Composite hole transport material and application thereof
By using composite hole transport materials, the problems of photoelectric conversion efficiency and stability of existing materials have been solved, resulting in more efficient and stable solar cell performance, especially in large-area and flexible devices.
Patent Information
- Application Number
- CN202510748309.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-05
- Publication Date
- 2025-11-07
AI Technical Summary
Existing hole transport layer materials such as PEDOT:PSS suffer from acidity and near-infrared absorption in organic and perovskite solar cells, which reduces photoelectric conversion efficiency and stability. Carbazole-based materials, due to their planar framework structure, result in surface inhomogeneity and poor repeatability.
A composite hole transport material is used, consisting of carbazole phosphate and phenyl phosphate. The material is mixed, dissolved, and spin-coated onto a substrate to form a hole transport layer, thereby improving surface coverage and flexibility.
It improves the energy conversion efficiency, fabrication repeatability, thermal stability, and bending stability of organic and perovskite solar cells, making it suitable for large-area solar cell devices.
Smart Images
Figure CN120916628A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of battery device preparation, in particular to a composite hole transport material and application thereof. BACKGROUND
[0002] In the research of organic solar cells and perovskite solar cells, the hole transport layer material is very important. The commonly used hole transport layer material is poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), which is widely used due to its appropriate work function, excellent conductivity and easy solution processing. However, its acidity and absorption spectrum in the near-infrared region reduce the photoelectric conversion efficiency and stability of the organic solar cell.
[0003] In recent years, more and more researches have been conducted on (2-(9H-carbazol-9-yl) ethyl) phosphonic acid (2PACz) and its derivatives. These materials generally connect the carbazole conjugated structure and the phosphonic acid group through an alkyl chain, and the hydrogen bond on the phosphonic acid group can promote the adsorption of the molecules on the electrode indium tin oxide (ITO) to form a self-assembled monolayer. However, due to the planar skeleton structure of carbazole, the material has strong aggregation, which leads to unevenness of the film surface, and is not conducive to hole transport and repeatability. SUMMARY
[0004] The present application aims to overcome the problems existing in the prior art and provide a composite hole transport material and application thereof.
[0005] To achieve the above-mentioned purpose, the present application provides a composite hole transport material, wherein the composite hole transport material comprises a carbazole phosphate material and a phenyl phosphate material.
[0006] The carbazole phosphate material has the following structure:
[0007]
[0008] wherein M is H, methyl, phenyl or halogen, and n is an integer of 1-10; the phenyl phosphate material has the following structure:
[0009]
[0010] wherein X and D are independently selected from at least one of the following structures:
[0011]
[0012] wherein R is a linear or branched alkyl group of C1-C 50 .
[0013] In the present application, the above structures (a)-(m) can be connected to the phenyl phosphate material at any position.
[0014] The second aspect of the present application provides an application of the composite hole transport material according to the first aspect as a hole transport layer in an organic solar cell and a perovskite solar cell.
[0015] The third aspect of the present application provides a hole transport layer comprising the composite hole transport material according to the first aspect.
[0016] The fourth aspect of the present application provides a preparation method of the hole transport layer according to the third aspect, wherein the preparation method comprises the following steps:
[0017] (1) mixing the carbazole phosphate material and the phenyl phosphate material, and then dissolving in a solvent to obtain a precursor solution;
[0018] (2) spin coating the precursor solution obtained in step (1) on a substrate, and then performing annealing treatment to obtain the hole transport layer.
[0019] The fifth aspect of the present application provides an organic solar cell or a perovskite solar cell comprising the hole transport layer according to the third aspect or the hole transport layer obtained by the preparation method according to the fourth aspect.
[0020] Through the above technical solution, the present application has the following beneficial technical effects:
[0021] (1) The composite hole transport material provided by the present application can effectively improve the energy conversion efficiency, preparation repeatability (good product rate) and thermal stability of the device when used as a hole transport layer of a solar cell device.
[0022] (2) When used for preparing a flexible solar cell device, the device's bending stability can also be significantly improved.
[0023] (3) Due to the advantage of high concentration resistance, the device performance can also be excellent when used in a large-area solar cell device. BRIEF DESCRIPTION OF DRAWINGS
[0024] Figure 1 C-AFM images of the hole transport layer interface prepared by application example 3, application comparative example 3-1 and TPP as a hole transport material; wherein (a) is application comparative example 3-1, (b) is application example 3, and (c) is a hole transport material with TPP.
[0025] Figure 2 UPS test images of the hole transport layer interface prepared by application example 3, application comparative example 3-1 and TPP as a hole transport material.
[0026] Figure 3 J-V curves and EQE curves of the devices prepared in application example 3 and application comparative example 3-1 of the present application were measured; wherein (a) is the J-V curve, and (b) is the EQE curve.
[0027] Figure 4 J-V curves of the devices prepared in application example 4 and application comparative example 4-1 of the present application were measured.
[0028] Figure 5 J-V curves of the devices prepared in application example 5 and application comparative example 5-1 of the present application were measured.
[0029] Figure 6 J-V curves of the devices prepared in application example 6 and application comparative example 6-1 of the present application were measured.
[0030] Figure 7 J-V curves of the devices prepared in application example 7 and application comparative example 7-1 of the present application were measured.
[0031] Figure 8 Concentration-fill factor dependence curve of the rigid organic solar cell device.
[0032] Figure 9 Efficiency distribution curve of the devices prepared in application example 3 and application comparative example 3-1 of the present application was measured.
[0033] Figure 10 Thermal stability curve of the devices prepared in application example 3 and application comparative example 3-1 of the present application was measured.
[0034] Figure 11 Bending stability curve of the devices prepared in application example 3 and application comparative example 3-1 of the present application was measured. DETAILED DESCRIPTION
[0035] The endpoints of the ranges and any values claimed herein are not to be understood as being limited to the exact values recited as implicitly disclosed by the above description. Ranges can be expressed as from one "value and / or to another value. When such ranges are recited, endpoints are included. Also, it will be understood that every range and / or value described herein constitutes and explicitly disclosed combination of those values. However, also, the combination of any such features will also be impliedly disclosed herein as a separate aspect of the application.
[0036] The first aspect of the present application provides a composite hole transport material, wherein the composite hole transport material comprises a phosphine oxide carbazole material and a phosphine oxide phenyl material;
[0037] The phosphine oxide carbazole material has the following structure:
[0038]
[0039] wherein M is H, methyl, phenyl or halogen, and n is an integer from 1 to 10; the phenyl phosphate material has the following structure:
[0040]
[0041] wherein X and D are each independently selected from at least one of the following structures:
[0042]
[0043] wherein R is a linear or branched alkyl group of C1-C 50 .
[0044] The present application dopes a phenyl phosphate material into a carbazole phosphate material, and the obtained composite hole transport material as a hole transport layer can improve surface coverage and flexibility, thereby improving the energy conversion efficiency, preparation repeatability, thermal stability of an organic solar cell device and perovskite solar cell device, and the bending stability of a flexible device. Due to the obvious advantage in high concentration resistance, it can also be used to prepare large-area solar cell devices while maintaining excellent device performance.
[0045] In some embodiments of the present application, the carbazole phosphate material is (2-(9H-carbazol-9-yl)ethyl)phosphonic acid (2PACz, ).
[0046] In some embodiments of the present application, the phenyl phosphate material is triphenyl phosphate (TPP, ).
[0047] In some embodiments of the present application, the mass ratio of the carbazole phosphate material to the phenyl phosphate material is 1:0.5-3, such as 1:0.5, 1:1, 1:1.5, 1:2, 1:3, etc., and any value within the range between any two of the above values, and preferably 1:2.
[0048] The second aspect of the present application provides an application of the composite hole transport material according to the first aspect as a hole transport layer in an organic solar cell and a perovskite solar cell.
[0049] In some embodiments of the present application, the organic solar cell is a rigid or flexible organic solar cell.
[0050] In some embodiments of the present application, the organic solar cell is a large-area organic solar cell.
[0051] In some embodiments of the present application, the perovskite solar cell is a rigid or flexible perovskite solar cell.
[0052] 2PACz is prone to aggregation, and uniformity in the film forming process has certain limitations, and stress concentration points are easily formed in the device preparation process, which is not conducive to the preparation of flexible and large-area devices. The present application can also obtain excellent application effects in large-area and flexible organic or perovskite solar cells.
[0053] The third aspect of the present application provides a hole transport layer comprising the composite hole transport material of the first aspect.
[0054] The fourth aspect of the present application provides a preparation method of the hole transport layer according to the third aspect, comprising the following steps:
[0055] (1) mixing the phosphoric acid carbazole material and the phosphoric acid phenyl ester material, and then dissolving in a solvent to obtain a precursor solution;
[0056] (2) spin coating the precursor solution obtained in step (1) on a substrate, and then performing annealing treatment to obtain the hole transport layer.
[0057] In some embodiments of the present application, the solvent is ethanol and / or methanol.
[0058] In some embodiments of the present application, the concentration of the precursor solution is 0.3-3 mg / mL -1 , preferably 0.9 mg / mL -1 .
[0059] In some embodiments of the present application, the substrate is a rigid substrate or a flexible substrate.
[0060] In some embodiments of the present application, the rigid substrate is an ITO / glass substrate.
[0061] In some embodiments of the present application, the flexible substrate is an ITO / PEN substrate.
[0062] In some embodiments of the present application, the speed of spin coating is 2000-4000 rpm, preferably 3000 rpm.
[0063] In some embodiments of the present application, the time of spin coating is 20-50 s, preferably 30 s.
[0064] In some embodiments of the present application, the temperature of annealing treatment is 70-150℃, preferably 100℃.
[0065] In some embodiments of the present application, the time of annealing treatment is 5-15 min, preferably 10 min.
[0066] The fifth aspect of the present application provides an organic solar cell or perovskite solar cell comprising the hole transport layer of the third aspect or the hole transport layer obtained by the preparation method of the fourth aspect. For example, rigid or flexible organic solar cell, large-area organic solar cell, rigid or flexible perovskite solar cell.
[0067] The present application will be described in detail below by way of examples.
[0068] The specific conditions not specified in the following examples and comparative examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be obtained by commercial means.
[0069] Example 1
[0070] A composite hole transport material comprising (2-(9H-carbazol-9-yl)ethyl) phosphonic acid (2PACz) and triphenyl phosphate (TPP) in a mass ratio of 1:1.
[0071] Example 2
[0072] A composite hole transport material comprising (2-(9H-carbazol-9-yl)ethyl) phosphonic acid (2PACz) and triphenyl phosphate (TPP) in a mass ratio of 1:1.5.
[0073] Example 3
[0074] A composite hole transport material comprising (2-(9H-carbazol-9-yl)ethyl) phosphonic acid (2PACz) and triphenyl phosphate (TPP) in a mass ratio of 1:2.
[0075] Application Example 1
[0076] This application example is used to illustrate the preparation of a rigid organic solar cell device.
[0077] (1) Solution preparation:
[0078] (2-(9H-carbazol-9-yl)ethyl) phosphonic acid (2PACz) and triphenyl phosphate (TPP) are mixed in a mass ratio of 1:1 to prepare an ethanol solution with a total concentration of 0.9 mg mL -1 of the precursor solution for the hole transport layer.
[0079] (2) Preparation of rigid organic solar cell device:
[0080] (a) The patterned ITO / glass is cleaned by ultrasonic treatment in detergent, tap water, deionized water, acetone and isopropyl alcohol for 10 minutes in sequence, and then dried in an oven at 100°C as a substrate;
[0081] (b) treating the ITO / glass substrate in a plasma chamber for 2 minutes; then spin-coating the precursor solution onto the pre-cleaned patterned ITO / glass substrate at 3000 rpm for 30 s, and then annealing at 100°C for 10 min to form a 5 nm hole transport layer;
[0082] (c) transferring into a glove box filled with N2, spin-coating the active layer solution at 3200 rpm for 40 s to form a photoactive layer of about 100 nm; wherein the PM6:BTP-eC9 blend (mass ratio of 1:1.2) is dissolved in chloroform to form a solution at a concentration of 16 mg mL -1 , and 1,4-diiodobenzene at 12 mg mL -1 as an additive; spin-coating the PNDIT-F3N solution at 4200 rpm on top of the photoactive layer to form a 5 nm electron transport layer; wherein the PNDIT-F3N is dissolved in a mixed solvent (methanol:acetic acid = 1000:0.4) to form a solution at a concentration of 1.2 mg mL -1 ;
[0083] (4) finally, depositing a 100 nm thick Ag electrode by thermal evaporation under vacuum conditions of 3.5 x 10 -4 Pa to obtain a rigid organic solar cell device with an area of 0.0315 cm 2 .
[0084] Application Example 2
[0085] This application example is used to illustrate the preparation of a rigid organic solar cell device.
[0086] The rigid organic solar cell device is prepared according to the method of application example 1, except that in step (1), the mass ratio of 2PACz to TPP is 1:1.5.
[0087] Application Example 3
[0088] This application example is used to illustrate the preparation of a rigid organic solar cell device.
[0089] The rigid organic solar cell device is prepared according to the method of application example 1, except that in step (1), the mass ratio of 2PACz to TPP is 1:2.
[0090] Application Example 4
[0091] This application example is used to illustrate the preparation of a flexible organic solar cell device.
[0092] The flexible organic solar cell device is prepared according to the method of application example 3, except that the ITO / glass substrate in step (2) is replaced by an ITO / PEN substrate.
[0093] Application Example 5
[0094] This application example is used to illustrate the preparation of a large-area rigid organic solar cell device.
[0095] A large-area rigid organic solar cell device was prepared according to the method of Application Example 3, except that the area of the device was 1 cm 2 ; and the total concentration of the ethanol solution was 3 mg mL -1 .
[0096] Application Example 6
[0097] This application example is used to illustrate the preparation of a rigid perovskite solar cell device.
[0098] A rigid perovskite solar cell device was prepared according to the method of Application Example 3, except that step (c) was replaced by:
[0099] (c') 5 nm of Al2O3 was deposited at low temperature (<100°C), a perovskite precursor solution was spin-coated on the Al2O3 modification layer (rotation speed 4000 rpm, time 30 s), and chlorobenzene was added dropwise as an anti-solvent during the spin-coating process to induce rapid crystallization; annealing was performed at 100°C for 10 minutes to form a dense, high-crystalline-quality perovskite film; phenethylammonium iodide (PEAI) was dissolved in isopropanol (3 mg / mL) and spin-coated (3000 rpm, 30 s) on the surface of the perovskite film to form a 2D / 3D heterostructure; PC 61 BM was dissolved in chlorobenzene (20 mg / mL) and stirred overnight; the PC 61 BM solution was spin-coated (3000 rpm, 30 s) on the PEAI-treated perovskite film without annealing; and BCP (bathocuproin) was dissolved in ethanol (0.5 mg / mL) to form an ultrathin layer (~5 nm) after spin-coating (3000 rpm, 30 s).
[0100] Application Example 7
[0101] This application example is used to illustrate the preparation of a flexible perovskite solar cell device.
[0102] A flexible perovskite solar cell device was prepared according to the method of Application Example 6, except that the ITO / glass substrate in step (2) was replaced by an ITO / PEN substrate.
[0103] Application Comparative Examples 3-1 to 7-1
[0104] The TPP in step (1) of Application Examples 3 to 7 was removed, respectively, to prepare the corresponding cell devices.
[0105] Test Example 1
[0106] (1) Interface surface performance characterization
[0107] The interface of the hole transport layer obtained in step (b) of application example 3 and application comparative example 3-1 and the interface of the hole transport layer obtained using TPP as the hole transport material were characterized by conductive atomic force microscopy (C-AFM), and the results are shown in Figure 1
[0108] As can be seen from Figure 1 , the interface of application example 3 can well cover the ITO electrode, reduce the roughness of the thin film, thereby reducing the defect states caused by the unevenness of the thin film, and improving the device yield of organic solar cells and perovskite solar cells.
[0109] (2) Ultraviolet photoelectron spectroscopy test
[0110] The interface of the hole transport layer obtained in step (b) of application example 3 and application comparative example 3-1 and the interface of the hole transport layer obtained using TPP as the hole transport material were tested by ultraviolet photoelectron spectroscopy, and the results are shown in Figure 2
[0111] By testing the ultraviolet photoelectron spectroscopy (UPS), the work function (WF) and the highest occupied orbital (HOMO) based on the three interfaces on ITO were obtained. It was found that the interface of application example 3 had a HOMO energy level closer to the HOMO (-5.46 eV) of the light-active layer donor material PM6 than the interface of application comparative example 3-1, which indicated that it was more conducive to the extraction and transport of hole carriers of PM6 to the ITO electrode.
[0112] Test example 2 battery device photovoltaic performance characterization
[0113] The J-V curve was measured under 100 mW / cm 2 of AM1.5G illumination using a AAA solar simulator (XES-70S1, SAN-EI Electric Co., Ltd). The simulator was calibrated using a standard photovoltaic cell equipped with a KG5 filter (certified by the National Institute of Metrology) and a Keithley 2400 source measurement device. The external quantum efficiency (EQE) curve was obtained using a solar cell spectral response measurement system (QE-R3011, Enli Technology Co. Ltd).
[0114] The relevant test data are listed in Table 1. Some of the curve graphs are shown in Figures 3-7
[0115] Table 1
[0116]
[0117] According to Table 1, it can be seen from the comparison of Application Examples 1-3 that the optimal device performance can be obtained when the mass ratio of 2PACz to TPP is 1:2, and the PCE can be as high as 20.11%; when the composite hole transport material of the application is applied to rigid or flexible organic solar cell devices, large-area rigid organic solar cell devices, and rigid or flexible perovskite solar cell devices, a series of performances superior to those of the control devices can be obtained.
[0118] In addition, by adjusting the concentration of 2PACz in the hole transport layer precursor solution (i.e. ethanol solution) in step (1) of Application Example 3 and Application Comparative Example 3-1, the following Figure 8 The concentration- fill factor (FF) dependence curve is shown in the table. It can be seen that as the concentration of 2PACz increases, the fill factor of the device based on the mixed interface (2PACz:TPP = 1:2) changes little; while the fill factor of the device based on pure 2PACz decreases as the concentration increases due to the increase of defect states caused by strong aggregation of 2PACz. The high-concentration resistance of the device based on the mixed interface can also achieve excellent performance when used in large-area rigid organic solar cell devices.
[0119] Test Example 3 Preparation repeatability
[0120] The PCE of the devices prepared in the same batch was tested, and the efficiency distribution curve is shown in Figure 9 It can be seen that the efficiency distribution of the device prepared in Application Example 3 is more concentrated than that of the device prepared in Application Example 3-1, thus improving the repeatability or yield of device preparation.
[0121] Test Example 4 Stability
[0122] The rigid organic solar cell devices prepared in Application Example 3 and Application Comparative Example 3-1 were tested for PCE under heating on a hot stage at 80°C in a nitrogen atmosphere, and the results are shown in Figure 10
[0123] As shown in Figure 10 , the thermal stability of the device prepared in Application Example 3 is significantly better than that of the device prepared in Application Example 3-1.
[0124] In addition, the flexible organic solar cell devices prepared in Application Example 4 and Application Comparative Example 4-1 were tested for bending stability, and the results are shown in Figure 11
[0125] As shown in Figure 11 As shown, the bending stability of the device prepared by using application example 4 is obviously better than that of the device prepared by using application example 4-1. This shows that doping TPP into 2PACz reduces the aggregation of 2PACz, reduces the stress concentration point, and thus reduces the damage of the stress concentration point to the upper light-active layer in the bending process, thereby improving the bending stability of the device.
[0126] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including that each technical feature is combined in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.
Claims
1. A composite hole transport material, characterized by, The composite hole transport material comprises a carbazol phosphate material and a phenyl phosphate material; The carbazol phosphate material has the following structure: wherein M is H, methyl, phenyl or halogen, and n is an integer from 1 to 10; The phenyl phosphate material has the following structure: wherein X and D are independently selected from at least one of the following structures: wherein R is a linear or branched alkyl group of C1-C 50 .
2. The composite hole transport material according to claim 1, wherein, The carbazol phosphate material is (2-(9H-carbazol-9-yl)ethyl) phosphonic acid. Preferably, the phenyl phosphate material is triphenyl phosphate.
3. The composite hole transport material according to claim 1 or 2, wherein, The mass ratio of the carbazol phosphate material to the phenyl phosphate material is 1:0.5-3, preferably 1:
2.
4. Use of the composite hole transport material according to any one of claims 1-3 as a hole transport layer in an organic solar cell and a perovskite solar cell.
5. Use according to claim 4, wherein, The organic solar cell is a rigid or flexible organic solar cell. Preferably, the organic solar cell is a large-area organic solar cell. Preferably, the perovskite solar cell is a rigid or flexible perovskite solar cell.
6. A hole transport layer comprising the composite hole transport material according to any one of claims 1-3.
7. A method of producing the hole transport layer according to claim 6, characterized by, The preparation method comprises the following steps: (1) mixing the carbazol phosphate material and the phenyl phosphate material, and then dissolving in a solvent to obtain a precursor solution; (2) spin-coating the precursor solution obtained in step (1) on a substrate, and then performing annealing treatment to obtain the hole transport layer.
8. The production method according to claim 7, wherein The solvent is ethanol and / or methanol. Preferably, the concentration of the precursor solution is 0.3-3 mg mL -1 , preferably 0.9 mg mL -1 .
9. The production method according to claim 7 or 8, wherein The substrate is a rigid substrate or a flexible substrate. Preferably, the rigid substrate is an ITO / glass substrate. Preferably, the flexible substrate is an ITO / PEN substrate. Preferably, the spin-coating speed is 2000-4000 rpm, preferably 3000 rpm. Preferably, the spin-coating time is 20-50 s, preferably 30 s. Preferably, the annealing temperature is 70-150°C, preferably 100°C. Preferably, the annealing time is 5-15 min, preferably 10 min.
10. An organic solar cell or a perovskite solar cell comprising the hole transport layer according to claim 6 or obtained by the preparation method according to any one of claims 7-9.