Multi-layer composite transport layer, perovskite solar module and method for manufacturing same

Abstract

The present invention relates to a multilayer composite transport layer, which includes a barrier transition layer, a transition layer, a hole transport layer, and a buffer layer, which are sequentially stacked according to the direction of incident light. The barrier transition layer is made of a fluorine-doped tin oxide material doped with an R element instead of an F element, and the R element is substituted for the F element in a ratio of 1% to 100%. The R element is at least one element selected from the group consisting of W, Nb, Ni, Al, and Si. The transition layer is made of a fluorine-doped tin oxide material doped with an R element instead of an F element. x A y SI z Sn m O n , or Cu x A y SI z Sn m O n (where x>0, y>=0, z>=0, m>=0, n>0, and A is aluminum or boron.) The manufacturing material of the hole transport layer is NIO x , Cu x The buffer layer is made of either NI or CuSCN. a E b N c O d , or Cu a E b N c O d (wherein a>0, b>=0, c>0, d>=0, and E is any one of Al, B, Si, Zn, Co, and Zr.) The present invention further discloses a perovskite solar module using the multilayer composite transport layer and a method for manufacturing the same. The perovskite solar module of the present invention is characterized by both high conversion efficiency and good long-term photothermal stability.

Description

[Technical Field]

[0001] The present invention belongs to the technical field of perovskite solar module manufacturing, and particularly relates to a multi-layer composite transport layer, a perovskite solar module and a manufacturing method thereof. [Background technology]

[0002] Common device structures for perovskite solar modules include positive-type and negative-type structures. A positive-type structure includes, from the light-incident surface, at least a transparent conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer, and a back electrode, in that order. A negative-type structure includes, from the light-incident surface, at least a transparent conductive layer, a hole transport layer, a perovskite active layer, an electron transport layer, and a back electrode, in that order. The maximum conversion efficiency of negative-type perovskite solar modules is slightly lower than that of positive-type perovskite solar modules, but the overall stability of the negative-type structure has been reported to be superior to that of positive-type structures. The main reasons for the low conversion efficiency of negative-type structures are generally believed to be the energy band mismatch at the first interface formed by the transparent conductive layer and the hole transport layer and the numerous interfacial defects at the second interface formed by the hole transport layer and the perovskite active layer.

[0003] Materials available for the hole transport layer are generally classified into three types: 1) inorganic oxides or inorganic salts, 2) organic polymers, and 3) organic small molecules. Among these, a representative choice for the first type of inorganic oxide or inorganic salt is NIO. x , V2O5, CuO, CuSCN, etc.; representative choices for the second type of organic polymers include P3HT, PTAA, etc.; representative choices for the third type of organic small molecules include spIro-OMeTAD and PAC zThese include self-assembled materials based on the NIO system. The first type of materials are readily available and low-cost, but their good hole transport performance comes from defects in the material itself, and a relatively high defect density is often required to achieve better hole transport performance. The relatively high defect density reduces the photothermal stability of the second interface between the hole transport layer and the perovskite active layer, making it difficult to achieve both high conversion efficiency and good stability. x For example, to improve hole mobility, uncoordinated NI 3+ It is necessary to increase the concentration of NI. 3+ is NIO x The second type of materials generally have the advantage of a long synthesis route, relatively good hole transport properties, and ease of obtaining negative-type devices with high conversion efficiencies. However, their greatest drawback is the low photostability of the polymer materials themselves, which easily decomposes under long-term outdoor light exposure, resulting in a rapid degradation of the performance of negative-type devices. The third type of materials can further improve the conversion efficiency of negative-type devices based on the second type of materials. However, like the second type of materials, they contain organic materials, which result in poor stability under long-term light exposure. To address these issues, methods such as using a composite structure of an inorganic hole transport layer and an organic hole transport layer or passivating the inorganic hole transport layer have been reported. However, the use of a composite structure of an inorganic hole transport layer and an organic hole transport layer is not an effective solution because the organic layer decomposes under long-term light exposure, eliminating the effectiveness of this composite structure. Passivating the inorganic hole transport layer often sacrifices conversion efficiency in exchange for improved stability, so this is only a temporary solution.

[0004] In addition, common transparent conductive layer materials, such as fluorine-doped tin oxide (FTO), are often doped with high concentrations of fluorine elements, which may migrate into the perovskite material during long-term use, causing the decomposition of the perovskite material and reducing the stability of the perovskite solar module, potentially shortening its service life.

[0005] In addition, existing hole transport layers are generally made from inorganic oxides, but hole transport layers made from inorganic oxides have the following problems: 1) The structure of inorganic oxides can be too dense, which can cause problems with hole transport. 2) Inorganic nanocrystals tend to aggregate during long-term use due to charge imbalance caused by surface defects. This aggregation affects the stability of the material. 3) There are many disordered dangling bonds on the surface of the inorganic interface, some of which react with the perovskite material. Summary of the Invention [Problem to be solved by the invention]

[0006] The technical problem to be solved by the present invention is to provide a multi-layer composite transport layer, a perovskite solar module, and a manufacturing method thereof, and the use of the multi-layer composite transport layer not only significantly improves the photostability of the perovskite solar module, but also improves the conversion efficiency of the perovskite solar module. Meanwhile, the doping of the manufacturing material of the multi-layer composite transport layer with a coupling agent improves the conductivity and stability of the hole transport layer made of inorganic oxide materials, so that the manufactured perovskite solar module has both high conversion efficiency and good stability. [Means for solving the problem]

[0007] The present invention is realized as follows: A semiconductor device includes a barrier transition layer, a transition layer, a hole transport layer, and a buffer layer, which are sequentially stacked according to the direction of incident light, and the barrier transition layer is made of a fluorine-doped tin oxide material doped with an R element instead of an F element, and the R element is at least one element selected from the group consisting of W, Nb, Ni, Al, and Si. The transition layer is made of a material selected from the group consisting of Ni, x A y SI z Sn m O n , or Cu x A y SI z Sn m On (where x>0, y>=0, z>=0, m>=0, n>0, and A is aluminum or boron.) The transition layer is made of a material containing at least one element selected from the group consisting of A, SI, and Sn. The hole transport layer is made of a material containing NIO x , Cu x The buffer layer is made of either NI or CuSCN. a E b N c O d , or Cu a E b N c O d (where a>0, b>=0, c>0, d>=0, and E is any one of the elements Al, B, Si, Zn, Co, and Zr.)

[0008] The present invention is realized as follows: A semiconductor device includes a barrier transition layer, a transition layer, a hole transport layer, and a buffer layer, which are sequentially stacked according to the direction of incident light, and the barrier transition layer is made of a fluorine-doped tin oxide material doped with an R element instead of an F element, and the R element is at least one element selected from the group consisting of W, Nb, Ni, Al, and Si. The transition layer is made of a material selected from the group consisting of Ni, x A y SI z Sn m O n , or Cu x A y SI z Sn m O n (where x>0, y>=0, z>=0, m>=0, n>0, and A is aluminum or boron.) The transition layer is made of a material containing at least one element selected from the group consisting of A, SI, and Sn. The hole transport layer is made of a material containing NIO x , Cu x The buffer layer is made of either NI or CuSCN. a E b N c O d , or Cua E b N c O d (wherein a>0, b>=0, c>0, d>=0, and E is any one of Al, B, SI, Zn, Co, and Zr), and a coupling agent is added to and doped into the manufacturing material of at least one of the barrier transition layer, transition layer, and buffer layer to obtain a corresponding coupling agent-containing array barrier transition layer and / or array transition layer and / or array buffer layer, and the thin film of the coupling agent-doped barrier transition layer, transition layer, and / or buffer layer includes a plurality of discretely arranged coupling agent-containing array molecular clusters and openings each having two adjacent molecular clusters, the openings connecting the upper and lower surfaces of the thin film, and the coupling agent is any one of a silane coupling agent, a cyanate coupling agent, an aluminate coupling agent, a phosphate coupling agent, and a borate coupling agent, and the length of the openings is 10 nm to 200 nm.

[0009] The present invention further provides a first type of perovskite solar module, the internal structure of which includes a sequentially stacked transparent conductive layer, a perovskite light-absorbing layer, an electron transport layer, and a back electrode, wherein the first type of multi-layer composite transport layer is disposed between the transparent conductive layer and the perovskite light-absorbing layer, the barrier transition layer of the multi-layer composite transport layer and the transparent conductive layer are in close contact, and the buffer layer of the multi-layer composite transport layer and the perovskite light-absorbing layer are in close contact.

[0010] The present invention further provides a second type of perovskite solar module, the internal structure of which includes a sequentially stacked transparent conductive layer, a perovskite light-absorbing layer, an electron transport layer, and a back electrode, wherein the second type of multi-layer composite transport layer is disposed between the transparent conductive layer and the perovskite light-absorbing layer, the barrier transition layer of the multi-layer composite transport layer and the transparent conductive layer are in close contact, and the buffer layer of the multi-layer composite transport layer and the perovskite light-absorbing layer are in close contact.

[0011] The present invention is realized as follows. Step 1: Clean the transparent conductive layer and treat it with ultraviolet light and ozone. Step 2 of fabricating a barrier transition layer on the transparent conductive layer using a vapor phase method or a liquid phase method, in which the vapor phase method is fabricating the transition layer using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; Step 3: forming a transition layer on the barrier-transition layer using a vapor phase method or a liquid phase method, in which the vapor phase method is formed using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; Step 4: forming a hole transport layer on the surface of the transition layer using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, or forming the hole transport layer by any one of a solution doctor blade coating, a slit coating, and a spray coating; Step 5: forming a buffer layer on the surface of the hole transport layer by a vapor or liquid phase method, wherein in the vapor phase method, the transition layer is formed by using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; and step 6 of sequentially fabricating a perovskite light-absorbing layer, an electron transport layer, and a back electrode on the surface of the buffer layer until the fabrication of the perovskite solar module is completed.

[0012] The present invention is realized as follows. Step I: cleaning the transparent conductive layer and treating it with ultraviolet light and ozone; Step II, in which a barrier transition layer is formed on the transparent conductive layer using a vapor phase or liquid phase method, in which the vapor phase method is formed using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; Step III: mixing a coupling agent with a solution of a material for preparing a transition layer to obtain a first composite precursor solution; irradiating the first composite precursor solution with UV light or treating it at high temperature; then coating the treated first composite precursor solution on the surface of the barrier transition layer, and annealing and drying it to obtain an array transition layer; Step IV: forming a hole transport layer on the surface of the array transition layer using any one of an ALD apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, or forming a hole transport layer by any one of doctor blade coating, slit coating, and spray coating; Step V is a step of forming a buffer layer on the surface of the hole transport layer by a vapor or liquid phase method, in which the vapor phase method is an atomic layer deposition (ALD) system, a chemical vapor deposition (CVD) system, a magnetron sputtering system, an electron beam evaporation system, or a thermal evaporation system to form the transition layer, and the liquid phase method is a mixed solution method, a hydrothermal method, a chemical bath method, or an in-situ doping method; and Step VI of sequentially fabricating a perovskite light-absorbing layer, an electron transport layer, and a back electrode on the surface of the buffer layer until the fabrication of the perovskite solar module is completed.

[0013] The present invention is realized as follows. Step 1: Clean the transparent conductive layer and treat it with ultraviolet light and ozone. Step 2 of forming a barrier transition layer on the transparent conductive layer using a vapor phase method or a liquid phase method, in which the vapor phase method is formed using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; Step 3: forming a transition layer on the barrier-transition layer using a vapor phase method or a liquid phase method, in which the vapor phase method is formed using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; Step 4: forming a hole transport layer on the surface of the transition layer using any one of an ALD apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, or forming the hole transport layer by any one of a solution doctor blade coating, a slit coating, and a spray coating; Step 5: mixing a coupling agent with a solution of a material for preparing a buffer layer to obtain a second composite precursor solution, irradiating the second composite precursor solution with UV light or treating it at high temperature, and then coating the treated second composite precursor solution on the surface of the hole transport layer, followed by annealing and drying to obtain an array buffer layer; and step 6 of sequentially fabricating a perovskite light-absorbing layer, an electron transport layer, and a back electrode on the surface of the array buffer layer until the fabrication of the perovskite solar module is completed.

[0014] The present invention is realized as follows. Step A is to clean the transparent conductive layer and treat it with ultraviolet light and ozone; Step B: mixing a coupling agent with a solution of materials for preparing a barrier transition layer to obtain a third composite precursor solution; irradiating the third composite precursor solution with UV light or treating it at high temperature; and then coating the treated third composite precursor solution on the surface of the transparent conductive layer, followed by annealing and drying to obtain an array barrier transition layer; Step C of forming a transition layer on the barrier-transition layer using a vapor phase method or a liquid phase method, in which the vapor phase method is formed using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; Step D: forming a hole transport layer on the surface of the transition layer using any one of an ALD apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, or forming a hole transport layer by any one of a solution doctor blade coating, a slit coating, and a spray coating; Step E of forming a buffer layer on the surface of the hole transport layer by a vapor phase method or a liquid phase method, in which in the vapor phase method, the buffer layer is formed by using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and in which the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; and step F of sequentially fabricating a perovskite light-absorbing layer, an electron transport layer, and a back electrode on the surface of the buffer layer until the fabrication of the perovskite solar module is completed. [Effects of the Invention]

[0015] Compared with the prior art, in the first type of multi-layer composite transport layer, perovskite solar module and manufacturing method thereof of the present invention, the multi-layer composite transport layer includes a barrier transition layer, a transition layer, a hole transport layer and a buffer layer, which are stacked in order according to the incident direction of light. The material for the barrier transition layer is a fluorine-doped tin oxide material doped with an R element instead of an F element, and the ratio of the R element to the F element ranges from 1% to 100%, and the R element is at least one element selected from the group consisting of W, Nb, Ni, Al and Si. The material for the transition layer is Ni. x A y SI z Sn m O n , or Cu x A y SI z Sn m O n (where x>0, y>=0, z>=0, m>=0, n>0, and A is aluminum or boron.) The transition layer is made of a material containing at least one element selected from the group consisting of A, SI, and Sn. The hole transport layer is made of a material containing NIO x , Cu x The buffer layer is made of either NI or CuSCN. a E b N c O d , or Cu a E b N c O d (wherein a>0, b>=0, c>0, d>=0, and E is any one of Al, B, Si, Zn, Co, and Zr.) The perovskite solar module of the present invention uses the multilayer composite transport layer, and the hole transport material maintains a high defect density and high hole mobility, so that the perovskite solar module including the multilayer composite transport layer has both high conversion efficiency and good long-term photothermal stability.

[0016] Meanwhile, compared with the prior art, in the second type of multi-layer composite transport layer, perovskite solar module and manufacturing method thereof of the present invention, the multi-layer composite transport layer includes a barrier transition layer, a transition layer, a hole transport layer and a buffer layer, which are sequentially stacked according to the direction of light incidence. The manufacturing material of the barrier transition layer is a fluorine-doped tin oxide material doped with an R element instead of an F element, and the ratio of the R element to the F element ranges from 1% to 100%, and the R element is at least one element selected from the group consisting of W, Nb, Ni, Al and Si. The manufacturing material of the transition layer is Ni. x A y SI z Sn m O n , or Cu x A y SI z Sn m O n (where x>0, y>=0, z>=0, m>=0, n>0, and A is aluminum or boron.) The transition layer is made of a material containing at least one element selected from the group consisting of A, SI, and Sn. The hole transport layer is made of a material containing NIO x , Cu x The buffer layer is made of either NI or CuSCN. a E b N c O d , or Cu a E b N c O d(where a>0, b>=0, c>0, d>=0, and E is any one of Al, B, SI, Zn, Co, and Zr.) A coupling agent is added to and doped into the manufacturing material of at least one of the barrier transition layer, transition layer, and buffer layer to obtain a corresponding coupling agent-containing array barrier transition layer and / or array transition layer and / or array buffer layer, and the thin film of the coupling agent-doped barrier transition layer and / or transition layer and / or buffer layer includes a plurality of discretely arranged coupling agent-containing array molecular clusters and openings where two adjacent molecular clusters are located, and the openings communicate with the upper and lower surfaces of the thin film. The coupling agent is any one of a silane coupling agent, a cyanate coupling agent, an aluminate coupling agent, a phosphate coupling agent, and a borate coupling agent. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 is a schematic plan view of the internal structure of one preferred embodiment of the first type of perovskite solar module of the present invention. [Figure 2] FIG. 2 is a schematic plan view of an example of the internal structure of a second type of perovskite solar module of the present invention. [Figure 3] FIG. 2 is a schematic plan view of another internal structure of the second type of perovskite solar module of the present invention. [Figure 4] FIG. 2 is a schematic plan view of yet another internal structure of the second type of perovskite solar module of the present invention. [Figure 5] FIG. 4 is a perspective schematic diagram of a multi-layer composite transport layer of another internal structure of the second type perovskite solar module in FIG. 3. [Figure 6] FIG. 2 is a schematic diagram comparing the conversion efficiency curves of the perovskite solar module manufactured in Example 1 of the present invention and the perovskite solar module of Comparative Example 1. [Figure 7] FIG. 2 is a schematic diagram comparing the conversion efficiency curves of the perovskite solar module produced in Example 1 of the present invention and the perovskite solar modules of Comparative Examples 2 and 3. [Figure 8] FIG. 2 is a diagram comparing the photoaging of the perovskite solar module produced in Example 1 of the present invention with the perovskite solar modules of Comparative Examples 1 to 3. [Figure 9] FIG. 2 is a schematic diagram comparing the conversion efficiency curves of the perovskite solar module manufactured in Example 3 of the present invention with those of the perovskite solar modules of Comparative Examples 1, 4, and 5. [Figure 10] FIG. 2 is a schematic diagram comparing the aging curves of the perovskite solar module produced in Example 3 of the present invention with those of the perovskite solar modules of Comparative Examples 1, 4, and 5. DETAILED DESCRIPTION OF THE INVENTION

[0018] In order to clarify the technical problems to be solved, the technical solutions and the beneficial effects of the present invention, the present invention will be described in more detail below with reference to the drawings and examples. It should be understood that the specific examples described herein are for the purpose of illustrating the present invention and are not intended to limit the present invention.

[0019] As shown in Figure 1, a preferred embodiment of the first type of multilayer composite transport layer of the present invention includes a barrier transition layer 1, a transition layer 2, a hole transport layer 3, and a buffer layer 4, which are sequentially stacked according to the direction of light incidence. The barrier transition layer 1 is made of a fluorine-doped tin oxide material doped with an R element instead of an F element, and the ratio of the R element to the F element ranges from 1% to 100%, and the R element is at least one element selected from the group consisting of W, Nb, Ni, Al, and Si. The transition layer 2 is made of Ni. x A y SI z Sn m O n , or Cu x A y SI z Sn m O n(where x>0, y>=0, z>=0, m>=0, n>0, and A is aluminum (Al) or boron (B).) The transition layer 2 is made of a material containing at least one element selected from the group consisting of A, SI, and Sn. The hole transport layer 3 is made of a material containing NIO x , Cu x The buffer layer 4 is made of one of Ni, O, and CuSCN. a E b N c O d , or Cu a E b N c O d , (where a>0, b>=0, c>0, d>=0, and E is any one of the elements Al, B, Si, Zn, Co, and Zr.)

[0020] 2 to 4, a preferred embodiment of the second type of multilayer composite transport layer of the present invention includes a barrier transition layer 1, a transition layer 2, a hole transport layer 3, and a buffer layer 4, which are sequentially stacked according to the direction of light incidence. The barrier transition layer 1 is made of a fluorine-doped tin oxide material doped with an R element instead of an F element, and the ratio of the R element to the F element ranges from 1% to 100%, and the R element is at least one element selected from the group consisting of W, Nb, Ni, Al, and Si. The transition layer 2 is made of Ni. x A y SI z Sn m O n , or Cu x A y SI z Sn m O n (where x>0, y>=0, z>=0, m>=0, n>0, and A is aluminum or boron.) The material for manufacturing the transition layer 2 contains at least one element selected from the group consisting of A, Si, and Sn. The material for manufacturing the hole transport layer 3 is NIO x , Cu x The buffer layer 4 is made of one of Ni, O, and CuSCN. a E b N c O d, or Cu a E b N c O d (where a>0, b>=0, c>0, d>=0, and E is any one of the elements Al, B, Si, Zn, Co, and Zr.)

[0021] A coupling agent is further added to and doped into the manufacturing material of at least one of the barrier transition layer 1, transition layer 2, and buffer layer 4, to obtain a corresponding array barrier transition layer and / or array transition layer and / or array buffer layer containing a coupling agent. The thin film of the barrier transition layer 1, transition layer 2, and / or buffer layer 4 doped with the coupling agent includes a plurality of discretely arranged coupling agent-containing array molecular clusters 11 and an opening 10 between two adjacent molecular clusters, and the opening 10 connects the upper and lower surfaces of the thin film in which it is located. The coupling agent is any one of a silane coupling agent, a cyanate coupling agent, an aluminate coupling agent, a phosphate coupling agent, and a borate coupling agent.

[0022] Specifically, the amount of the coupling agent added is 0.5 to 5% of the volume of the nanoparticle suspension used to produce the barrier transition layer 1 and / or transition layer 2 and / or buffer layer 3, and the concentration of the nanoparticle suspension is 0.1 to 10 wt.%.

[0023] Specifically, the length of the opening 10 is 10 nm to 200 nm.

[0024] Specifically, in the first type multilayer composite transport layer and the second type multilayer composite transport layer of the present invention, the thickness of the barrier transition layer 1 is 1 nm to 30 nm, the thickness of the transition layer 2 is 0.2 nm to 30 nm, the thickness of the hole transport layer 3 is 1 nm to 100 nm, and the thickness of the buffer layer 4 is 0.2 nm to 50 nm.

[0025] Furthermore, as shown in Figure 1, the present invention further discloses a first type of perovskite solar module, whose internal structure includes a transparent conductive layer 6, a perovskite light-absorbing layer 7, an electron transport layer 8, and a back electrode 9, which are sequentially stacked. The first type of multilayer composite transport layer 5 is disposed between the transparent conductive layer 6 and the perovskite light-absorbing layer 7. The barrier transition layer 1 and the transparent conductive layer 6 of the multilayer composite transport layer 5 are in close contact with each other, and the buffer layer 4 and the perovskite light-absorbing layer 7 are in close contact with each other. The transition layer 2 and the hole transport layer 3 of the multilayer composite transport layer 5 are disposed between the barrier transition layer 1 and the buffer layer 4, and the transition layer 2 and the barrier transition layer 1 are in close contact with each other, and the hole transport layer 3 and the buffer layer 4 are in close contact with each other.

[0026] 2 to 4, the present invention further discloses a second type of perovskite solar module, in which the internal structure includes a transparent conductive layer 6, a perovskite light-absorbing layer 7, an electron transport layer 8, and a back electrode 9, which are sequentially stacked. The second type of multilayer composite transport layer 5 is disposed between the transparent conductive layer 6 and the perovskite light-absorbing layer 7. The barrier transition layer 1 and the transparent conductive layer 6 of the multilayer composite transport layer 5 are in close contact with each other, and the buffer layer 4 and the perovskite light-absorbing layer 7 are in close contact with each other. The transition layer 2 and the hole transport layer 3 of the multilayer composite transport layer 5 are disposed between the barrier transition layer 1 and the buffer layer 4, and the transition layer 2 and the barrier transition layer 1 are in close contact with each other, and the hole transport layer 3 and the buffer layer 4 are in close contact with each other.

[0027] In the first and second type perovskite solar modules of the present invention, the molecular formula of the material making up the perovskite light-absorbing layer 7 is ABX3, where A is at least one cation selected from the group consisting of cesium, rubidium, amines, amidines, and bases; B is any one divalent metal cation selected from the group consisting 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 any one anion selected from the group consisting of iodine, bromine, chlorine, astatine, thiocyanate, and acetate.

[0028] The multi-layer composite transport layer of the second type of perovskite solar module of the present invention has the following characteristics: First, the nanoparticles simply form openings during coating, solving the problem of an overly dense inorganic oxide layer structure. This eliminates the influence of the thickness of the transition and buffer layers on the electrical tunneling effect, reducing non-radiative recombination at the interface between the perovskite light-absorbing layer and the hole-transporting layer without affecting carrier transport. 2. Inorganic nanocrystals tend to aggregate during long-term use due to charge imbalances caused by surface defects. This aggregation affects the stability of the material. The adhesive and dispersing properties of coupling agents prevent this phenomenon, improving the stability of materials and devices. 3. There are many irregular dangling bonds at the interface of inorganic materials. By using a coupling agent, the dangling bonds on the surface of the inorganic material can be passivated, suppressing the photocatalytic reaction at the interface between the inorganic material and perovskite, and further improving stability.

[0029] Furthermore, with reference to FIG. 1 , the present invention further discloses a method for manufacturing said first type of perovskite solar module, comprising the steps of: Step 1: The transparent conductive layer 6 is cleaned and treated with ultraviolet light and ozone. Step 2: Fabricate the barrier transition layer 1 on the transparent conductive layer 6 using a vapor or liquid phase method. In the vapor phase method, the transition layer is fabricated using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus. In the liquid phase method, the processing method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method. Step 3: The transition layer 2 is fabricated on the barrier transition layer 1 using a gas phase method or a liquid phase method. In the gas phase method, the transition layer is fabricated using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus. In the liquid phase method, the transition layer is fabricated using any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method. Step 4: The hole transport layer 3 is fabricated on the surface of the transition layer 2 using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, or by any one of a solution doctor blade coating, a slit coating, and a spray coating method. Step 5: A buffer layer 4 is fabricated on the surface of the hole transport layer 3 using a gas phase or liquid phase method. In the gas phase method, the transition layer is fabricated using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus. In the liquid phase method, the processing method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method. Step 6: Sequentially fabricate the perovskite light-absorbing layer 7, the electron transport layer 8, and the back electrode 9 on the surface of the buffer layer 4 until completing the fabrication of the perovskite solar module.

[0030] Furthermore, as shown in FIG. 2, the present invention further discloses a method for manufacturing the second type of perovskite solar module, including the following steps: Step I: The transparent conductive layer 6 is washed and treated with ultraviolet light and ozone. Step II: The barrier transition layer 1 is fabricated on the transparent conductive layer 6 using a vapor or liquid phase method. In the vapor phase method, the barrier transition layer 1 is fabricated using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus. In the liquid phase method, the barrier transition layer 1 is fabricated using any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method. Step III: Mix a coupling agent with a solution of the material for producing the transition layer 2 to obtain a first composite precursor liquid, irradiate the first composite precursor liquid with UV light or treat it at high temperature, and then coat the treated first composite precursor liquid on the surface of the barrier transition layer 1, anneal and dry it to obtain the array transition layer 2. Step IV: The hole transport layer 3 is fabricated on the surface of the transition layer 2 using any one of an ALD apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, or by any one of a solution doctor blade coating, a slit coating, and a spray coating method. Step V: A buffer layer 4 is fabricated on the surface of the hole transport layer 3 using a gas phase method or a liquid phase method. In the gas phase method, the transition layer 4 is fabricated using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus. In the liquid phase method, the processing method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method. Step VI: Sequentially fabricate the perovskite light-absorbing layer 7, the electron transport layer 8, and the back electrode 9 on the surface of the buffer layer 4 until completing the fabrication of the perovskite solar module.

[0031] Furthermore, as shown in FIG. 3, the present invention further discloses a method for manufacturing the second type of perovskite solar module, including the following steps: Step 1: The transparent conductive layer 6 is cleaned and treated with ultraviolet light and ozone. Step 2: The barrier transition layer 1 is fabricated on the transparent conductive layer 6 using a vapor or liquid phase method. In the vapor phase method, the barrier transition layer 1 is fabricated using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus. In the liquid phase method, the barrier transition layer 1 is fabricated using any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method. Step 3: The transition layer 2 is fabricated on the barrier transition layer 1 using a gas phase method or a liquid phase method. In the gas phase method, the transition layer 2 is fabricated using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus. In the liquid phase method, the transition layer 2 is fabricated using any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method. Step 4: The hole transport layer 3 is fabricated on the surface of the transition layer 2 using any one of an ALD apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, or by any one of a solution doctor blade coating, a slit coating, and a spray coating method. Step 5: Mix the coupling agent with the solution of the material for preparing the buffer layer 4 to obtain a second composite precursor solution, irradiate the second composite precursor solution with UV light or treat it at high temperature, and then coat the treated second composite precursor solution on the surface of the hole transport layer 3, anneal and dry it to obtain the array buffer layer 4. Step 6: Sequentially fabricate the perovskite light-absorbing layer 7, the electron transport layer 8, and the back electrode 9 on the surface of the buffer layer 4 until completing the fabrication of the perovskite solar module.

[0032] Furthermore, as shown in FIG. 4, the present invention further discloses a method for manufacturing the second type of perovskite solar module, including the following steps: Step A: The transparent conductive layer 6 is washed and treated with ultraviolet light and ozone. Step B: Mix a coupling agent with a solution of materials for preparing the barrier transition layer 1 to obtain a third composite precursor solution, irradiate the third composite precursor solution with UV light or treat it at high temperature, and then coat the treated third composite precursor solution on the surface of the transparent conductive layer 6, anneal and dry it to obtain an array barrier transition layer 1. Step C: The transition layer 2 is fabricated on the barrier transition layer 1 using a gas phase method or a liquid phase method. In the gas phase method, the transition layer 2 is fabricated using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus. In the liquid phase method, the transition layer 2 is fabricated using any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method. Step D: Fabricate a hole transport layer 3 on the surface of the transition layer 2 using any one of an ALD apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, or fabricate the hole transport layer 3 by any one of a solution doctor blade coating, a slit coating, and a spray coating method. Step E: A buffer layer 4 is fabricated on the surface of the hole transport layer 3 using a gas phase method or a liquid phase method. In the gas phase method, the buffer layer 4 is fabricated using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method. Step F: Sequentially fabricate the perovskite light-absorbing layer 7, the electron transport layer 8, and the back electrode 9 on the surface of the buffer layer 4 until completing the fabrication of the perovskite solar module.

[0033] Specifically, the conditions for the UV light irradiation treatment are a light wavelength range of 265 nm to 365 nm and a light irradiation treatment time of 5 mIin to 60 mIin, and the conditions for the high-temperature treatment are a heating temperature range of 50 to 100°C and a heating treatment time of 5 mIin to 60 mIin.

[0034] The perovskite solar module structure and its manufacturing method of the present invention will be further described below through specific examples. Example 1

[0035] Furthermore, as shown in FIG. 1, an embodiment of the method for manufacturing the first type of perovskite solar module of the present invention includes the following steps: Step 11: The glass on which the FTO transparent conductive layer 6 was fabricated was washed with dishwashing detergent, deionized water, acetone, isopropyl alcohol, and ultrasonic waves, each for 30 min. Then, it was blown dry with N2 and treated in a UVO-zone for 10 min. Step 12: Prepare the barrier transition layer 1 by chemical vapor deposition of Al-doped tin oxide, with an Al doping ratio of 5-10%. Step 13: Using a magnetron sputtering device, a transition layer 2 having a thickness of 0.2 nm to 30 nm (the structural formula of the material of the transition layer 2 is NI 0.15 Al 0.05 Sn 0.8 O 1.825 ) was fabricated on the surface of the barrier transition layer 1. Step 14: Using a 4000R, a 0.15M ethanol solution of nickel acetylacetonate was spin-coated on the surface of the transition layer 2 for 30 seconds, and then fired at 400° C. for 30 minutes to produce a nickel oxide hole transport layer 3. Step 15: Using the solution combustion method, a buffer layer 4 (the structural formula of the material for the buffer layer 4 is NIN 0.3 O 0.7 ) was prepared by dissolving 29 mg of NINO3·6H2O and 3 mg of urea solution in 1 ml of deionized water, stirring, and then spray-coating a buffer layer 4 thin film with a thickness of 0.2 nm to 50 nm on the surface of the nickel oxide hole transport layer 3. The buffer layer 4 was then heated in a N2 atmosphere at 400°C for 30 min, and then heated in air at 200°C for 10 min. Step 16: A perovskite light-absorbing layer 7 was fabricated on the surface of the buffer layer 4 by a one-step solution method. Step 17: An electron transport layer 8 (PCBM) and a barrier layer (BCP) were coated on the surface of the perovskite light-absorbing layer 7 in sequence. Step 18: A back electrode 9 (Ag) was fabricated on the surface of the electron transport layer 8 and the barrier layer to complete the fabrication of the perovskite solar module. Example 2

[0036] Furthermore, as shown in FIG. 1, an embodiment of the method for manufacturing the second type of perovskite solar module of the present invention includes the following steps: Step 21: The glass on which the FTO transparent conductive layer 6 was fabricated was washed with dishwashing detergent, deionized water, acetone, isopropyl alcohol, and ultrasonic waves, each for 30 min. Then, it was blown dry with N2 and treated with UV O-zone for 10 min. Step 22: Nb-doped tin oxide was fabricated by magnetron sputtering to fabricate the barrier transition layer 1. The Nb doping ratio was 3 to 8%. Step 23: Using the mixed solution method, a transition layer 2 of 0.2 nm to 30 nm (the structural formula of the material of the transition layer 2 is Cu 0.05 Al 0.2 Sn 0.75 O 1.85 ) was prepared on the surface of the barrier-transition layer 1, that is, 1.4 mg of CuCl2, 5.4 mg of AlCl3, and 28.5 mg of SnCl2 were dissolved in 1 ml of deionized water and stirred, and then a thin film of the transition layer 2 having a thickness of 0.2 nm to 30 nm was prepared on the surface of the barrier-transition layer 1 using a blade coating method, and the thin film was heated in air at 500°C for 1 hour to obtain the desired transition layer 2. Step 24: Cu using a magnetron sputtering system x A hole transport layer 3 was fabricated on the surface of the transition layer 2 . Step 25: Buffer layer 4 (the structural formula of the material for buffer layer 4 is Cu) is formed by magnetron sputtering. 0.4 Al 0.6 O 1.1 ) to Cu x O hole transport layer 3 was fabricated on the surface. Step 26: A perovskite light-absorbing layer 7 was fabricated on the surface of the buffer layer 4 by a one-step solution method. Step 27: An electron transport layer 8 (C60) and a barrier layer (zirconium acetylacetonate) were coated on the surface of the perovskite light-absorbing layer 7 in sequence. Step 28: A back electrode 9 (Ag) was fabricated on the surface of the electron transport layer 8 and the barrier layer to complete the fabrication of the perovskite solar module.

[0037] The multi-layer composite transport layer of the first type of perovskite solar module of the present invention has the following characteristics:

[0038] 1. Conventional transparent conductive layers, such as FTO, are n-type doped. In this invention, p-type doping, such as Al, B, or SI, is introduced into the transition layer, creating a doping concentration gradient and energy level transition between the transparent conductive layer and the hole transport layer. Furthermore, the buffer layer replaces organic materials with nitrogen-containing inorganic materials, which has good photothermal stability and passivates surface defects in the hole transport layer, thereby improving the stability of the second interface between the hole transport layer and the perovskite light-absorbing layer.

[0039] 2. The perovskite solar module of the present invention employs a multi-layer composite transport layer, which significantly improves the photostability of the perovskite solar module. x When used as a hole transport layer, NI is mainly 2+ , N.I. 3+ , and a small amount of NI 4+ It exists in the form of NI 3+ promotes carrier transport, but NI 3+ The presence of high-valent NI also induces NI photocatalysis and affects the photostability of perovskite solar modules. The transition layer proposed in this invention utilizes NI in the transition layer. 3+ While controlling the ratio of NI to high-valent NI, it enables the hole transport material to transition to perovskite material, thereby significantly improving the photostability of perovskite solar modules.

[0040] 3. Common transparent conductive layers, such as FTO, have a high concentration of fluorine doping. During long-term use of a perovskite solar module, fluorine ions may migrate into the active layer of the perovskite solar module. The barrier transition layer of the present invention can effectively inhibit this migration and improve the photostability of the perovskite solar module.

[0041] Figure 6 shows the conversion efficiency curve of the perovskite solar module (i.e., a four-layer hole transport layer composite structure) fabricated in Example 1 of the present invention, and the conversion efficiency curve of an existing perovskite solar module (i.e., a single-layer hole transport layer) including a single-layer hole transport layer in Comparative Example 1. Figure 6 shows that the open circuit voltage of the four-layer hole transport layer composite structure of the present invention is significantly improved, reaching 1.16 V, while the open circuit voltage of the single-layer hole transport layer is 1.014 V.

[0042] FIG. 7 shows the conversion efficiency curve of the perovskite solar module fabricated in Example 1 of the present invention (i.e., a four-layer hole transport layer composite structure). Comparative Example 2 shows the conversion efficiency curve of a perovskite solar module with a composite hole transport layer structure including a barrier transition layer, a transition layer, and a hole transport layer (i.e., barrier transition layer / transition layer / hole transport layer). The open-circuit voltage of Comparative Example 2 reaches 1.07 V, and the short-circuit current and fill factor of the single-layer hole transport layer of Comparative Example 1 are significantly improved. Comparative Example 2 differs from Example 1 in that it does not have a buffer layer. Comparative Example 3 shows the conversion efficiency curve of a perovskite solar module with a composite hole transport layer structure of a hole transport layer and a buffer layer (i.e., hole transport layer / buffer layer). From FIG. 7, it can be seen that the open-circuit voltage of Comparative Example 3 is significantly improved to 1.11 V, but the short-circuit current and fill factor are both poor. Compared with the above structures, the four-layer hole transport composite structure of Example 1 of the present invention has significantly improved open circuit voltage, short circuit current, and fill factor, with Voc reaching 1.16 V and Jsc reaching 23 mA / cm. 2 The FF increased to over 80% and the efficiency reached 21.49%.

[0043] FIG. 8 shows the photoaging test curves of the perovskite solar module (i.e., a four-layer hole transport composite structure) fabricated in Example 1 of the present invention. Comparative Example 1 is the photoaging test curve of an existing perovskite solar module (i.e., a single-layer hole transport layer) including a single-layer hole transport layer. Comparative Example 2 is the photoaging test curve of a perovskite solar module (i.e., a barrier transition layer / transition layer / hole transport layer) having a composite hole transport layer structure including a barrier transition layer, a transition layer, and a hole transport layer. Comparative Example 3 is the photoaging test curve of a perovskite solar module (i.e., a hole transport layer / buffer layer) having a composite hole transport layer structure of a hole transport layer and a buffer layer. From FIG. 8, it can be seen that the photostability of Comparative Examples 2 and 3 is significantly improved, while the photostability of Example 1 of the present invention is significantly improved compared to Comparative Examples 1 to 3, showing no decay even after approximately 5,000 hours of photoaging. Example 3

[0044] Furthermore, as shown in FIG. 2, one embodiment of the method for manufacturing the second type of perovskite solar module of the present invention includes the following steps: Step 31: The glass on which the FTO transparent conductive layer 6 was formed was washed with dishwashing detergent, deionized water, acetone, isopropyl alcohol, and ultrasonic waves, each for 30 min each. Then, it was blown dry with N2 and treated with UV O-zone for 10 min. Step 32: Al-doped tin oxide is deposited by chemical vapor deposition to form a barrier transition layer 1 having a thickness of 1 nm to 30 nm. The Al doping ratio is 5 to 10%. Step 33: 3-aminopropyltriethoxysilane and a suspension of Al2O3 and SnO2 nanoparticles (10 wt%, 100 nm) were mixed in IPA at a volume ratio of 1%, stirred, and then irradiated with a 365 nm UV lamp for 10 min. The mixed suspension was then coated onto the barrier transition layer 1 using a blade coating method, and the wet film was heated and annealed to form an array transition layer 2 with a thickness of 0.2 nm to 30 nm. Step 34: Using a 4000R, a 0.15 M ethanol solution of nickel acetylacetonate was spin-coated on the surface of the transition layer 2 for 30 seconds, and then fired at 400°C for 30 minutes to produce a nickel oxide hole transport layer 3 with a thickness of 1 nm to 100 nm. Step 35: Using a solution combustion method, a buffer layer 4 (the structural formula of the material for the buffer layer 4 is NIN 0.3 O 0.7 ) was prepared by dissolving 29 mg of NINO3·6H2O and 3 mg of urea solution in 1 ml of deionized water, stirring, and then spray-coating a buffer layer 4 thin film with a thickness of 0.2 nm to 50 nm on the surface of the nickel oxide hole transport layer 3. The buffer layer 4 was then heated in a N2 atmosphere at 400°C for 30 min, and then heated in air at 200°C for 10 min. Step 36: A perovskite light-absorbing layer 7 was fabricated on the surface of the buffer layer 4 by a one-step solution method. Step 37: An electron transport layer 8 (PCBM) and a barrier layer (BCP) were coated on the surface of the perovskite light-absorbing layer 7 in sequence. Step 38: A back electrode 9 (Ag) was fabricated on the surface of the electron transport layer 8 to complete the fabrication of the perovskite solar module. Example 4

[0045] Furthermore, as shown in both Figures 3 and 5, another embodiment of the method for manufacturing the second type of perovskite solar module of the present invention includes the following steps: Step 41: The glass on which the FTO transparent conductive layer 6 was formed was washed with dishwashing detergent, deionized water, acetone, isopropyl alcohol, and ultrasonic wave for 30 min each, then blown dry with N2 and treated with UV O-zone for 10 min. Step 42: Nb-doped tin oxide was fabricated by magnetron sputtering to fabricate the barrier transition layer 1. The Nb doping ratio was 3 to 8%. Step 43: Using the mixed solution method, a transition layer 2 of 1 nm to 100 nm (the structural formula of the material of the transition layer 2 is Cu 0.05 Al 0.2 Sn 0.75 O 1.85) was prepared on the surface of the barrier-transition layer 1, and 1.4 mg of CuCl2, 5.4 mg of AlCl3, and 28.5 mg of SnCl2 were dissolved in 1 ml of deionized water and stirred. After that, a thin film of the transition layer 2 having a thickness of 1 nm to 80 nm was prepared on the surface of the barrier-transition layer 1 using a blade coating method, and the thin film was heated in air at 500°C for 1 hour to obtain the desired transition layer 2. Step 44: Cu using a magnetron sputtering system x A hole transport layer 3 was fabricated on the surface of the transition layer 2 . Step 45: Vinyltriethoxysilane and Cu x The suspension of SiO and SiO nanoparticles (10 wt%, 80 nm) was mixed with deionized water at a volume ratio of 3%. After stirring, the mixed solution was heated at 80-100 °C and stirred for 30 min. The mixed suspension was then applied to Cu using a blade coating method for use. x The array buffer layer 4 containing the openings 10 was obtained by coating the layer on the hole transport layer 3 and annealing it. Step 46: A perovskite light-absorbing layer 7 was fabricated on the surface of the buffer layer 4 by a one-step solution method. Step 47: An electron transport layer 8 (C60) and a barrier layer (zirconium acetylacetonate) were coated sequentially on the surface of the perovskite light-absorbing layer 7. Step 48: A back electrode 9 (Ag) was fabricated on the surface of the electron transport layer 8 to complete the fabrication of the perovskite solar module.

[0046] The multi-layer composite transport layer of the second type of perovskite solar module of the present invention has the following characteristics:

[0047] 1. Conventional transparent conductive layers, such as FTO, are n-type doped. In this invention, p-type doping, such as Al, B, or SI, is introduced into the transition layer, creating a doping concentration gradient and energy level transition between the transparent conductive layer and the hole transport layer. Furthermore, the buffer layer replaces organic materials with nitrogen-containing inorganic materials, which has good photothermal stability and passivates surface defects in the hole transport layer, thereby improving the stability of the second interface between the hole transport layer and the perovskite light-absorbing layer.

[0048] 2. The perovskite solar module of the present invention employs a multi-layer composite transport layer, which significantly improves the photostability of the perovskite solar module. x When used as a hole transport layer, NI is mainly 2+ , N.I. 3+ , and a small amount of NI 4+ It exists in the form of NI 3+ promotes carrier transport, but NI 3+ The presence of high-valent NI also induces NI photocatalysis and affects the photostability of perovskite solar modules. The transition layer proposed in this invention utilizes NI in the transition layer. 3+ While controlling the ratio of NI to high-valent NI, it enables the hole transport material to transition to perovskite material, thereby significantly improving the photostability of perovskite solar modules.

[0049] 3. Common transparent conductive layers, such as FTO, have a high concentration of fluorine doping. During long-term use of a perovskite solar module, fluorine ions may migrate into the active layer of the perovskite solar module. The barrier transition layer of the present invention can effectively inhibit this migration and improve the photostability of the perovskite solar module.

[0050] 4. The nanoparticles simply form openings during coating, solving the problem of an overly dense inorganic oxide layer structure. This eliminates the influence of the thickness of the transition and buffer layers on the electrical tunneling effect, reducing non-radiative recombination at the interface between the perovskite light-absorbing layer and the hole-transporting layer without affecting carrier transport. 5. Inorganic nanocrystals tend to aggregate during long-term use due to charge imbalances caused by surface defects. This aggregation affects the stability of the material. The adhesive and dispersing properties of coupling agents prevent this phenomenon, improving the stability of materials and devices.

[0051] 6. There are many irregular dangling bonds at the interface of inorganic materials. By using a coupling agent, the dangling bonds on the surface of the inorganic material can be passivated, suppressing the photocatalytic reaction at the interface between the inorganic material and perovskite, and further improving stability.

[0052] FIG. 9 shows the conversion efficiency curves of the perovskite solar module manufactured in Example 3 of the present invention (i.e., the hole transport layer includes a four-layer composite structure / array-shaped transition layer). Comparative Example 1 is the conversion efficiency curve of a conventional perovskite solar module including a single-layer hole transport layer (i.e., single-layer hole transport layer). Comparative Example 4 is the conversion efficiency curve of a perovskite solar module including a barrier transition layer, an array-shaped transition layer, and a hole transport layer (i.e., barrier transition layer / array-shaped transition layer / hole transport layer). Comparative Example 5 is the conversion efficiency curve of a perovskite solar module including a hole transport layer and an array-shaped buffer layer (i.e., hole transport layer / array-shaped transition layer). Comparative Example 4 differs from Example 3 in that a buffer layer is not provided. Comparative Example 5 differs from Example 4 in that a barrier transition layer and an array-shaped transition layer are not provided. 9 shows that the perovskite solar modules of Comparative Examples 4 and 5 have significantly improved efficiency compared to the perovskite solar module device of Comparative Example 1, and the open circuit voltage and short circuit current of the perovskite solar module of Example 3 are significantly improved compared to the devices of Comparative Examples 1, 4, and 5, with the open circuit voltage of Example 3 reaching 1.15 V and the FF reaching 80.44%. Furthermore, a comparison of FIG. 7 and FIG. 9 shows that the efficiency of the perovskite solar cell device fabricated with a four-layer composite structure including an array structure is also superior to that of the four-layer composite structure without an array, with a short circuit current of 23.02 mA / cm. 2 to 24.46mA / cm 2 It was found that the conversion efficiency improved significantly from 21.49% to 22.61%, and the conversion efficiency improved by approximately 5.2%.

[0053] FIG. 10 shows the photoaging test curves of the perovskite solar module manufactured in Example 3 of the present invention (i.e., the hole transport layer includes a four-layer composite structure / array-shaped transition layer). Comparative Example 1 is the photoaging test curve of a conventional perovskite solar module including a single-layer hole transport layer (i.e., a single-layer hole transport layer). Comparative Example 4 is the photoaging test curve of a perovskite solar module including a barrier transition layer, an array-shaped transition layer, and a hole transport layer (i.e., a barrier transition layer / array-shaped transition layer / hole transport layer). Comparative Example 5 is the photoaging test curve of a perovskite solar module including a hole transport layer and an array-shaped buffer layer (i.e., a hole transport layer / array-shaped transition layer). Comparative Example 4 differs from Example 3 in that a buffer layer is not provided. Comparative Example 5 differs from Example 4 in that a barrier transition layer and an array-shaped transition layer are not provided. 10, the perovskite solar module of Example 3 of the present invention has significantly improved photostability compared to the perovskite solar modules of Comparative Examples 1, 4, and 5, with Example 3 showing no decay even after 5,000 hours of photoaging. Furthermore, a comparison of Figures 8 and 10 reveals that the photostability of the perovskite solar cell device fabricated with the four-layer composite structure including the array structure is slightly better than that of the four-layer composite structure without the array, with the conversion efficiency of the solar cells of both structures showing no decay even after 5,000 hours of photoaging.

[0054] The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. 1. A multi-layer composite transport layer comprising: The barrier transition layer includes a barrier layer, a transition layer, a hole transport layer, and a buffer layer, which are sequentially stacked according to the direction of light incidence. The barrier transition layer is made of a fluorine-doped tin oxide material doped with an R element instead of an F element, and the R element is substituted for the F element in a ratio of 1% to 100%. The R element is at least one element selected from the group consisting of W, Nb, Ni, Al, and Si. The transition layer is made of a material selected from the group consisting of Ni, ｘ A ｙ SI ｚ Sn ｍ O ｎ , or Cu ｘ A ｙ SI ｚ Sn ｍ O ｎ (wherein x>0, y>=0, z>=0, m>=0, n>0, and A is aluminum or boron), and the material for manufacturing the transition layer contains at least one element selected from A, SI, and Sn, and the material for manufacturing the hole transport layer is NiO ｘ , Cu ｘ The buffer layer is made of one of NI, O, and CuSCN. ａ E ｂ N ｃ O ｄ , or Cu ａ E ｂ N ｃ O ｄ (where a>0, b>=0, c>0, d>=0, and E is any one of the elements Al, B, Si, Zn, Co, and Zr).

2. 1. A multi-layer composite transport layer comprising: The barrier transition layer includes a barrier layer, a transition layer, a hole transport layer, and a buffer layer, which are sequentially stacked according to the direction of light incidence. The barrier transition layer is made of a fluorine-doped tin oxide material doped with an R element instead of an F element, and the R element is substituted for the F element in a ratio of 1% to 100%. The R element is at least one element selected from the group consisting of W, Nb, Ni, Al, and Si. The transition layer is made of a material selected from the group consisting of Ni, ｘ A ｙ SI ｚ Sn ｍ O ｎ , or Cu ｘ A ｙ SI ｚ Sn ｍ O ｎ (wherein x>0, y>=0, z>=0, m>=0, n>0, and A is aluminum or boron), and the material for manufacturing the transition layer contains at least one element selected from A, SI, and Sn, and the material for manufacturing the hole transport layer is NiO ｘ , Cu ｘ The buffer layer is made of one of NI, O, and CuSCN. ａ E ｂ N ｃ O ｄ , or Cu ａ E ｂ N ｃ O ｄ wherein a>0, b>=0, c>0, d>=0, and E is any one of Al, B, SI, Zn, Co, and Zr; wherein a coupling agent is added to and doped into the manufacturing material of at least one of the barrier-transition layer, transition layer, and buffer layer to obtain a corresponding coupling-agent-containing array barrier-transition layer and / or array transition layer and / or array buffer layer; and wherein the thin film of the barrier-transition layer and / or transition layer and / or buffer layer doped with the coupling agent comprises a plurality of discretely arranged coupling-agent-containing array molecular clusters and openings each having two adjacent molecular clusters, the openings connecting the upper and lower surfaces of the thin film; and the coupling agent is any one of a silane coupling agent, a thianate coupling agent, an aluminate coupling agent, a phosphate coupling agent, and a borate coupling agent; and the length of the openings is 10 nm to 200 nm.

3. 3. The multilayer composite transport layer of claim 2, wherein the coupling agent is added in an amount of 0.5-5% by volume of the nanoparticle suspension used to fabricate the barrier transition layer and / or transition layer and / or buffer layer, and the nanoparticle suspension has a concentration of 0.1-10 wt.%.

4. 3. The multilayer composite transport layer of claim 1, wherein the barrier transition layer has a thickness of 1 nm to 30 nm, the transition layer has a thickness of 0.2 nm to 30 nm, the hole transport layer has a thickness of 1 nm to 100 nm, and the buffer layer has a thickness of 0.2 nm to 50 nm.

5. A perovskite solar module, the internal structure of which includes a transparent conductive layer, a perovskite light absorbing layer, an electron transport layer, and a back electrode, which are sequentially stacked, respectively, 10. A perovskite solar module, comprising: a multi-layer composite transport layer according to claim 1 disposed between the transparent conductive layer and the perovskite light-absorbing layer; a barrier transition layer of the multi-layer composite transport layer and the transparent conductive layer in close contact with each other; and a buffer layer of the multi-layer composite transport layer and the perovskite light-absorbing layer in close contact with each other.

6. A perovskite solar module, the internal structure of which includes a transparent conductive layer, a perovskite light absorbing layer, an electron transport layer, and a back electrode, which are sequentially stacked, respectively, 10. A perovskite solar module, comprising: a multi-layer composite transport layer according to claim 2 disposed between the transparent conductive layer and the perovskite light-absorbing layer; a barrier transition layer of the multi-layer composite transport layer and the transparent conductive layer in close contact with each other; and a buffer layer of the multi-layer composite transport layer and the perovskite light-absorbing layer in close contact with each other.

7. Step 1: cleaning the transparent conductive layer and treating it with ultraviolet light and ozone; Step 2 of fabricating a barrier transition layer on the transparent conductive layer using a vapor phase or liquid phase method, wherein the vapor phase method is fabricating the transition layer using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; Step 3 of manufacturing a transition layer on the barrier-transition layer using a vapor phase method or a liquid phase method, in which the vapor phase method is one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; Step 4: forming a hole transport layer on the surface of the transition layer using any one of an atomic layer deposition (ALD) device, a chemical vapor deposition (CVD) device, a magnetron sputtering device, an electron beam evaporation device, and a thermal evaporation device, or forming a hole transport layer by any one of a solution doctor blade coating, a slit coating, and a spray coating process; Step 5 of forming a buffer layer on the surface of the hole transport layer by a vapor or liquid phase method, in which the vapor phase method is any one of atomic layer deposition (ALD), chemical vapor deposition (CVD), magnetron sputtering, electron beam evaporation, and thermal evaporation to form the transition layer, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; and step 6. sequentially fabricating a perovskite light-absorbing layer, an electron transport layer, and a back electrode on the surface of the buffer layer until completing the fabrication of the perovskite solar module.

8. 7. A method for manufacturing a perovskite solar module according to claim 6, comprising the steps of: Step I: cleaning the transparent conductive layer and treating it with ultraviolet light and ozone; Step II of forming a barrier transition layer on the transparent conductive layer using a vapor phase or liquid phase method, in which the vapor phase method is formed using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; Step III: mixing a coupling agent with a solution of a material for preparing a transition layer to obtain a first composite precursor solution; irradiating the first composite precursor solution with UV light or treating it at high temperature; then coating the treated first composite precursor solution on the surface of the barrier transition layer, and annealing and drying it to obtain an array transition layer; Step IV: forming a hole transport layer on the surface of the array transition layer using any one of an ALD device, a chemical vapor deposition (CVD) device, a magnetron sputtering device, an electron beam evaporation device, and a thermal evaporation device, or forming the hole transport layer by any one of a solution doctor blade coating, a slit coating, and a spray coating process; Step V is a step of forming a buffer layer on the surface of the hole transport layer by a vapor or liquid phase method, in which the vapor phase method is to form the transition layer by using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; and Step VI. sequentially fabricating a perovskite light absorbing layer, an electron transport layer, and a back electrode on the surface of the buffer layer until completing the fabrication of a perovskite solar module.

9. Step 1: cleaning the transparent conductive layer and treating it with ultraviolet light and ozone; Step 2 of forming a barrier transition layer on the transparent conductive layer using a vapor phase method or a liquid phase method, in which the vapor phase method is formed using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; Step 3 of manufacturing a transition layer on the barrier-transition layer using a vapor phase method or a liquid phase method, in which the vapor phase method is one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; Step 4: forming a hole transport layer on the surface of the transition layer using any one of an ALD device, a chemical vapor deposition (CVD) device, a magnetron sputtering device, an electron beam evaporation device, and a thermal evaporation device, or forming the hole transport layer by any one of a solution doctor blade coating, a slit coating, and a spray coating process; Step 5: mixing a coupling agent with a solution of a material for preparing a buffer layer to obtain a second composite precursor solution, irradiating the second composite precursor solution with UV light or treating it at high temperature, and then coating the treated second composite precursor solution on the surface of the hole transport layer, followed by annealing and drying to obtain an array buffer layer; and step 6. sequentially fabricating a perovskite light-absorbing layer, an electron transport layer, and a back electrode on the surface of the array buffer layer until completing the fabrication of the perovskite solar module.

10. Step A: cleaning the transparent conductive layer and treating it with ultraviolet light and ozone; Step B: mixing a coupling agent with a solution of materials for preparing a barrier transition layer to obtain a third composite precursor solution; irradiating the third composite precursor solution with UV light or treating it at high temperature; then coating the treated third composite precursor solution on the surface of the transparent conductive layer, and annealing and drying it to obtain an array barrier transition layer; Step C of forming a transition layer on the barrier-transition layer by a vapor or liquid phase method, wherein the vapor phase method is formed by using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; Step D: forming a hole transport layer on the surface of the transition layer using any one of an ALD apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, or forming the hole transport layer by any one of a solution doctor blade coating, a slit coating, and a spray coating; Step E of forming a buffer layer on the surface of the hole transport layer by a vapor phase method or a liquid phase method, in which in the vapor phase method, the buffer layer is formed by using any one of an atomic layer deposition (ALD) apparatus, a chemical vapor deposition (CVD) apparatus, a magnetron sputtering apparatus, an electron beam evaporation apparatus, and a thermal evaporation apparatus, and in which the liquid phase method is any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method; and step F of sequentially fabricating a perovskite light-absorbing layer, an electron transport layer, and a back electrode on the surface of the buffer layer until completing the fabrication of the perovskite solar module.

Images