Perovskite solar cell based on hole transport layer modification and preparation method thereof
By adding rare earth metals to the inorganic hole transport layer to form a composite thin film layer with a concentration gradient distribution, the energy level and surface defects are optimized, solving the problems of low conductivity and surface defects in the inorganic hole transport layer, and achieving high efficiency and improved stability of perovskite solar cells.
Patent Information
- Application Number
- CN202410976093.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-19
- Publication Date
- 2026-01-20
AI Technical Summary
The low conductivity, numerous surface defects, and difficulty in supporting sufficiently thick perovskite films in existing inorganic hole transport layers result in low fill factor and current density in perovskite solar cells, limiting their photoelectric conversion efficiency.
Rare earth metals are added to the precursor solution of inorganic hole transport materials. By controlling the reaction process, the rare earth metals are distributed in a concentration gradient in the hole transport layer, forming a composite thin film layer with a bottom layer of hole transport layer, a middle layer of hole transport layer doped with rare earth metal ions, and an upper layer of hole transport modification layer. This optimizes the energy level and surface defects, forming a heterojunction to promote carrier transport.
The photoelectric conversion efficiency and stability of perovskite solar cells have been improved, with the photoelectric conversion efficiency increased to 18.3%, and 92% of the initial efficiency can still be retained after UV aging.
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Figure CN121368263A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of perovskite preparation, and particularly relates to a perovskite solar cell based on hole transport layer modification and a preparation method thereof. BACKGROUND
[0002] The perovskite solar cell has two structures, i.e. a positive type and a reverse type. The reverse type perovskite solar cell uses some inorganic materials (metal oxides, CuSCN, CuI, etc.) to replace the organic materials (PEDOT:PSS, spiro-OMeTAD, PTAA, etc.) which are easy to decompose and have high cost as a hole transport layer, so as to effectively improve the carrier mobility and stability of the perovskite solar cell. However, the inorganic hole transport layer has the disadvantages of low conductivity, more surface defects and difficulty in supporting a perovskite film thick enough, which leads to low fill factor (FF) and current density (Jsc) of the perovskite solar cell, thereby limiting the photoelectric conversion efficiency of the cell. Therefore, it is imperative to design a new type of inorganic hole transport layer and modify it, so as to improve the interface between the hole transport layer and the perovskite absorption layer and optimize the crystal grains of the perovskite.
[0003] Some existing technologies, such as using an organic polymer as an interface modification layer coated on the hole transport layer and doping the hole transport layer, can only improve one of the efficiency and stability of the perovskite solar cell, and cannot take both into account. SUMMARY
[0004] The technical problem to be solved by the application is to provide a perovskite solar cell based on hole transport layer modification and a preparation method thereof. The rare earth metal is added to an inorganic hole transport material precursor solution by taking advantage of the characteristic that the rare earth metal is enriched on the surface of the inorganic hole transport material. The concentration gradient distribution of the rare earth metal in the hole transport layer is controlled through a reaction process, so as to gradually react to form a composite film layer with a bottom layer of a hole transport layer, an intermediate layer of a hole transport layer doped with rare earth metal ions and an upper layer of a hole transport modification layer. The energy level and surface defects of the original inorganic hole transport layer can be greatly optimized. The hole transport modification layer formed in situ is very dense and belongs to a semiconductor material, can form a heterojunction with the perovskite, promotes the efficient transport of carriers, and thus improves the photoelectric conversion efficiency and stability of the perovskite solar cell.
[0005] The application is implemented by providing a perovskite solar cell based on hole transport layer modification, the internal structure of which comprises, from bottom to top, a transparent substrate, a conductive layer, a hole transport layer, a perovskite layer, an electron transport layer and a back electrode layer, and a hole transport layer doped with rare earth metal ions and a hole transport modification layer are further arranged between the hole transport layer and the perovskite layer, the perovskite layer is arranged on the surface of the hole transport modification layer, the hole transport modification layer is arranged between the hole transport layer doped with rare earth metal ions and the perovskite layer, and the hole transport layer doped with rare earth metal ions is arranged between the hole transport layer and the hole transport modification layer.
[0006] Further, the rare earth metal ions are at least one of divalent or trivalent ions of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).
[0007] Further, the hole transport layer is prepared from any one of metal oxides, metal thiocyanates, metal sulfides and metal iodides.
[0008] Further, the hole transport modification layer is a thin film layer formed by a compound with a molecular formula of REMO y wherein RE is a rare earth metal ion, M is a metal ion in the hole transport layer preparation material, O is an oxygen ion, and y ranges from 1 to 5.
[0009] Further, the perovskite layer has a molecular structure formula of ABX3, wherein A is at least one monovalent anion of cesium, rubidium, an amine group, an amidine group and an alkali group, B is at least one divalent metal cation of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, and X is at least one anion of iodine, bromine, chlorine, astatine, thiocyanate and acetate.
[0010] Further, the electron transport layer is at least one of PCBM, SnO2, PCBM, C60, TiO2, ZnO and ZnO-ZnS.
[0011] Further, the back electrode is any one of silver, copper, gold and aluminum.
[0012] The application is implemented by further providing a preparation method of the perovskite solar cell based on hole transport layer modification as described above, comprising the following steps. Step one, the conductive layer prepared on the transparent substrate is cleaned with deionized water, acetone and isopropyl alcohol in sequence. Step two, the compound containing rare earth metal ions and the compound for preparing the hole transport layer are mixed in a molar ratio of 0.1 to 0.3 to prepare a hole transport precursor solution, the hole transport precursor solution is coated on the surface of the conductive layer by any one of the processing methods of slit continuous coating, spraying, printing, blade coating, spin coating, and electrochemical deposition, to obtain a hole transport precursor wet film, the transparent substrate coated with the hole transport precursor wet film is placed in a tube furnace, O2 gas and N2 gas are simultaneously introduced into the tube furnace, and heating and sintering are performed to form a composite film layer with a bottom layer of a hole transport layer, an intermediate layer of a hole transport layer doped with rare earth metal ions, and an upper layer of a hole transport modification layer; wherein the concentration of the hole transport precursor solution is in the range of 0.1 to 0.5 M, and the solvent of the hole transport precursor solution is at least one of isopropyl alcohol, 2-methoxy ethanol, ethanol, and tetrahydrofuran; Step three, a perovskite layer, an electron transport layer, and a back electrode layer are sequentially prepared on the surface of the hole transport modification layer to complete the preparation of the perovskite solar cell.
[0013] Further, in step two, the ratio of O2 gas to N2 gas is in the range of 0:10 to 3:7, the sintering temperature is 500℃ to 600℃, and the sintering time is 30min to 2h.
[0014] Further, in step two, the concentration of the precursor solution is in the range of 0.1 to 0.5 M, and the solvent of the precursor solution is a mixture of one or more of isopropyl alcohol, 2-methoxy ethanol, ethanol, and tetrahydrofuran.
[0015] The compound containing rare earth metal ions is mixed with the compound for preparing the hole transport layer to prepare a composite film layer with a bottom layer of a hole transport layer, an intermediate layer of a hole transport layer doped with rare earth metal ions, and an upper layer of a hole transport modification layer, wherein the hole transport layer doped with rare earth metal ions can greatly optimize the energy level and surface defects of the original inorganic hole transport layer, thereby optimizing the performance of the perovskite solar cell. y The hole transport modification layer is very dense and belongs to a semiconductor material, which can form a heterojunction with perovskite, promoting the efficient transport of carriers, thereby improving the photoelectric conversion efficiency and stability of the perovskite solar cell.
[0016] Compared with the prior art, the perovskite solar cell based on the modification of the hole transport layer and the preparation method thereof have the following advantages. BRIEF DESCRIPTION OF DRAWINGS
[0017] Figure 1 Structure diagram of a preferred embodiment of the perovskite solar cell based on the modification of the hole transport layer of the present application; Figure 2 Efficiency comparison diagram of the perovskite solar cells prepared in Example 1 and the comparative examples of the present application; Figure 3 Stability comparison diagram of the perovskite solar cells prepared in Example 1 and the comparative examples of the present application. DETAILED DESCRIPTION
[0018] In order to make the technical problems to be solved by the present application, the technical solutions and the beneficial effects more clearly understood, the present application will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application, and are not used to limit the present application.
[0019] Please refer to Figure 1 The preferred embodiment of the perovskite solar cell based on the modification of the hole transport layer of the present application has the following internal structure: a transparent substrate 1, a conductive layer 2, a hole transport layer 3, a perovskite layer 6, an electron transport layer 7 and a back electrode layer 8, which are sequentially arranged from bottom to top. A hole transport layer 4 doped with rare earth metal ions and a hole transport modification layer 5 are arranged between the hole transport layer 3 and the perovskite layer 6. The perovskite layer 6 is arranged on the surface of the hole transport modification layer 5. The hole transport modification layer 5 is arranged between the hole transport layer 4 doped with rare earth metal ions and the perovskite layer 6. The hole transport layer 4 doped with rare earth metal ions is arranged between the hole transport layer 3 and the hole transport modification layer 5.
[0020] The rare earth metal ion is at least one of divalent or trivalent ions of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).
[0021] The preparation material of the hole transport layer 3 is any one of metal oxide, metal thiocyanate, metal sulfide and metal iodide.
[0022] The hole transport modification layer 5 is a thin film layer formed by a compound with a molecular formula of REMO y The compound is formed by a compound with a molecular formula of REMO
[0023] The molecular structure of the perovskite layer 6 is ABX3, wherein A is at least one monovalent anion of cesium, rubidium, amine group, amidine group and alkali group, B is at least one divalent metal cation of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, and X is at least one anion of iodine, bromine, chlorine, astatine, thiocyanate, acetate.
[0024] The electron transport layer 7 is at least one of PCBM, SnO2, PCBM, C60, TiO2, ZnO and ZnO-ZnS.
[0025] The back electrode 8 is any one of silver, copper, gold and aluminum.
[0026] The application further discloses a preparation method of the perovskite solar cell based on the hole transport layer modification. Step one, the conductive layer 2 prepared on the transparent substrate 1 is sequentially cleaned by using deionized water, acetone and isopropyl alcohol.
[0027] Step two, the compound containing rare earth metal ions and the compound for preparing the hole transport layer 3 are mixed in a molar ratio of 0.1-0.3 to prepare a hole transport precursor solution, the hole transport precursor solution is coated on the surface of the conductive layer 2 by any one of the processing methods of slot die continuous coating, spraying, printing, blade coating, spin coating, and electrochemical deposition, to obtain a hole transport precursor wet film, the transparent substrate 1 coated with the hole transport precursor wet film is placed in a tube furnace, O2 gas and N2 gas are simultaneously introduced into the tube furnace, and sintering is performed to make the hole transport precursor wet film form a composite film layer with a bottom layer of the hole transport layer 3, a middle layer of the rare earth metal ion-doped hole transport layer 4, and an upper layer of the hole transport modification layer 5. Step three, a perovskite layer 6, an electron transport layer 7, and a back electrode layer 8 are sequentially prepared on the surface of the hole transport modification layer 5, and the preparation of the perovskite solar cell is completed. The concentration of the hole transport precursor solution is in the range of 0.1-0.5M, and the solvent of the hole transport precursor solution is at least one of isopropanol, 2-methoxyethanol, ethanol, and tetrahydrofuran.
[0028] In step two, the ratio of O2 gas to N2 gas is in the range of 0:10-3:7, the sintering temperature is 500-600℃, and the sintering time is 30min-2h.
[0029] The perovskite solar cell based on hole transport layer modification and the preparation method thereof of the present application will be further illustrated by specific examples. Example 1
[0030] The first embodiment of the preparation method of the perovskite solar cell based on hole transport layer modification of the present application comprises the following steps: Step 11, a 5*5cm FTO conductive layer 2 has been prepared on a glass plate of the transparent substrate 1, and the glass plate is ultrasonically cleaned with deionized water, acetone, and isopropanol for 30min each, dried with N2 blowing, and then treated with ultraviolet ozone for 10min.
[0031] Step 12, the hole transport layer 2, the rare earth metal ion-doped hole transport layer 4, and the REMO y Hole transport modification layer 5: 0.4mmol of nickel nitrate hexahydrate and 0.1mmol of lanthanum nitrate are dissolved in 1mL of ethanol solution and stirred for 30min, then the solution is dropped on the FTO conductive layer 2, spin-coated at a speed of 2000rpm / s for 30s, and after spin-coating, the glass plate is placed in a tube furnace with an atmosphere of O2:N2=1:9, and reacted at 500℃ for 30min, to obtain a composite film layer with a bottom layer of NiO x Hole transport layer 3, middle layer of rare earth metal ion-doped hole transport layer 4, and upper layer of LaNiO3 hole transport modification layer 5.
[0032] Step 13, preparing perovskite layer 6 on LaNiO3 hole transport modification layer 5: 1 mmol of FAI, 0.2 mmol of MABr, 0.2 mmol of PbBr2 and 1 mmol of PbI2 are added to 1 mL of mixed solution of DMF:DMSO=4:1 (v / v) to obtain perovskite precursor solution by stirring at room temperature for 2 h. Then 500 μL of the precursor solution is spin-coated on LaNiO3 hole transport modification layer 5 at a speed of 4500 r / s for 30 s, while 200 μL of filtered chlorobenzene solution is added dropwise at the 8th s of spin-coating. After spin-coating, the glass plate is placed on a hot stage at 100℃ for annealing for 20 min to obtain perovskite layer 6.
[0033] Step 14, preparing PCBM as electron transport layer 7 on perovskite layer 6.
[0034] Step 15, evaporating Ag back electrode layer 8 on electron transport layer 7 to complete the preparation of perovskite solar cell. Example 2
[0035] The second embodiment of the preparation method of perovskite solar cell based on hole transport layer modification of the application comprises the following steps: Step 21, a 5*5 cm glass plate with AZO conductive layer 2 prepared on the transparent substrate 1 is sequentially cleaned with deionized water, acetone and isopropanol for 30 min each, and then dried by N2 blowing and treated by ultraviolet ozone for 10 min.
[0036] Step 22, hole transport layer 2, hole transport layer 4 doped with rare earth metal ions and REMO y Hole transport modification layer 5: 1 mol of copper acetate and 0.3 mol of dysprosium acetate are dissolved in 100 mL of deionized water to prepare an electrolyte, which is then stirred for 30 min. The cleaned AZO conductive layer 2 is used as the working electrode, the Pt electrode is used as the counter electrode, and the saturated calomel electrode (SCE) is used as the reference electrode. The above electrolyte is subjected to ionization at a constant potential of -1 V (vs. SCE) for 60 s. The copper hydroxide and lanthanum hydroxide precursors on the AZO conductive layer 2 are carefully washed with deionized water. Then the glass plate is transferred to a tube furnace, annealed at 500℃ for 2 hours in N2 environment, to obtain a composite thin film layer with CuO x Hole transport layer 3, intermediate layer is hole transport layer doped with rare earth metal ions, and upper layer is Dy2Cu2O5 hole transport modification layer 5.
[0037] Step 23: Prepare perovskite layer 6 on Dy2Cu2O5 hole transport modified layer 5: Add 1 mmol of FAI, 0.2 mmol of MABr, 0.2 mmol of PbBr2 and 1 mmol of PbI2 to 1 mL of a mixed solution of DMF:DMSO = 4:1 (v / v) and stir at room temperature for 2 h to obtain perovskite precursor solution. Then take 500 μL of this precursor solution and spin-coat it onto Dy2Cu2O5 hole transport modified layer 5 at a speed of 4500 r / s for 30 s. At the same time, add 200 μL of filtered chlorobenzene solution dropwise when spin-coating reaches the 8th s mark. After spin-coating is completed, place it on a hot plate at 100℃ and anneal for 20 min to obtain perovskite layer 6.
[0038] Step 24: Prepare C60 as electron transport layer 7 on the perovskite layer 6.
[0039] Step 25: Deposit Au back electrode layer 8 on electron transport layer 7 to complete the fabrication of perovskite solar cell.
[0040] Comparative Example Perovskite solar cells were prepared according to the method of Example 1, except that lanthanum nitrate was not added in step 12, and the other steps were the same as in Example 1.
[0041] The perovskite solar cells prepared in Example 1 and the comparative example were subjected to performance tests, and the results were as follows: Figure 2 The efficiency comparison chart shown and Figure 3 The stability comparison chart is shown.
[0042] like Figure 2 As shown, the perovskite solar cell prepared in Example 1 achieved a photoelectric conversion efficiency of 18.3%, while the unmodified perovskite solar cell in the comparative example had a photoelectric conversion efficiency of only 16.1%. Figure 3 As shown, when the UV aging energy reaches 106 kWh, the perovskite solar cell prepared in Example 1 can still retain 92% of its initial efficiency, while the perovskite solar cell prepared in the comparative example only retains 43%. This demonstrates that the present invention can indeed effectively improve the photoelectric conversion efficiency and stability of perovskite solar cells, achieving the expected results.
[0043] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A perovskite solar cell based on modification of hole transport layer, the internal structure of which comprises, from bottom to top in sequence, a transparent substrate, a conductive layer, a hole transport layer, a perovskite layer, an electron transport layer and a back electrode layer, characterized in that, The perovskite layer is arranged on the surface of the hole transport modification layer. 2.The perovskite solar cell based on modification of hole transport layer according to claim 1, wherein, The rare earth metal ion is at least one of divalent or trivalent ions of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. 3.The perovskite solar cell based on modification of hole transport layer according to claim 2, wherein, The preparation material of the hole transport layer is any one of metal oxide, metal thiocyanate, metal sulfide and metal iodide. 4.The perovskite solar cell based on modification of hole transport layer according to claim 3, wherein, The hole transport modification layer is a thin film layer formed by a compound with a molecular formula of REMO y wherein RE is a rare earth metal ion, M is a metal ion in a hole transport layer preparation material, O is an oxygen ion, and y is in a range of 1 to 5. 5.The perovskite solar cell based on modification of hole transport layer according to claim 1, wherein, The molecular structure of the perovskite layer is ABX3, wherein A is at least one monovalent anion of cesium, rubidium, amine group, amidine group and alkali group, B is at least one divalent metal cation of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, and X is at least one anion of iodine, bromine, chlorine, astatine, thiocyanate and acetate. 6.The perovskite solar cell based on modification of hole transport layer according to claim 1, wherein, The electron transport layer is at least one of PCBM, SnO2, PCBM, C60, TiO2, ZnO and ZnO-ZnS. 7.The perovskite solar cell based on modification of hole transport layer according to claim 1, wherein, The back electrode is any one of silver, copper, gold and aluminum.
8. A method for producing the perovskite solar cell based on a modification of a hole transport layer according to any one of claims 1 to 7, characterized by, The method comprises the following steps: Step one, the conductive layer prepared on the transparent substrate is sequentially cleaned with deionized water, acetone and isopropanol; Step two, a compound containing a rare earth metal ion is mixed with a compound for preparing a hole transport layer at a molar ratio of 0.1 to 0.3 to prepare a hole transport precursor solution, the hole transport precursor solution is coated on the surface of the conductive layer by any one of slot die continuous coating, spraying, printing, blade coating, spin coating and electrochemical deposition to obtain a hole transport precursor wet film, the transparent substrate coated with the hole transport precursor wet film is placed in a tube furnace, O2 gas and N2 gas are simultaneously introduced into the tube furnace, and heating and sintering are performed to form a composite film layer with a bottom layer of a hole transport layer, an intermediate layer of a hole transport layer doped with a rare earth metal ion and an upper layer of a hole transport modification layer; wherein the concentration of the hole transport precursor solution ranges from 0.1 to 0.5 M, and the solvent of the hole transport precursor solution is at least one of isopropanol, 2-methoxyethanol, ethanol and tetrahydrofuran; Step three, a perovskite layer, an electron transport layer and a back electrode layer are sequentially prepared on the surface of the hole transport modification layer to complete the preparation of the perovskite solar cell. 9.The method of claim 8, wherein the perovskite solar cell is modified with a hole transport layer. In step two, the ratio of O2 gas to N2 gas ranges from 0:10 to 3:7, the heating and sintering temperature ranges from 500°C to 600°C, and the sintering time ranges from 30 minutes to 2 hours. 10.The method of claim 8, wherein the perovskite solar cell is modified with a hole transport layer. In step two, the concentration of the precursor solution ranges from 0.1 to 0.5 M, and the solvent of the precursor solution is a mixture of one or more of isopropanol, 2-methoxyethanol, ethanol and tetrahydrofuran.