Halide semiconductor n-p homojunction and preparation method and application thereof
By introducing TPFS on the surface of halide semiconductors to construct np homojunctions, the interfacial recombination problem in halide semiconductor solar cells is solved, improving device performance and stability, and making it suitable for large-scale commercial production.
Patent Information
- Application Number
- CN202510276546.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-10
- Publication Date
- 2026-02-06
AI Technical Summary
In halide semiconductor solar cells, nonradiative recombination at the heterojunction between the halide semiconductor and the charge transport layer significantly affects device performance and stability, resulting in a large gap between the output efficiency and the Shockley-Queisser limit.
Trichloro[3-(pentafluorophenyl)propyl]silane (TPFS) was introduced onto the surface of a halide semiconductor using a full solution method to construct a halide semiconductor np homojunction. By changing the work function of the semiconductor surface and passivating surface defects, an ideal pn junction was formed.
It effectively improves the work function of halide semiconductor surfaces, suppresses interfacial recombination, enhances thin film stability, and improves the photovoltaic performance and stability of solar cells, making it suitable for large-scale commercial production.
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of solar cells, and particularly relates to a halide semiconductor n-p homojunction and a preparation method and application thereof. BACKGROUND
[0002] Solar cell technology is a technology that converts solar radiation energy into electrical energy, mainly through photovoltaic effect. With the growing global demand for clean energy, the development of solar cell technology is constantly advancing, covering many aspects from material innovation to production process optimization. Organic-inorganic hybrid halide semiconductor solar cells (PSCs) as a promising next-generation photovoltaic technology have attracted widespread attention from academia and industry due to their high efficiency, low cost, and huge application potential. Organic-inorganic hybrid halide semiconductors as solar light absorbers have excellent optoelectronic properties, including high absorption coefficient, low exciton binding energy, long carrier diffusion, and tunable band gap. Recently, the certified efficiency of single-junction PSCs has approached that of silicon cells. However, the non-radiative recombination at the heterojunction interface between halide semiconductors and charge transport layers significantly affects the device performance and stability of PSCs, especially leading to a large gap between output efficiency and Shockley-Queisser limit.
[0003] The advantages of halide semiconductor n-p homojunction mainly lie in the good interface matching of n-type and p-type doped halide semiconductor materials, which is due to the high chemical stability and structural stability of halide semiconductor materials, which can effectively reduce the interface defects or mismatch between n-type and p-type halide semiconductor materials, and can form an ideal pn junction. Therefore, exploring a simple and effective strategy to construct n-p homojunction halide semiconductors and improve the quality of halide semiconductor heterojunction to suppress non-radiative recombination in halide semiconductor solar cells (PSCs) is an urgent need to promote their industrial production. SUMMARY
[0004] To solve the technical problems existing in halide semiconductors, the application provides a halide semiconductor n-p homojunction and a preparation method and application thereof.
[0005] To achieve the above-mentioned purposes, the technical solutions adopted by the application are as follows:
[0006] The application provides a halide semiconductor n-p homojunction, which is a halide semiconductor n-p homojunction constructed by introducing trichloro[3-(pentafluorophenyl)propyl]silane (TPFS) on the surface of a halide semiconductor.
[0007] The n-p homojunction in the application refers to an interface structure composed of two different types of semiconductors (n-type semiconductor and p-type semiconductor) of the same material.
[0008] The application further provides a preparation method of the halide semiconductor n-p homojunction, which comprises the following steps:
[0009] (1) preparing a halide semiconductor thin film: dissolving lead iodide in a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide, depositing the obtained solution 1 on an n-type semiconductor substrate, and annealing to obtain a lead iodide thin film; dissolving formamidinium iodide and methylammonium chloride in a first organic solvent, spin-coating the obtained solution 2 on the lead iodide thin film, and annealing to obtain a halide semiconductor thin film;
[0010] (2) constructing a halide semiconductor n-p homojunction: dissolving TPFS in a second organic solvent, spin-coating the obtained solution 3 on the halide semiconductor thin film obtained in the step (1), and annealing to obtain a halide semiconductor n-p homojunction.
[0011] In the step (1), the n-type semiconductor substrate is a metal oxide such as tin oxide or titanium oxide; preferably, tin oxide.
[0012] In the step (1), the lead iodide in the solution 1 has a concentration of 1.1-1.8 M, and 3-8% RbCl is doped; preferably, the lead iodide has a concentration of 1.5 M, and 5% RbCl is doped.
[0013] In the step (1), the mixed volume ratio of the N,N-dimethylformamide and dimethyl sulfoxide is 15:1-5:1; preferably, the mixed volume ratio of the N,N-dimethylformamide and dimethyl sulfoxide is 9:1.
[0014] In the step (1), the first organic solvent is selected from one or more of isopropanol or ethanol; preferably, isopropanol.
[0015] The volume of the first organic solvent in the step (1) is 0.5-2 mL; wherein the volume of the isopropanol organic solvent is 1 mL.
[0016] The mass ratio of the formamidinium iodide and the methyl amine chloride in the step (1) is (60-120):(5-30); preferably, the mass ratio of the formamidinium iodide and the methyl amine chloride is 90:15.
[0017] The deposition condition of the solution 1 in the step (1) is 500-5000 rpm / 10-100 s, and the annealing condition is 50-150℃ annealing for 0.5-5.0 min; preferably, the deposition condition is 2000 rpm / 30 s, and the annealing condition is 70℃ annealing for 1 min.
[0018] The spin coating condition of the solution 2 in the step (1) is 500-5000 rpm / 10-100 s, and the annealing condition is 0-90% humidity air annealing for 1-100 min at 50-200℃; preferably, the spin coating condition is 1800 rpm / 30 s, and the annealing condition is 35% humidity air annealing for 10 min at 150℃.
[0019] The second organic solvent in the step (2) is selected from one or more of isopropanol or ethanol and the like; preferably, isopropanol.
[0020] The concentration of TPFS in the solution 3 in the step (2) is 1-100 mg / mL; preferably, the concentration of TPFS is 5 mg / mL.
[0021] The spin coating condition of the solution 3 in the step (2) is 500-5000 rpm / 10-100 s, and the annealing condition is 50-150℃ annealing for 1-100 min; preferably, the spin coating condition is 4000 rpm / 30 s, and the annealing condition is 100℃ annealing for 5 min.
[0022] The application further provides a halide semiconductor n-p homojunction prepared by the above method.
[0023] The application further provides the use of the halide semiconductor n-p homojunction as described above, or the use of the preparation method as described above in the preparation of a halide semiconductor solar cell, a light-emitting diode and the like optoelectronic device.
[0024] Compared with the prior art, the beneficial effects of the present application include: the introduction of TPFS in the present application can effectively increase the surface work function of the halide semiconductor, so that the surface of the halide semiconductor is converted from n-type to p-type, and a halide semiconductor n-p homojunction is constructed, which helps to extract holes and block electrons, and suppresses interface recombination. At the same time, TPFS can passivate the surface defects of the halide semiconductor and enhance the stability of the halide semiconductor thin film. The present application provides a method for constructing a halide semiconductor n-p homojunction, which has simple process, low cost, mild and controllable conditions, and is suitable for large-scale commercial production. This means that in the implementation process, the required equipment, technology and raw material cost are relatively low, making the production process more economical and efficient. In addition, the operating conditions of this process are relatively mild and can be carried out in a common temperature and pressure environment, avoiding the need for complex conditions and high energy consumption. Therefore, not only can the production cost be reduced, but also the wear and tear of the equipment and the energy consumption can be reduced. In terms of controllability, this process can accurately adjust the relevant parameters to ensure the stability of the production process and the consistency of the product quality, further reducing the production fluctuations and quality problems caused by improper operation. These characteristics make this method particularly suitable for large-scale commercial production, because it can maintain high production efficiency and low product cost even in large-scale production, thereby promoting its widespread application in industrial production. BRIEF DESCRIPTION OF DRAWINGS
[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.
[0026] Figure 1 The ultraviolet photoelectron spectrum of the halide semiconductor thin film prepared in the present application Comparative Example 1 and Example 2;
[0027] Figure 2 The energy level diagram of the halide semiconductor n-p homojunction prepared in the present application Example 2;
[0028] Figure 3 The steady-state fluorescence spectrum of the halide semiconductor thin film prepared in the present application Comparative Example 1 and Example 2;
[0029] Figure 4 The transient fluorescence spectrum of the halide semiconductor thin film prepared in the present application Comparative Example 1 and Example 2. DETAILED DESCRIPTION
[0030] The application will be further described in conjunction with the following specific examples and drawings. The process, conditions, experimental methods, etc. for implementing the application, except for the following specifically mentioned contents, are the general knowledge and common sense in the art, and the application has no special limitation.
[0031] The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the application or its application or uses. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.
[0032] In all examples shown and discussed here, any specific value should be interpreted as merely exemplary, not as a limitation. Thus, other examples of the exemplary embodiments can have different values.
[0033] The application discloses a halide semiconductor n-p homojunction and a preparation method and application thereof. The preparation method introduces trichloro[3-(pentafluorophenyl)propyl]silane (TPFS) into the surface of the halide semiconductor by a solution method to construct the halide semiconductor n-p homojunction. The trichloro[3-(pentafluorophenyl)propyl]silane can greatly improve the work function of the surface of the halide semiconductor, so that the surface of the halide semiconductor is converted from n-type to p-type, which is helpful for hole extraction and electron blocking and inhibits interface recombination. In addition, the trichloro[3-(pentafluorophenyl)propyl]silane can passivate the surface defects of the halide semiconductor and enhance the stability of the halide semiconductor thin film. The application has simple process, low cost, and is conducive to large-area preparation and commercial application of the halide semiconductor optoelectronic device.
[0034] The test materials used in the examples are conventional biochemical reagents unless otherwise specified.
[0035] Example 1
[0036] This example is used to illustrate the implementation and application of the solution method for preparing the halide semiconductor n-p homojunction in a solar cell, and the steps are as follows:
[0037] 1) Preparation of tin oxide film: dilute the tin oxide hydrogel dispersion liquid from 15% to 2.67%, spin coat on an indium tin oxide conductive glass substrate (ITO) at 4000 rpm / 30 s, and then place on a heating table at 150 DEG C for 30 min annealing to obtain a SnO2 film.
[0038] 2) Preparation of halide semiconductor thin film: 1.5M lead iodide doped with 5% RbCl was dissolved in a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide with a volume ratio of 9:1, and spin-coated on the tin oxide thin film obtained in step 1) at 1500 rpm / 30 s, and annealed at 70°C for 1 min to obtain a lead iodide thin film; 90 mg of formamidinium iodide and 15 mg of methylammonium chloride were dissolved in 1 mL of isopropanol, and the obtained solution was spin-coated on the PbI2 at 1800 rpm / 30 s, and annealed at 150°C for 15 min in 35% humidity air to obtain a halide semiconductor thin film.
[0039] 3) Preparation of halide semiconductor n-p homojunction: TPFS was dissolved in isopropanol at a concentration of 3 mg / mL, and spin-coated on the halide semiconductor thin film prepared above at 4000 rpm / 30 s, and then annealed at 100°C for 5 min to obtain a halide semiconductor n-p homojunction.
[0040] 4) Preparation of hole transport layer: Spiro-OMeTAD (2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene) was dissolved in chlorobenzene at a concentration of 72.3 mg / mL, and doped with 17.5 μL of Li-TFSI (lithium bis(trifluoromethane)sulfonimide, 520 mg / mL in acetonitrile) and 28.8 μL of tBP (4-tert-butylpyridine); the solution was spin-coated on the halide semiconductor n-p homojunction obtained in step 3) at 4000 rpm / 30 s.
[0041] 5) Preparation of metal electrode: 5 nm of molybdenum oxide and 100 nm of Ag film were evaporated on the hole transport layer, and the cell area was 0.051 cm 2 to obtain a halide semiconductor solar cell.
[0042] Example 2
[0043] This example is used to illustrate the implementation application of the solution method for preparing a halide semiconductor n-p homojunction in a solar cell, wherein the preparation of a tin oxide thin film, a halide semiconductor thin film, a hole transport layer, and a metal electrode is the same as in Example 1 of the present application, except that step 3) is as follows:
[0044] 3) Preparation of halide semiconductor n-p homojunction: TPFS was dissolved in isopropanol at a concentration of 5 mg / mL, and spin-coated on the halide semiconductor thin film prepared above at 4000 rpm / 30 s, and then annealed at 100°C for 5 min to obtain a halide semiconductor n-p homojunction.
[0045] Example 3
[0046] This example is used to illustrate the implementation of the solution method for preparing halide semiconductor n-p homojunction in solar cells, wherein the preparation of tin oxide film, halide semiconductor film, the preparation of hole transport layer and the preparation of metal electrode are the same as those in Example 1 of the present application, except that step 3) is different.
[0047] 3) Preparation of halide semiconductor n-p homojunction: TPFS was dissolved in isopropanol with a concentration of 8 mg / mL, and spin-coated on the above-prepared halide semiconductor film at 4000 rpm / 30 s, followed by annealing at 100°C for 5 min to obtain the halide semiconductor n-p homojunction.
[0048] Comparative Example 1
[0049] This comparative example is used to illustrate the implementation of the solution method for preparing halide semiconductor n-p homojunction in solar cells, wherein the preparation of tin oxide film, halide semiconductor film, the preparation of hole transport layer and the preparation of metal electrode are the same as those in Example 1 of the present application, except that step 3) is not included.
[0050] Example 4
[0051] Short-circuit current density-voltage test: The short-circuit current density-voltage (J-V) characteristic curve was measured by a Keithley 2400 system and a solar simulator (SS-F5-3A, Enli Tech.) in a nitrogen glove box. A NREL-certified silicon cell (KG-5) was used to calibrate the light intensity (AM 1.5G, 100 mW cm -2 ). The measurement range was 1.2 V to -0.2 V with a step of 0.02 V. The test results are shown in Table 1.
[0052] Table 1: Photovoltaic performance parameters of halide semiconductor solar cells obtained in Examples 1-3 and Comparative Example 1 of the present application.
[0053]
[0054]
[0055] As can be seen from the results in Table 1, compared with Comparative Example 1, the halide semiconductor n-p homojunction-based solar cells prepared in Examples 1-3 of the present application are superior to Comparative Example 1 in terms of open-circuit voltage (V oc ), short-circuit current (J sc ), fill factor (FF) and energy conversion efficiency (PCE).
[0056] Performance characterization results of the halide semiconductor film prepared in Comparative Example 1:
[0057] It was found by ultraviolet photoelectron spectroscopy that, as Figure 1As shown, the halide semiconductor thin film deposited on tin oxide has a low work function of 4.25 eV, and its Fermi level to valence band top distance is 1.30 eV. Based on its 1.53 eV band gap, the Fermi level is closer to the conduction band, exhibiting n-type conductivity. Steady-state fluorescence spectra (…) Figure 3 The weak fluorescence intensity indicated the presence of numerous defects in the halide semiconductor film. Transient fluorescence spectroscopy revealed... Figure 4 After contact with HTL, the transient fluorescence spectrum decayed slowly, still exhibiting a high carrier lifetime (5.59 ns), indicating poor interfacial hole extraction efficiency. The resulting device exhibited poor performance, achieving only 22.5% power conversion efficiency, 1.117 V open-circuit voltage, and 25.49 mA cm⁻¹. -2 The short-circuit current and 79.14% fill factor are mainly attributed to nonradiative recombination losses caused by interface defects and energy level mismatch.
[0058] Performance characterization results of the halide semiconductor np homojunction prepared in Example 2 of this invention:
[0059] Compared to Comparative Example 1, this invention, by introducing TPFS, significantly increases the work function of the halide semiconductor thin film to 4.85 eV, while reducing the distance from its Fermi level to the valence band top to 0.70 eV. Based on its 1.53 eV band gap, the Fermi level is closer to the valence band, exhibiting p-type conductivity, indicating the formation of an np homojunction in the halide semiconductor. Figure 2 ). Through steady-state fluorescence spectra ( Figure 3 The fluorescence intensity was significantly enhanced, indicating that the surface defects of the halide semiconductor film were effectively passivated. Transient fluorescence spectra revealed (…). Figure 4 After contact with HTL, the transient fluorescence spectrum decayed significantly faster, and the carrier lifetime decreased to 3.06 ns, indicating an enhanced interface hole extraction efficiency. The introduction of TPFS effectively improves the work function of the halide semiconductor surface, transforming it from n-type to p-type and constructing an np homojunction. This facilitates hole extraction and electron blocking, suppressing interface recombination. Simultaneously, TPFS can passivate surface defects in the halide semiconductor, enhancing the stability of the halide semiconductor thin film. The performance of the halide semiconductor solar cell modified with TPFS was significantly improved, achieving an open-circuit voltage of 1.185 V and an open-circuit voltage of 25.72 mA cm⁻¹. -2 The invention provides a method for constructing a halide semiconductor np homojunction, characterized by short-circuit current, 84.84% fill factor, and 25.90% power conversion efficiency. This method is simple, low-cost, and operates under mild and controllable conditions, making it suitable for large-scale commercial production.
[0060] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
[0061] As used herein, the term "comprising" is an open term, i.e. it includes what the claims recite but not excluding other items.
[0062] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. Although the embodiments of this description have been described herein, it should be understood that various modifications, substitutions, changes, and omissions can be made therein without departing from the spirit of the embodiments. Therefore, the scope of the description is not to be understood as being limited with respect to the particular embodiments described herein. Rather it should be understood to cover all alternatives, modifications, equivalents, and variations that fall within the scope of the present description.
[0063] Although the present application has been described in detail with reference to the specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the application. Accordingly, the scope of the present application is not to be limited to the above specific embodiments but is only limited by the scope of the appended claims.
Claims
1. A halide semiconductor np homojunction, characterized in that, The halide semiconductor NP homojunction refers to a halide semiconductor NP homojunction constructed by introducing trichloro[3-(pentafluorophenyl)propyl]silane onto the surface of a halide semiconductor.
2. A method for preparing a halide semiconductor np homojunction, characterized in that, The preparation method includes the following steps: (1) Preparation of halide semiconductor thin film: lead iodide is dissolved in a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide, and the resulting solution 1 is deposited on an n-type semiconductor substrate and annealed to obtain a lead iodide thin film; formamidine ammonium iodide and methyl ammonium chloride are dissolved in a first organic solvent, and the resulting solution 2 is spin-coated on the lead iodide thin film and annealed to obtain a halide semiconductor thin film; (2) Constructing a halide semiconductor np homojunction: Dissolve trichloro[3-(pentafluorophenyl)propyl]silane in a second organic solvent, spin-coat the resulting solution 3 onto the halide semiconductor film obtained in step (1), and anneal to obtain a halide semiconductor np homojunction.
3. The preparation method according to claim 2, characterized in that, In step (1), the n-type semiconductor substrate is one or both of tin oxide and titanium oxide.
4. The preparation method according to claim 2, characterized in that, In step (1), the lead iodide concentration in solution 1 is 1.1-1.8M, and it is doped with 3-8% RbCl; and / or, the volume ratio of N,N-dimethylformamide to dimethyl sulfoxide in the N,N-dimethylformamide and dimethyl sulfoxide mixed solvent is 15:1-5:
1.
5. The preparation method according to claim 2, characterized in that, In step (1), the mass ratio of formammonium iodide to methylamine chloride is (60-120):(5-30); and / or, in step (1), the first organic solvent is selected from one or both of isopropanol and ethanol; and / or, the volume of the first organic solvent is 0.5-2 mL.
6. The preparation method according to claim 2, characterized in that, In step (1), the deposition conditions of solution 1 are 500-5000 rpm / 10-100 s, and the annealing conditions are annealing at 50-150℃ for 0.5-5.0 min; and / or, the spin coating conditions of solution 2 are 500-5000 rpm / 10-100 s, and the annealing conditions are annealing at 50-200℃ for 1-100 min in air with 0-90% humidity.
7. The preparation method according to claim 2, characterized in that, In step (2), the concentration of trichloro[3-(pentafluorophenyl)propyl]silane in solution 3 is 0-100 mg / mL; and / or, the second organic solvent is selected from one or both of isopropanol and ethanol.
8. The preparation method according to claim 2, characterized in that, In step (2), the spin coating conditions for solution 3 are 500-5000 rpm / 10-100 s, and the annealing conditions are annealing at 50-150℃ for 1-100 min.
9. A halide semiconductor np homojunction prepared by the preparation method according to any one of claims 2-8.
10. The application of the halide semiconductor np homojunction as described in claim 1 or 9, or the preparation method as described in any one of claims 2-8, in the preparation of halide semiconductor solar cells and light-emitting diodes.