cell efficiency is significantly improved, with increases in both the open-circuit voltage, short-circuit current, and fill factor. Moreover, by using a combination of a primary amine group-containing and pyrene-structured material and PDIN as the electron transport layer (Examples 2-3), the device efficiency increased to 19%.

[0112] Figure 1 Figs. are the current density-voltage (J-V) diagrams of the organic solar cells prepared in Examples 1-3 and Comparative Examples 1-3. From Figure 1 it can be seen that after introducing PTAI, all the device performance parameters are significantly improved. When using PTA and PDIN as the electron transport layer, as can be seen from Example 2 and Comparative Example 2, the short-circuit current is significantly increased, resulting in an improvement in device performance. In Comparative Example 3, 1-pyrenesulfonate sodium salt (PYS) without a primary amine but containing a sodium sulfonate group was used, and only a PCE efficiency of 11.25% was obtained.

[0113] Figure 2 Figs. are the light stability diagrams of the devices in Example 1 and Example 3. From Figure 2 it can be seen that by introducing PTAI between PDIN and Ag, the light stability of the device is significantly improved, and PTAI effectively enhances the light stability.

[0114] It will be apparent to those skilled in the art that the present invention is not limited to the details of the above-described exemplary embodiments, and that the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention. Therefore, in any regard, 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. Accordingly, all changes that fall within the meaning and scope of the equivalent elements of the claims are intended to be embraced within the present invention.

[0115] In addition, it should be understood that although this specification is described in terms of embodiments, not every embodiment only contains an independent technical solution. This narrative manner 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. An organic solar cell containing a primary amine group and a pyrene structure, characterized in that the organic solar cell containing a primary amine group and a pyrene structure comprises, from bottom to top in sequence: a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode; wherein, the electron transport layer includes a first electron transport layer, and the material of the first electron transport layer is selected from organic compounds containing a primary amine group and a pyrene structure; the organic compound containing a primary amine group and a pyrene structure specifically has the following structure: R1, R2, R3, and R4 do not exist, or are independently selected from alkyl derivatives and aryl derivatives with a primary amino group as the end group; and, at least one of R1, R2, R3, and R4 exists; all carbon atoms on the alkyl derivative are unsubstituted, or one or more carbon atoms are substituted by one or more of oxygen atom, amino group, sulfone group, carbonyl group, aryl group, alkenyl group, alkynyl group, ester group, cyano group, and nitro group; or all hydrogen atoms on the alkyl derivative are unsubstituted, or one or more hydrogen atoms are substituted by one or more of halogen, hydroxyl group, amino group, carboxyl group, cyano group, nitro group, aryl group, alkenyl group, and alkynyl group; the aryl derivative is selected from groups containing one or more benzene ring structures, wherein all hydrogen atoms on the benzene rings are unsubstituted, or one or more hydrogen atoms at any position on one or more benzene rings are substituted by one or more of halogen, hydroxyl group, amino group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group, carboxyl group, ester group, cyano group, or nitro group.

2. The organic solar cell containing a primary amine group and a pyrene structure according to claim 1, wherein It further includes a second electron transport layer; the second electron transport layer is disposed between the first electron transport layer and the cathode; or the second electron transport layer is disposed between the active layer and the first electron transport layer.

3. The organic solar cell containing a primary amine group and a pyrene structure according to claim 2, wherein The material of the second electron transport layer is selected from one or more of PDIN and PDIN derivatives.

4. The organic solar cell containing a primary amine group and a pyrene structure according to claim 1, wherein The organic compound containing a primary amine group and a pyrene structure is selected from one of the following structures:

5. The organic solar cell containing a primary amine group and a pyrene structure according to claim 1, wherein The material of the active layer is selected from one or more of PBDB-T-F:L8-BO, PBDB-T-F:BTP-eC9, and D18-CI:L8-BO.

6. The organic solar cell containing a primary amine group and a pyrene structure according to claim 1, characterized in that, The material of the hole transport layer is selected from one or more of PEDOT:PSS, NiOx, and carbazole phosphate-based SAM hole transport materials.

7. The preparation method of the organic solar cell containing a primary amine group and a pyrene structure according to any one of claims 1-6, characterized in that, It includes the following steps: S1. Coat the anode on the upper surface of the substrate; S2. Spin-coat the hole transport layer on the upper surface of the anode and perform annealing treatment; S3. Spin-coat the active layer on the upper surface of the hole transport layer by solution method and perform annealing treatment; S4. Spin-coat the electron transport layer on the upper surface of the active layer by solution method; S5. Prepare the cathode by vacuum evaporation method to obtain an organic solar cell containing a primary amine group and a pyrene structure.

8. The preparation method of the organic solar cell containing a primary amine group and a pyrene structure according to claim 7, characterized in that step S4 further includes the following steps: Spin-coat the first electron transport layer on the upper surface of the active layer; or Spin-coat the second electron transport layer on the upper surface of the active layer, and then spin-coat the first electron transport layer; or Spin-coat a first electron transport layer on the upper surface of the active layer, and then spin-coat a second electron transport layer.

9. The method for preparing an organic solar cell containing a primary amine group and a pyrene structure according to claim 7, characterized in that In step S2, the temperature of the annealing treatment is 100-150 °C; In step S3, the temperature of the annealing treatment is 90-120 °C.

10. Application of the organic solar cell containing a primary amine group and a pyrene structure according to any one of claims 1-6 in a semiconductor.

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