Multifunctional organic semiconductor material taking cyano phosphonic acid as anchoring group as well as preparation method and application of multifunctional organic semiconductor material
By using a multifunctional organic semiconductor material with cyanophosphonic acid as the anchor group in perovskite solar cells, the problem of poor surface wetting of the hole transport material PTAA is solved, efficient carrier and hole transmission is achieved, and the photoelectric conversion efficiency of perovskite solar cells is improved.
Patent Information
- Application Number
- CN202411586570.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-08
- Publication Date
- 2025-02-28
AI Technical Summary
In existing perovskite solar cells, the commonly used hole transport material PTAA is limited by the poor wetting of perovskite solution on its surface, resulting in poor film formation quality and high interfacial defect density, which limits the improvement of device performance and commercial application.
Using a multifunctional organic semiconductor material with cyanophosphonic acid as the anchoring group, the surface superimbrication and interface defect control are achieved through the joint action of cyano and phosphonic acid, and the efficiency of carrier transportation and hole transport is improved. The material is self-assembled single-molecular layers (SAMs) in the form of high stability and low cost.
It effectively improves carrier transport and hole transmission efficiency, optimizes the photoelectric performance of perovskite solar cells, improves the comprehensive performance of the device, and the photoelectric conversion efficiency reaches 24.5%.
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Figure CN119528979A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of perovskite solar cells and relates to the preparation of organic semiconductor materials, in particular to a multifunctional organic semiconductor material with cyanophosphonic acid as an anchoring group and a preparation method and application thereof. Background Art
[0002] As the global demand for renewable energy continues to grow, solar cells, as a green energy conversion device, have attracted widespread attention. In particular, perovskite solar cells (PSCs) have become one of the most promising new generation photovoltaic technologies after silicon-based solar cells due to their excellent photoelectric conversion efficiency, simple preparation process and low production cost. The latest certified efficiency has reached 26.7% (National Renewable Energy Laboratory, NREL, 2024).
[0003] Compared with the traditional formal structure (nip) PSCs, the inverted structure (pin) PSCs have the advantages of low-temperature processing, compatibility with large-scale manufacturing, low hysteresis, and good stability. Therefore, they have considerable development prospects in the field of perovskite photovoltaics in the future. At present, the hole transport material (HTMs) poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA) hole transport layer commonly used in trans devices has poor wettability of perovskite solution on its surface, resulting in poor film quality and high interface defect state density. These problems limit its further performance improvement and commercial application. Therefore, the development of high-performance, new hole transport materials for trans devices is crucial to the performance of the device.
[0004] In recent years, self-assembled monolayers (SAMs) as hole transport materials have the characteristics of simple structure and flexible design. They can effectively adjust the interface energy level and reduce defect states based on molecular engineering. SAMs-type hole transport layers can be tightly bonded to the substrate through chemical bonds and have high stability. At the same time, the monolayer has a minimum layer thickness, which is also conducive to reducing parasitic absorption and improving the upper limit of device efficiency. Therefore, the development of new SAM materials with simple structure, low cost and excellent performance is a key issue that needs to be solved to promote the industrialization of PSCs. Summary of the invention
[0005] In view of the shortcomings of the prior art, the object of the present invention is to provide a multifunctional organic semiconductor material with cyanophosphonic acid as an anchoring group. The present invention uses cyano and phosphonic acid as bifunctional anchoring groups. This amphiphilic small molecule hole transport material can achieve surface superwetting and interface defect control, effectively improve the transport of carriers, and improve the hole transport efficiency. The SAMs molecule is simple to handle, has low cost and good stability. Another object of the present invention is to provide a method for preparing the organic semiconductor material.
[0006] The present invention is achieved through the following technical solutions:
[0007] A multifunctional organic semiconductor material with cyanophosphonic acid as an anchoring group, the chemical structure of which is shown below:
[0008]
[0009] A further improvement of the present invention is:
[0010] A method for preparing a multifunctional organic semiconductor material using cyanophosphonic acid as an anchoring group comprises the following steps: S1: allowing compound 1 to undergo a substitution reaction with 4-bromo-2-fluoro-1-methoxybenzene to generate an intermediate 2;
[0011]
[0012] S2: Substitution reaction of intermediate 2 with trans-4-bromocinnamaldehyde to generate intermediate 3;
[0013]
[0014] S3: Substitution reaction of intermediate 3 with diethyl(cyanomethyl)phosphonate to generate intermediate 4;
[0015]
[0016] S4: hydrolyzing the intermediate 4 to generate the target product, i.e., the self-assembled monolayer material;
[0017]
[0018] Furthermore, in S1, under argon protection, dimethylphenylsilane is used as solvent, and compound 1 and 4-bromo-2-fluoro-1-methoxybenzene are subjected to substitution reaction in the presence of bis(tri-tert-butylphosphine)palladium(0) and sodium tert-butoxide to generate compound 2; wherein the molar ratio of compound 1, 4-bromo-2-fluoro-1-methoxybenzene, bis(tri-tert-butylphosphine)palladium(0) and sodium tert-butoxide is 1:1~2:0.01~0.1:1~2.
[0019] Furthermore, in S2, under the protection of argon, using dimethylphenylsilane as solvent, compound 1 and trans-4-bromocinnamaldehyde undergo a substitution reaction under the action of bis(tri-tert-butylphosphine)palladium(0) and sodium tert-butoxide to generate compound 3; wherein the molar ratio of compound 1, trans-4-bromocinnamaldehyde, bis(tri-tert-butylphosphine)palladium(0) and sodium tert-butoxide is 1:1~2:0.01~0.1:1~2.
[0020] Furthermore, in S3, under argon protection, compound 3 is reacted with diethyl (cyanomethyl)phosphonate in acetonitrile and piperidine solution to generate compound 4; wherein the molar ratio of compound 3 to diethyl (cyanomethyl)phosphonate is 1:1-5.
[0021] Furthermore, in S4, compound 4 and bromotrimethylsilane are mixed in dichloromethane, and a hydrolysis reaction is carried out under an argon atmosphere to obtain the target product; wherein the molar ratio of compound 4 to bromotrimethylsilane is 1:5-10.
[0022] Furthermore, in S1, the temperature of the substitution reaction is 70-100° C., and the time is 1-2 h.
[0023] In S2, the temperature of the substitution reaction is 100-150° C., and the time is 10-25 hours.
[0024] In S3, the reaction temperature is 70-90° C. and the reaction time is 1-3 h.
[0025] In S4, the hydrolysis reaction is carried out at room temperature for 10 to 24 hours.
[0026] A further improvement of the present invention is:
[0027] The application of the above-mentioned multifunctional organic semiconductor material with cyanophosphonic acid as the anchoring group in perovskite solar cells.
[0028] The beneficial effects of the present invention are:
[0029] 1. The present invention provides a multifunctional organic semiconductor material based on cyanophosphonic acid as an anchoring group, and a preparation method and application thereof. The present invention introduces the combined effect of cyano and phosphonic acid. The introduction of the strong electron-withdrawing cyano increases the deprotonation ability of the phosphonic acid and the hydrophilicity of the anchoring group, so that the small molecule material has a unique amphiphilic characteristic, which realizes the wettability of the surface, better regulates the defects of the interface, enables the self-assembled monolayer to be firmly attached to the ITO surface to ensure efficient hole selection and transport, is beneficial to optimize the photoelectric properties of the perovskite, and can effectively improve the overall performance of the device.
[0030] 2. At the same time, the F atoms in the aromatic amine enhance the interfacial interaction between the hole transport layer and the perovskite layer, further regulate the crystallization of the perovskite and passivate the bottom interface defects of the perovskite, inhibiting the non-radiative recombination of the interface.
[0031] 3. The self-assembled monolayer organic semiconductor material provided by the present invention is used as a hole transport layer in perovskite solar cells. The test results show that the short-circuit photocurrent density of the battery device reaches 25.53 mA cm -2 , the open circuit voltage is 1.15V, the fill factor is 0.8380, and the photoelectric conversion efficiency reaches 24.5%, which has practical significance for improving the efficiency of perovskite solar cells. BRIEF DESCRIPTION OF THE DRAWINGS
[0032] Figure 1 The NMR spectrum of formula WZ prepared by the present invention;
[0033] Figure 2 This is the JV curve of an inverse perovskite solar cell prepared using the WZ self-assembled monolayer prepared according to the present invention. DETAILED DESCRIPTION
[0034] The present invention is described in detail below in conjunction with specific embodiments.
[0035] The embodiment of the present invention provides a method for synthesizing a multifunctional organic semiconductor material WZ using cyanophosphonic acid as an anchoring group.
[0036]
[0037] The synthetic route is as follows:
[0038]
[0039] Example 1: Synthesis of multifunctional organic semiconductor material WZ with cyanophosphonic acid as anchor group
[0040] (1) Synthesis of the compound of formula 2:
[0041] Under argon protection, compound 1 (5.64 g, 40 mmol), 4-bromo-2-fluoro-1-methoxybenzene (8.06 g, 40 mmol), sodium tert-butoxide (5.76 g, 60 mmol), bis(tri-tert-butylphosphine)palladium (0) (2.04 mg, 4 mmol) and dimethylphenylsilane (60 mL) were added to a 100 mL single-mouth round-bottom flask in sequence, and the mixed solution was heated to 90° C. and refluxed for 1 h. After the reaction solution was cooled to room temperature, ethyl acetate and water were added for extraction, and the organic phase was distilled under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 50 / 1 to 10 / 1) to obtain 6.47 g of compound 2 as a light green solid with a yield of 55%.
[0042] The structural characterization data of the compound of formula 2 are: 1 H NMR (400MHz, Chloroform-d) δ6.90 (t, J = 9.0Hz, 2H), 6.81 (m, 2H), 6.72 (m, 2H), 5.43 (s, 1H), 3.87 (s, 6H).
[0043] (2) Synthesis of the compound of formula 3:
[0044] Under argon protection, compound 2 (5.83 g, 22 mmol), trans-4-bromocinnamaldehyde (4.64 g, 22 mmol), sodium tert-butoxide (3.17 g, 33 mmol), bis(tri-tert-butylphosphine)palladium (0) (1.12 g, 2.2 mmol) and dimethylphenylsilane (60 mL) were added to a 100 mL single-mouth round-bottom flask in sequence, and the mixed solution was heated to 130° C. and refluxed for 24 h. After the reaction solution was cooled to room temperature, ethyl acetate and water were added for extraction, and the organic phase was distilled under reduced pressure. The crude product was subjected to column chromatography (eluent: petroleum ether / ethyl acetate = 20 / 1 to 4 / 1) to obtain 5.21 g of compound 3 as a gray solid with a yield of 60%.
[0045] The structural characterization data of the compound of formula 3 are: 1 H NMR (400MHz, Chloroform-d) δ9.64 (d, J = 7.8Hz, 1H), 7.45–7.35 (m, 3H), 6.98–6.83 (m, 8H), 6.59 (m, 1H), 3.90 (s, 6H).
[0046] (3) Synthesis of compound of formula 4:
[0047] Under argon protection, compound 3 (5.21 g, 13 mmol), diethyl (cyanomethyl) phosphonate (2.33 g, 13 mmol), piperidine (3 mL), and acetonitrile (60 mL) were added to a 100 mL two-necked bottle in sequence. The reaction solution was heated to 165 ° C and reacted for 18 h. After the reaction solution was cooled to room temperature, the excess diethyl (cyanomethyl) phosphonate was distilled off under reduced pressure, and the crude product was subjected to column chromatography (eluent: dichloromethane / ethyl acetate = 50 / 1 to 10 / 1) to obtain 1.46 g of compound 4 as a blue solid with a yield of 20%.
[0048] The structural characterization data of the compound of formula 4 are: 1H NMR(500MHz,Chloroform-d)δ7.77–7.65(m,1H),7.35–7.23(m,2H),7.19(s,1H),7. 05–7.02(m,1H),6.82(m,8H),4.18–4.05(m,4H),3.83(s,6H),1.32(t,J=7.1Hz,6H).
[0049] (4) Synthesis of formula WZ:
[0050] Under argon protection, compound 4 (1.46 g, 3 mmol), bromotrimethylsilane (6.04 g, 26 mmol) and 15 mL of dichloromethane were added to a 100 mL two-necked bottle, and the mixture was reacted at room temperature for 24 h. The solvent was removed by distillation under reduced pressure, and 5 mL of methanol and 15 mL of water were added to the obtained solid in turn, and stirring was continued for 3 h. The reaction solution was filtered and washed with water to obtain a crude product. The crude product was recrystallized from ethanol and water to obtain 1.18 g of the target product as a blue solid with a yield of 90%.
[0051] The structural characterization data of the compound of formula WZ are: 1 H NMR (400MHz, Methanol-d4) δ7.83–7.37(m,3H),7.26–7.07(m,2H),7.08–6.90(m,3H),6.89–6.79(m,5H),3.88(d,J=5.1Hz,6H).
[0052] Example 2: Synthesis of multifunctional organic semiconductor material WZ with cyanophosphonic acid as anchor group
[0053] (1) Synthesis of compound of formula 2:
[0054] Under argon protection, compound 1 (5.64 g, 40 mmol), 4-bromo-2-fluoro-1-methoxybenzene (8.06 g, 40 mmol), sodium tert-butoxide (5.76 g, 60 mmol), bis(tri-tert-butylphosphine)palladium (0) (0.2 mg, 0.4 mmol) and dimethylphenylsilane (60 mL) were added to a 100 mL single-mouth round-bottom flask in sequence, and the mixed solution was heated to 90° C. and refluxed for 1 h. After the reaction solution was cooled to room temperature, ethyl acetate and water were added for extraction, and the organic phase was distilled under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 50 / 1 to 10 / 1) to obtain 6.47 g of compound 2 as a light green solid with a yield of 61%.
[0055] (2) Synthesis of the compound of formula 3:
[0056] Under argon protection, compound 2 (6.47 g, 24 mmol), trans-4-bromocinnamaldehyde (7.72 g, 36.6 mmol), sodium tert-butoxide (3.52 g, 36.6 mmol), bis(tri-tert-butylphosphine)palladium (0) (1.25 g, 2.4 mmol) and dimethylphenylsilane (60 mL) were added to a 100 mL single-mouth round-bottom flask in sequence, and the mixed solution was heated to 130° C. and refluxed for 24 h. After the reaction solution was cooled to room temperature, ethyl acetate and water were added for extraction, and the organic phase was distilled under reduced pressure. The crude product was subjected to column chromatography (eluent: petroleum ether / ethyl acetate = 20 / 1 to 4 / 1) to obtain 6.26 g of compound 3 as a gray solid with a yield of 65%.
[0057] (3) Synthesis of compound of formula 4:
[0058] Under argon protection, compound 3 (6.26 g, 16 mmol), diethyl (cyanomethyl) phosphonate (3.37 g, 19 mmol), piperidine (3 mL), and acetonitrile (60 mL) were added to a 100 mL two-necked bottle in sequence. The reaction solution was heated to 165 ° C and reacted for 18 h. After the reaction solution was cooled to room temperature, the excess diethyl (cyanomethyl) phosphonate was distilled off under reduced pressure, and the crude product was subjected to column chromatography (eluent: dichloromethane / ethyl acetate = 50 / 1 to 10 / 1) to obtain 2.19 g of compound 4 as a blue solid with a yield of 25%.
[0059] (4) Synthesis of formula WZ:
[0060] Under argon protection, compound 4 (2.19 g, 4 mmol), bromotrimethylsilane (6.04 g, 40 mmol) and 15 mL of dichloromethane were added to a 100 mL two-necked bottle, and the mixture was reacted at room temperature for 24 h. The solvent was removed by distillation under reduced pressure, and 5 mL of methanol and 15 mL of water were added to the obtained solid in turn, and stirring was continued for 3 h. The reaction solution was filtered and washed with water to obtain a crude product. The crude product was then recrystallized from ethanol and water to obtain 1.97 g of the target product as a blue solid with a yield of 90%.
[0061] Example 3: Characterization and performance verification
[0062] The self-assembled monolayer hole transport material WZ prepared in Example 1 has a nuclear magnetic resonance spectrum as shown in Figure 1 shown.
[0063] This embodiment provides an inverted perovskite solar cell prepared by using the formula WZ prepared in Example 1 as a self-assembled monolayer, and the perovskite solar cell is prepared according to the method of the literature: G.Qu; S.Cai; Y.Qiao; et al.Joule, 2024, 8, 2123-2134. Test light source: AM 1.5 (solar simulator-Oriel 91160-1000, 300W), data acquisition using Keithley 2400 digital source meter. Test results are shown in Figure 2 The short-circuit photocurrent density of the battery device reached 25.53 mA cm -2 , the open circuit voltage is 1.15V, the fill factor (FF) is 0.8380, and the photoelectric conversion efficiency reaches 24.5%.
[0064] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent transformation or modification made according to the spirit of the present invention should be included in the protection scope of the present invention.
Claims
1. A multifunctional organic semiconductor material with cyanophosphonic acid as an anchoring group, characterized in that: The chemical structure is shown below:
2. The method for preparing a multifunctional organic semiconductor material with cyanophosphonic acid as an anchoring group according to claim 1, characterized in that: The following steps are involved: S1: Compound 1 undergoes a substitution reaction with 4-bromo-2-fluoro-1-methoxybenzene to generate intermediate 2; S2: Substitution reaction of intermediate 2 with trans-4-bromocinnamaldehyde to generate intermediate 3; S3: Substitution reaction of intermediate 3 with diethyl(cyanomethyl)phosphonate to generate intermediate 4; S4: hydrolyzing the intermediate 4 to generate the target product, i.e., the self-assembled monolayer material; 3. The method for preparing a multifunctional organic semiconductor material with cyanophosphonic acid as an anchoring group according to claim 2, characterized in that: In S1, under argon protection, dimethylphenylsilane is used as solvent, and compound 1 and 4-bromo-2-fluoro-1-methoxybenzene are subjected to substitution reaction under the action of bis(tri-tert-butylphosphine)palladium(0) and sodium tert-butoxide to generate compound 2; wherein the molar ratio of compound 1, 4-bromo-2-fluoro-1-methoxybenzene, bis(tri-tert-butylphosphine)palladium(0) and sodium tert-butoxide is 1:1~2:0.01~0.1:1~2.
4. The method for preparing a multifunctional organic semiconductor material with cyanophosphonic acid as an anchoring group according to claim 2, characterized in that: In S2, under the protection of argon, dimethylphenylsilane is used as a solvent, and compound 1 and trans-4-bromocinnamaldehyde are subjected to a substitution reaction under the action of bis(tri-tert-butylphosphine)palladium(0) and sodium tert-butoxide to generate compound 3; wherein the molar ratio of compound 1, trans-4-bromocinnamaldehyde, bis(tri-tert-butylphosphine)palladium(0) and sodium tert-butoxide is 1:1~2:0.01~0.1:1~2.
5. The method for preparing a multifunctional organic semiconductor material with cyanophosphonic acid as an anchoring group according to claim 2, characterized in that: In S3, under argon protection, compound 3 is reacted with diethyl (cyanomethyl)phosphonate in acetonitrile and piperidine solution to generate compound 4; wherein the molar ratio of compound 3 to diethyl (cyanomethyl)phosphonate is 1:1-5.
6. The method for preparing a multifunctional organic semiconductor material with cyanophosphonic acid as an anchoring group according to claim 2, characterized in that: In S4, compound 4 and bromotrimethylsilane are mixed in dichloromethane, and a hydrolysis reaction is carried out under an argon atmosphere to obtain the target product; wherein the molar ratio of compound 4 to bromotrimethylsilane is 1:5-10.
7. The method for preparing a multifunctional organic semiconductor material with cyanophosphonic acid as an anchoring group according to claim 2, characterized in that: In S1, the temperature of the substitution reaction is 70-100°C and the time is 1-2h; And / or, in S2, the temperature of the substitution reaction is 100-150° C., and the time is 10-25 h; And / or, in S3, the reaction temperature is 70-90° C. and the reaction time is 1-3 h; And / or, in S4, the hydrolysis reaction is carried out at room temperature for 10 to 24 hours.
8. Use of the multifunctional organic semiconductor material with cyanophosphonic acid as an anchoring group as claimed in claim 1 in perovskite solar cells.