Composite transport layer and perovskite solar cell, and preparation method therefor

Abstract

The present invention relates to a composite transport layer and a perovskite solar cell, and a preparation method therefor. The composite transport layer comprises a transition layer, a hole transport layer and a buffer layer, which are sequentially stacked in a light incident direction. The preparation material for the transition layer is NixAySizSnmOn or CuxAySizSnmOn, wherein x>0, y≥0, z≥0, m≥0, n>0, and A is aluminum or boron; and the preparation material for the transition layer at least comprises any one element of A, Si and Sn. The preparation material for the hole transport layer is any one of NiOx, CuxO and CuSCN. The preparation material for the buffer layer is NiaEbNcOd or CuaEbNcOd, wherein a>0, b≥0, c>0, d≥0, and E is any one element of Al, B, Si, Zn, Co and Zr. The composite transport layer is used in the perovskite solar cell of the present invention, and the high defect density and high hole mobility of the hole transport material are reserved, such that the perovskite solar cell comprising the composite transport layer has the characteristics of both a high conversion efficiency and good long-term photo-thermal stability.

Description

A composite transmission layer and perovskite solar cell and preparation method thereof Technical Field

[0001] The present invention belongs to the technical field of perovskite solar cell preparation, and in particular relates to a composite transmission layer and a perovskite solar cell and a preparation method thereof. Background Art

[0002] Common perovskite solar cell device structures include positive-type NIP cell devices and inverted-type PIN cell devices. Positive-type devices, in this case, include at least the following: a transparent conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer, and a back electrode, starting from the light-incident surface. Inverted-type devices, in this case, include at least the following: a transparent conductive layer, a hole transport layer, a perovskite active layer, an electron transport layer, and a back electrode, starting from the light-incident surface. Compared to positive-type devices, inverted-type devices do not require the use of highly photocatalytically active TiO2 or the expensive hole transport material Spiro-OMeTAD. They can be prepared at low temperatures, have simple processes, and exhibit excellent stability. Despite this, the majority of current high conversion efficiencies are in positive-type devices, with the highest reaching 26%, while the conversion efficiencies of inverted-type devices are mostly concentrated between 22% and 24%. Further optimization of the hole transport layer and interface in inverted-type devices is crucial for improving the conversion efficiency of inverted-type devices.

[0003] The main reasons for the low conversion efficiency of inverted PIN cell devices are: the energy band mismatch between the first interface formed by the transparent conductive layer and the hole transport layer, and the large number of interface defects between the second interface formed by the hole transport layer and the perovskite active layer. The optional materials for the hole transport layer are generally divided into three categories: 1) inorganic oxides or inorganic salts; 2) organic polymers; 3) organic small molecules. Among them, the typical options for the first type of inorganic oxides or inorganic salts include NiO x , V2O5, CuO, CuSCN, etc.; Typical options for the second type of organic polymers include P3HT, PTAA, etc.; Typical options for the third type of organic small molecules include spiro-OMeTAD and PAC z Self-assembly materials, etc. The first type of materials are easy to obtain and low in cost, but their good hole transport performance comes from the defects in the materials themselves. A higher defect density is often required to obtain better hole transport performance. However, a higher defect density will deteriorate 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, in order to improve its hole mobility, it is necessary to increase the uncoordinated Ni 3+ concentration, but high concentration of Ni 3+ It also promotes NiO xThe source of the photocatalytic reaction at the perovskite interface. Materials in the second category generally require a longer synthesis path, have better hole transport properties, and are more easily obtained with high conversion efficiency inversion devices. However, their biggest drawback is the poor photostability of the polymer materials themselves. They are prone to self-decomposition under long-term outdoor light exposure, resulting in rapid performance degradation of the inversion device. Materials in the third category can further improve the conversion efficiency of inversion devices based on materials in the second category. However, similar to materials in the second category, due to the use of organic matter, they lack stability under long-term light exposure. To address these issues, there have been reports of using a composite structure of an inorganic hole transport layer and an organic hole transport layer or a method of passivating the inorganic hole transport layer. However, using a composite structure of an inorganic hole transport layer and an organic hole transport layer is a poor solution because the organic layer will still decompose under long-term light exposure, eliminating the effect of the composite structure. Passivating the inorganic hole transport layer often sacrifices conversion efficiency in exchange for improved stability, making it a stopgap measure.

[0004] Furthermore, existing hole transport layers are typically made from inorganic oxides. These materials present the following challenges: 1) the structure formed by inorganic oxides can be too dense, hindering hole conduction; 2) inorganic nanocrystals can easily aggregate over time due to charge imbalances caused by surface defects, which can affect material stability; and 3) the inorganic interface has a large number of disordered dangling bonds, some of which can react with the perovskite material.

[0005] Existing hole transport layers cannot enable perovskite solar cells to achieve both high conversion efficiency and good stability.

[0006] Summary of the Invention

[0007] The technical problem to be solved by the present invention is to provide a composite transport layer and a perovskite solar cell and a method for preparing the same. The hole transport layer uses a composite structure, with a transition layer and a buffer layer provided on the upper and lower surfaces of the hole transport layer, respectively. This retains the high defect density and high hole mobility of the hole transport material, significantly improving not only the light stability of the perovskite solar cell but also the conversion efficiency of the perovskite solar cell. Furthermore, a coupling agent is doped into the preparation material of the composite transport layer to improve the conductivity and stability of the hole transport layer made of an inorganic oxide material, thereby enabling the perovskite solar cell to achieve both high conversion efficiency and good stability.

[0008] The present invention is implemented in this way, providing a first composite transmission layer, comprising a transition layer, a hole transport layer and a buffer layer stacked in sequence according to the light incident direction, wherein the preparation material of the transition layer is Ni x A y Si z Snm O n or Cu x A y Si z Sn m O n , wherein x>0, y>=0, z>=0, m>=0, n>0, A is aluminum (Al) or boron (B), the preparation material of the transition layer contains at least one element of A, Si, Sn, and the preparation material of the hole transport layer is NiO x 、Cu x O, CuSCN, the buffer layer is made of Ni 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.

[0009] The present invention is implemented in this way, and also provides a second composite transmission layer, including a transition layer, a hole transport layer and a buffer layer stacked in sequence according to the light incident direction, wherein the preparation 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 , wherein x>0, y>=0, z>=0, m>=0, n>0, A is aluminum or boron, the preparation material of the transition layer contains at least one element of A, Si, Sn, and the preparation material of the hole transport layer is NiO x 、Cu x O, CuSCN, the buffer layer is made of Ni 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. A coupling agent is also doped into the materials used to prepare the transition layer and / or buffer layer, resulting in a corresponding array transition layer and / or array buffer layer containing the coupling agent. The film formed from the transition layer and / or buffer layer doped with the coupling agent comprises a plurality of discretely arranged array molecular clusters containing the coupling agent and openings separating two adjacent molecular clusters, each opening connecting the upper and lower surfaces of the film. The coupling agent is any one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a phosphate coupling agent, and a borate coupling agent.

[0010] The present invention is implemented in this way and also provides a first perovskite solar cell, the internal structure of which includes a transparent conductive layer, a perovskite light absorbing layer, an electron transport layer and a back electrode stacked together in sequence, and the first composite transport layer as described above is arranged between the transparent conductive layer and the perovskite light absorbing layer, the transition layer of the composite transport layer is in contact with the transparent conductive layer, and its buffer layer is in contact with the perovskite light absorbing layer.

[0011] The present invention is implemented in this way and also provides a second perovskite solar cell, the internal structure of which includes a transparent conductive layer, a perovskite light absorbing layer, an electron transport layer and a back electrode stacked together in sequence, and a second composite transport layer as described above is arranged between the transparent conductive layer and the perovskite light absorbing layer, the transition layer of the composite transport layer is in contact with the transparent conductive layer, and its buffer layer is in contact with the perovskite light absorbing layer.

[0012] The present invention is implemented as follows: a method for preparing the first perovskite solar cell as described above is also provided, comprising the following steps:

[0013] Step 1: Cleaning and UV-ozone treating the transparent conductive layer;

[0014] Step 2: Prepare a transition layer on the transparent conductive layer using a vapor phase method or a liquid phase method. The vapor phase method is to use any one of an atomic layer deposition device ALD, a chemical vapor deposition device CVD, a magnetron sputtering device, an electron beam evaporation device, and a thermal evaporation device to prepare the transition layer. The liquid phase method is to use any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method to prepare the transition layer.

[0015] Step 3: preparing 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, and a thermal evaporation device, or preparing a hole transport layer by any one of a solution doctor blade coating, a slit coating, and a spray coating method;

[0016] Step 4: Prepare a buffer layer on the surface of the hole transport layer using a vapor phase method or a liquid phase method. The vapor phase method is to use any one of an atomic layer deposition device ALD, a chemical vapor deposition device CVD, a magnetron sputtering device, an electron beam evaporation device, and a thermal evaporation device to prepare the buffer layer. The liquid phase method is to use any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method to prepare the buffer layer.

[0017] Step 5: Prepare a perovskite light absorbing layer, an electron transport layer and a back electrode in sequence on the surface of the buffer layer until the preparation of the perovskite solar cell is completed.

[0018] The present invention is implemented in this way, and also provides a method for preparing the second perovskite solar cell as described above, comprising the following steps:

[0019] Step I: cleaning and UV-ozone treating the transparent conductive layer;

[0020] Step II: mixing a coupling agent with a material solution for preparing a transition layer to obtain a first composite precursor solution, subjecting the first composite precursor solution to UV light treatment or high temperature treatment, and then coating the treated first composite precursor solution on the surface of the transparent conductive layer, annealing and drying to obtain a transition layer;

[0021] Step III, preparing 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 preparing a hole transport layer by any one of a solution doctor blade coating, a slit coating, and a spray coating method;

[0022] Step IV, preparing a buffer layer on the surface of the hole transport layer using a vapor phase method or a liquid phase method, the vapor phase method is to use 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 to prepare the buffer 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;

[0023] Step V: sequentially prepare a perovskite light absorbing layer, an electron transport layer, and a back electrode on the surface of the buffer layer until the preparation of the perovskite solar cell is completed.

[0024] The present invention is implemented in this way, and also provides a method for preparing the second perovskite solar cell as described above, comprising the following steps:

[0025] Step 1: Cleaning and UV-ozone treating the transparent conductive layer;

[0026] Step 2: preparing a transition layer on the transparent conductive layer using a vapor phase method or a liquid phase method. The vapor phase method is to use 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 to prepare the transition layer. The liquid phase method is to use any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method.

[0027] Step 3: preparing 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 preparing a hole transport layer by any one of a solution doctor blade coating, a slit coating, and a spray coating method;

[0028] Step 4: mixing the coupling agent with the material solution for preparing the buffer layer to obtain a second composite precursor solution, subjecting the second composite precursor solution to UV light treatment or high temperature treatment, and then coating the treated second composite precursor solution on the surface of the hole transport layer, annealing and drying to obtain the buffer layer;

[0029] Step 5: sequentially prepare a perovskite light absorbing layer, an electron transport layer, and a back electrode on the surface of the buffer layer until the preparation of the perovskite solar cell is completed.

[0030] The present invention is implemented in this way, and also provides a method for preparing the second perovskite solar cell as described above, comprising the following steps:

[0031] Step A, cleaning and UV-ozone treating the transparent conductive layer;

[0032] Step B: mixing a coupling agent with a material solution for preparing a transition layer to obtain a first composite precursor solution, subjecting the first composite precursor solution to UV light treatment or high temperature treatment, and then coating the treated first composite precursor solution on the surface of the transparent conductive layer, and annealing and drying to obtain the transition layer;

[0033] Step C, preparing 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 preparing the hole transport layer by any one of a solution doctor blade coating, a slit coating, and a spray coating method;

[0034] Step D: mixing a coupling agent with a solution of a material for preparing a buffer layer to obtain a second composite precursor solution, subjecting the second composite precursor solution to UV light treatment or high temperature treatment, and then coating the treated second composite precursor solution on the surface of the hole transport layer, and annealing and drying to obtain a buffer layer;

[0035] Step E: sequentially preparing a perovskite light absorbing layer, an electron transport layer, and a back electrode on the surface of the buffer layer until the preparation of the perovskite solar cell is completed.

[0036] The present invention utilizes the difference in wettability between the nanoparticles used to prepare the transition layer and / or buffer layer and the partially cross-linked coupling agent to form a continuous, regular, and discrete array of coupling agent-containing molecular clusters and openings separating two adjacent molecular clusters during film coating, thereby preparing an "array-shaped" transition layer and / or buffer layer containing the coupling agent.

[0037] Compared with the prior art, the first composite transport layer and perovskite solar cell and their preparation method of the present invention include a transition layer, a hole transport layer and a buffer layer stacked in sequence according to the light incident direction. The preparation 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 , wherein x>0, y>=0, z>=0, m>=0, n>0, A is aluminum or boron, the preparation material of the transition layer contains at least one element of A, Si, Sn, and the preparation material of the hole transport layer is NiO x 、Cu x O, CuSCN, the buffer layer is made of Ni 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 hole transport layer of the present invention uses a composite structure, with a transition layer and a buffer layer disposed on the upper and lower surfaces of the hole transport layer, respectively. This retains the high defect density and high hole mobility of the hole transport material, enabling the perovskite solar cell containing the composite transport layer to achieve both high conversion efficiency and good long-term photothermal stability.

[0038] On the other hand, compared with the prior art, the second composite transport layer and perovskite solar cell and preparation method thereof of the present invention include a transition layer, a hole transport layer and a buffer layer stacked in sequence according to the light incident direction. The preparation material of the transition layer is Ni x A y Si z Sn m O n or Cu x A y Si zSn m O n , wherein x>0, y>=0, z>=0, m>=0, n>0, A is aluminum or boron, the preparation material of the transition layer contains at least one element of A, Si, Sn, and the preparation material of the hole transport layer is NiO x 、Cu x O, CuSCN, the buffer layer is made of Ni 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. A coupling agent is also doped into the materials used to prepare the transition layer and / or buffer layer, yielding a corresponding array transition layer and / or array buffer layer containing the coupling agent. The film formed from the transition layer and / or buffer layer doped with the coupling agent comprises a plurality of discretely arranged array molecular clusters containing the coupling agent and openings separating two adjacent molecular clusters, each opening connecting the upper and lower surfaces of the film. The coupling agent is any one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a phosphate coupling agent, and a borate coupling agent. The hole transport layer of the present invention uses a composite array structure, and a coupling agent is added to the preparation material of the transition layer and / or the buffer layer to obtain an array transition layer and / or an array buffer layer, thereby improving the conductivity and stability of the hole transport layer made of inorganic oxide materials, so that the prepared perovskite solar cell not only greatly improves the light stability of the perovskite solar cell, but also improves the conversion efficiency of the perovskite solar cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] FIG1 is a schematic plan view of the internal structure of a preferred embodiment of a first perovskite solar cell according to the present invention;

[0040] FIG2 is a schematic plan view of a first internal structure of a second perovskite solar cell according to the present invention;

[0041] FIG3 is a schematic plan view of a second internal structure of a second perovskite solar cell according to the present invention;

[0042] FIG4 is a schematic plan view of a third internal structure of the second perovskite solar cell of the present invention;

[0043] FIG5 is a schematic diagram showing a comparison of conversion efficiency curves of the perovskite solar cell prepared in Example 1 of the present invention and the perovskite solar cell prepared in Comparative Example 1;

[0044] FIG6 is a schematic diagram comparing the conversion efficiency of the perovskite solar cell prepared in Example 1 of the present invention and the perovskite solar cells prepared in Comparative Examples 2 and 3;

[0045] FIG7 is a comparison curve of aging test results of the perovskite solar cell prepared in Example 1 of the present invention and the perovskite solar cells of Comparative Examples 1 to 3;

[0046] FIG8 is a perspective schematic diagram of a composite transport layer of a second internal structure of the second perovskite solar cell in FIG3 ;

[0047] FIG9 is a schematic diagram comparing conversion efficiency curves of the perovskite solar cell prepared in Example 5 of the present invention and the perovskite solar cells of Comparative Examples 1, 3, and 4;

[0048] FIG10 is a schematic diagram comparing aging curves of the perovskite solar cell prepared in Example 5 of the present invention and the perovskite solar cells of Comparative Examples 1, 3, and 4. DETAILED DESCRIPTION

[0049] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0050] As shown in FIG1 , a preferred embodiment of the first composite transport layer of the present invention includes a transition layer 1, a hole transport layer 2 and a buffer layer 3 stacked in sequence according to the light incident direction. The transition layer 1 is made 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, A is aluminum (Al) or boron (B). The transition layer is made of at least one element among A, Si, and Sn. The hole transport layer 2 is made of NiO. x 、Cu x O, CuSCN. The buffer layer 3 is made of Ni 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.

[0051] Please refer to Figures 2 to 4 at the same time, the preferred embodiment of the second composite transport layer of the present invention includes a transition layer 1, a hole transport layer 2 and a buffer layer 3 stacked in sequence according to the light incident direction. The preparation material of the transition layer 1 is 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, A is aluminum or boron, and the material of the transition layer 1 contains at least one element among A, Si, and Sn. The material of the hole transport layer 2 is NiO x 、Cu x O, CuSCN. The buffer layer 3 is made of Ni 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.

[0052] A coupling agent is also doped into the materials used to prepare the transition layer 1 and / or the buffer layer 3. The film formed from the transition layer 1 and / or the buffer layer 3 doped with the coupling agent comprises a plurality of discretely arranged array molecular clusters 11 containing the coupling agent, and openings 10 separating two adjacent molecular clusters. Each opening 10 connects the upper and lower surfaces of the film. The coupling agent can be any one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a phosphate coupling agent, and a borate coupling agent.

[0053] Specifically, the amount of the coupling agent added is 0.5-5% of the volume of the nanoparticle suspension to be added to prepare the transition layer 1 and / or the buffer layer 3, and the concentration of the nanoparticle suspension is 0.1-10 wt.%.

[0054] Specifically, the length of the opening 10 (ie, the interval between two adjacent molecular clusters) is 10 nm to 200 nm.

[0055] Specifically, in the first composite transport layer and the second composite transport layer of the present invention, the thickness of the transition layer 1 is 0.2 nm to 30 nm, the thickness of the hole transport layer 2 is 1 nm to 100 nm, and the thickness of the buffer layer 3 is 0.2 nm to 50 nm.

[0056] Referring again to FIG. 1 , the present invention further discloses a first perovskite solar cell. The internal structure of the perovskite solar cell comprises a transparent conductive layer 5, a perovskite light-absorbing layer 6, an electron transport layer 7, and a back electrode 8, stacked in sequence. The first composite transport layer 4, as described above, is disposed between the transparent conductive layer 5 and the perovskite light-absorbing layer 6. The transition layer 1 of the composite transport layer 4 is in contact with the transparent conductive layer 5, and the buffer layer 3 thereof is in contact with the perovskite light-absorbing layer 6. The hole transport layer 2 is located between the transition layer 1 and the buffer layer 3.

[0057] Referring to Figures 2-4 , the present invention also discloses a second perovskite solar cell. The internal structure of the perovskite solar cell comprises a transparent conductive layer 5, a perovskite light-absorbing layer 6, an electron transport layer 7, and a back electrode 8, stacked in sequence. A second composite transport layer 4, as previously described, is disposed between the transparent conductive layer 5 and the perovskite light-absorbing layer 6. The transition layer 1 of the composite transport layer 4 is in contact with the transparent conductive layer 5, and the buffer layer 3 thereof is in contact with the perovskite light-absorbing layer 6. The hole transport layer 2 is located between the transition layer 1 and the buffer layer 3.

[0058] In the first perovskite solar cell and the second perovskite solar cell of the present invention, the molecular formula of the material for preparing the perovskite light-absorbing layer 6 is ABX3, wherein A is at least one cation selected from the group consisting of cesium, rubidium, amine, amidine, and alkali; B is any one of divalent metal cations 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 of an anion selected from the group consisting of iodine, bromine, chlorine, astatine, thiocyanate, and acetate.

[0059] The composite transport layer of the second perovskite solar cell of the present invention has the following characteristics:

[0060] 1. The nanoparticles simply form openings during coating, which solves the problem of the inorganic oxide layer structure being too dense, eliminates the influence of the thickness of the transition layer and the buffer layer on the electrical tunneling, reduces the non-radiative recombination between the interface of the perovskite light absorption layer and the hole transport layer, and does not affect the carrier transport.

[0061] 2. Inorganic nanocrystals tend to aggregate over long periods of use due to charge imbalance caused by surface defects. Once aggregated, this can affect material stability. The bonding and dispersing effects of coupling agents prevent this phenomenon, improving material and device stability.

[0062] 3. There are a large number of disordered dangling bonds on the surface of the inorganic interface. The use of coupling agents can also play a role in passivating the dangling bonds on the surface of the inorganic matter, thereby inhibiting the photocatalytic reaction at the interface between the inorganic matter and the perovskite, and further improving the stability.

[0063] Referring again to FIG. 1 , the present invention further discloses a method for preparing the first perovskite solar cell as described above, comprising the following steps:

[0064] Step 1: Clean and treat the transparent conductive layer 5 with UV-ozone.

[0065] Step 2: Prepare a transition layer 1 on the transparent conductive layer 5 using a vapor phase method or a liquid phase method. The vapor phase method is to use any one of an atomic layer deposition device (ALD), a chemical vapor deposition device (CVD), a magnetron sputtering device, an electron beam evaporation device, or a thermal evaporation device to prepare the transition layer. The liquid phase method is to use any one of a mixed solution method, a hydrothermal method, a chemical bath method, or an in-situ doping method to prepare the transition layer 1.

[0066] Step 3: Prepare a hole transport layer 2 on the surface of the transition layer 1 using any one of an atomic layer deposition device ALD device, a chemical vapor deposition device CVD device, a magnetron sputtering device, an electron beam evaporation device, and a thermal evaporation device, or prepare the hole transport layer 2 by any one of a solution blade coating, a slit coating, and a spray coating method.

[0067] Step 4: Prepare a buffer layer 3 on the surface of the hole transport layer 2 using a vapor phase method or a liquid phase method. The vapor phase method uses any one of an atomic layer deposition device (ALD), a chemical vapor deposition device (CVD), a magnetron sputtering device, an electron beam evaporation device, or a thermal evaporation device to prepare the buffer layer; the liquid phase method uses any one of a mixed solution method, a hydrothermal method, a chemical bath method, or an in-situ doping method to prepare the buffer layer 3.

[0068] Step 5: A perovskite light absorbing layer 6, an electron transport layer 7 and a back electrode 8 are sequentially prepared on the surface of the buffer layer 3 until the preparation of the perovskite solar cell is completed.

[0069] Referring again to FIG. 2 , the present invention further discloses a method for preparing the second perovskite solar cell as described above, comprising the following steps:

[0070] Step I: Cleaning and UV-ozone treatment of the transparent conductive layer 5.

[0071] Step II: Mix the coupling agent with the material solution for preparing the transition layer 1 to obtain a first composite precursor solution, subject the first composite precursor solution to UV light treatment or high temperature treatment, and then coat the treated first composite precursor solution on the surface of the transparent conductive layer 5, anneal and dry to obtain the array transition layer 1.

[0072] Step III: Prepare a hole transport layer 2 on the surface of the transition layer 1 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 prepare the hole transport layer 2 by any one of a solution blade coating, a slit coating, and a spray coating process.

[0073] Step IV: Prepare a buffer layer 3 on the surface of the hole transport layer 2 using a gas phase method or a liquid phase method. The gas phase method is to use any one of atomic layer deposition ALD equipment, chemical vapor deposition CVD equipment, magnetron sputtering equipment, electron beam evaporation equipment, and thermal evaporation equipment to prepare the buffer layer 3. 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.

[0074] Step V: sequentially prepare a perovskite light absorbing layer 6, an electron transport layer 7 and a back electrode 8 on the surface of the buffer layer 3 until the preparation of the perovskite solar cell is completed.

[0075] Referring again to FIG. 3 , the present invention further discloses a method for preparing the second perovskite solar cell as described above, comprising the following steps:

[0076] Step 1: Clean and treat the transparent conductive layer 5 with ultraviolet ozone.

[0077] Step 2: Prepare a transition layer 1 on the transparent conductive layer 5 using a vapor phase method or a liquid phase method. The vapor phase method is to use any one of atomic layer deposition ALD equipment, chemical vapor deposition CVD equipment, magnetron sputtering equipment, electron beam evaporation equipment, and thermal evaporation equipment to prepare the transition layer 1. 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.

[0078] Step 3: Prepare a hole transport layer 2 on the surface of the transition layer 1 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 prepare the hole transport layer 2 by any one of a solution blade coating, a slit coating, and a spray coating process.

[0079] Step 4: Mix the coupling agent with the material solution for preparing the buffer layer 3 to obtain a second composite precursor solution, subject the second composite precursor solution to UV light treatment or high temperature treatment, and then coat the treated second composite precursor solution on the surface of the hole transport layer 2, anneal and dry to obtain the array buffer layer 3.

[0080] Step 5: sequentially prepare a perovskite light absorbing layer 6, an electron transport layer 7 and a back electrode 8 on the surface of the buffer layer 3 until the preparation of the perovskite solar cell is completed.

[0081] Referring again to FIG. 4 , the present invention further discloses a method for preparing the second perovskite solar cell as described above, comprising the following steps:

[0082] Step A: cleaning and UV-ozone treating the transparent conductive layer 5.

[0083] Step B: Mix the coupling agent with the material solution for preparing the transition layer 1 to obtain a first composite precursor solution, subject the first composite precursor solution to UV light treatment or high temperature treatment, and then coat the treated first composite precursor solution on the surface of the transparent conductive layer 5, anneal and dry to obtain the array transition layer 1.

[0084] Step C: Prepare a hole transport layer 2 on the surface of the transition layer 1 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 prepare the hole transport layer 2 by any one of a solution blade coating, a slit coating, and a spray coating process.

[0085] Step D: Mix the coupling agent with the material solution for preparing the buffer layer 3 to obtain a second composite precursor solution, subject the second composite precursor solution to UV light treatment or high temperature treatment, and then coat the treated second composite precursor solution on the surface of the hole transport layer 2, anneal and dry to obtain the array buffer layer 3.

[0086] Step E: sequentially prepare a perovskite light absorbing layer 6, an electron transport layer 7 and a back electrode 8 on the surface of the buffer layer 3 until the preparation of the perovskite solar cell is completed.

[0087] Specifically, the UV light treatment conditions are: the light wavelength range is 265nm to 365nm, and the light treatment time is 5min to 60min. The high temperature treatment conditions are: the heating temperature range is 50 to 100°C, and the heating treatment time is 5min to 60min.

[0088] The perovskite solar cell structure and preparation method of the present invention are further illustrated below through specific examples.

[0089] Example 1

[0090] Referring again to FIG. 1 , an embodiment of a method for preparing a first perovskite solar cell according to the present invention includes the following steps:

[0091] Step 11: The glass on which the FTO transparent conductive layer 5 is prepared is cleaned with detergent, deionized water, acetone, and isopropyl alcohol ultrasonically for 30 minutes each, then blown dry with N2 and treated in a UV O-zone for 10 minutes.

[0092] Step 12: Using magnetron sputtering equipment, a transition layer 1 with a thickness of 0.2 nm to 30 nm is prepared on the surface of the transparent conductive layer 5 of FTO. The structural formula of the material of the transition layer 1 is Ni 0.15 Al 0.05 Sn 0.8 O 1.825 .

[0093] Step 13: Spin-coat a 0.15M nickel acetylacetonate ethanol solution on the surface of the transition layer 1 at 4000R for 30s, and then burn at 400°C for 30min to prepare a nickel oxide hole transport layer 2 with a thickness of 1nm to 100nm.

[0094] Step 14: Prepare the buffer layer 3 by solution combustion method. The structural formula of the buffer layer 3 material is NiN 0.3 O 0.7 , 29 mg of NiNO3·6H2O and 3 mg of urea were dissolved in 1 ml of deionized water, stirred, and then a 0.2 nm to 50 nm thick buffer layer 3 film was prepared on the surface of the nickel oxide hole transport layer 2 by spray coating, and heated at 400°C for 30 min in N2 atmosphere and at 200°C for 10 min in air;

[0095] Step 15: Prepare the perovskite light absorbing layer 6 on the surface of the buffer layer 3 using a one-step solution method.

[0096] Step 16: sequentially coating an electron transport layer 7 (PCBM) and a barrier layer (BCP) on the surface of the perovskite light absorbing layer 6.

[0097] Step 17: Prepare a back electrode 8 (Ag) on ​​the surface of the electron transport layer 7 and the barrier layer until the preparation of the perovskite solar cell is completed.

[0098] Example 2

[0099] Referring again to FIG. 1 , an embodiment of a second method for preparing a perovskite solar cell according to the present invention includes the following steps:

[0100] Step 21: The glass on which the FTO transparent conductive layer 5 is prepared is cleaned with detergent, deionized water, acetone, and isopropyl alcohol ultrasonically for 30 minutes each, then blown dry with N2 and treated in a UV O-zone for 10 minutes.

[0101] Step 22: Prepare a transition layer 1 on the surface of the transparent conductive layer 5 of FTO using a mixed solution method. The structural formula of the material of the transition layer 1 is Cu 0.05 Al 0.2 Sn 0.75 O 1.851.4 mg of CuCl2, 5.4 mg of AlCl3, and 28.5 mg of SnCl2 were dissolved in 1 ml of deionized water, stirred and set aside. A transition layer 1 film with a thickness of 0.2 nm to 30 nm was prepared on the surface of the transparent conductive layer 5 of FTO by a doctor blade method, and heated at 500°C in air for 1 hour to obtain the required transition layer 1.

[0102] Step 23: Use magnetron sputtering equipment to prepare a Cu layer with a thickness of 1 nm to 100 nm on the surface of the transition layer 1. x O hole transport layer 2.

[0103] Step 24, in Cu x The buffer layer 3 is prepared on the surface of the hole transport layer 2 by magnetron sputtering. The structural formula of the buffer layer 3 material is Cu 0.4 Al 0.6 O 1.1 .

[0104] Step 25: Prepare the perovskite light absorbing layer 6 on the surface of the buffer layer 3 using a one-step solution method.

[0105] Step 26: sequentially coating an electron transport layer 7 (C60) and a barrier layer of zirconium acetylacetonate on the surface of the perovskite light absorbing layer 6.

[0106] Step 27: Prepare a back electrode 8 (Ag) on ​​the surface of the electron transport layer 7 and the barrier layer until the preparation of the perovskite solar cell is completed.

[0107] Example 3

[0108] Referring again to FIG. 1 , an embodiment of a third method for preparing a perovskite solar cell according to the present invention includes the following steps:

[0109] Step 31: The glass on which the FTO transparent conductive layer 5 is prepared is cleaned with detergent, deionized water, acetone, and isopropyl alcohol ultrasonically for 30 minutes each, then blown dry with N2 and treated in a UV O-zone for 10 minutes.

[0110] Step 32: prepare a 0.1M NiCl3, 0.1M AlCl3 hydrochloric acid solution, Fe as a catalyst, and treat for 10min to 30min. The treated FTO transparent conductive layer is heated in air at 500℃ for 30min to prepare an in-situ generated transition layer 1 of FTO, which has a structure of Ni. 0.1 Al 0.11 Sn 0.8 O 1.9 .

[0111] Step 33: Spin-coat a 0.15M nickel acetylacetonate ethanol solution on the surface of the transition layer 1 at 4000R for 30s, and then burn at 400°C for 30min to prepare a nickel oxide hole transport layer 2.

[0112] Step 34: Prepare a buffer layer 3 on the surface of the hole transport layer 2 by CVD equipment under NH3 and O2 atmospheres respectively. The structural formula of the buffer layer 3 material is Ni 0.9 Al 0.1 N 0.1 O 0.9 .

[0113] Step 35: Prepare the perovskite light absorbing layer 6 on the surface of the buffer layer 3 using a one-step solution method.

[0114] Step 36: sequentially coat the electron transport layer 7 (C60 and SnO2) on the surface of the perovskite light absorption layer 6.

[0115] Step 37: Prepare a back electrode 8 (Cu) on the surface of the electron transport layer 7 until the preparation of the perovskite solar cell is completed.

[0116] Example 4

[0117] Referring again to FIG. 1 , an embodiment of a fourth method for preparing a perovskite solar cell according to the present invention includes the following steps:

[0118] Step 41: The glass on which the FTO transparent conductive layer 5 is prepared is cleaned with detergent, deionized water, acetone, and isopropyl alcohol ultrasonically for 30 minutes each, then blown dry with N2 and treated in a UV O-zone for 10 minutes.

[0119] Step 42: Prepare a transition layer 1 on the surface of the transparent conductive layer 5 of FTO using a CVD device. The structural formula of the material of the transition layer 1 is Cu 0.05 Al 0.2 Sn 0.75 O 1.85 .

[0120] Step 43: Prepare the CuSCN hole transport layer 2 on the surface of the transition layer 1 by using a solution method.

[0121] Step 44: deposit a nanocrystalline mixture of Cu2O and Al2O3 on the surface of the CuSCN hole transport layer 2 by scraping to prepare Cu 0.5 Al 0.5 O buffer layer 3.

[0122] Step 45 : Prepare the perovskite light absorbing layer 6 on the surface of the buffer layer 3 using a one-step solution method.

[0123] Step 46: sequentially coat the electron transport layer 7 (SnO 2 ) on the surface of the perovskite light absorbing layer 6 .

[0124] Step 47: Prepare a back electrode 8 (Ag) on ​​the surface of the electron transport layer 7 until the preparation of the perovskite solar cell is completed.

[0125] The composite transport layer of the first perovskite solar cell of the present invention has the following characteristics:

[0126] 1. Conventional transparent conductive layers, such as FTO, are n-type doped. This invention introduces p-type dopants such as Al, B, and Si 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 matter with nitrogen-containing inorganics, which have excellent photothermal stability and passivate surface defects in the hole transport layer, improving the stability of the second interface between the hole transport layer and the perovskite light-absorbing layer.

[0127] 2. The perovskite solar cell of the present invention has greatly improved the light stability of the perovskite solar cell due to the use of a composite transmission layer. x As the hole transport layer, Ni is mainly composed of Ni 2+ 、Ni 3+ and a small amount of Ni 4+ exists in the form of 3+ Can improve carrier transport, but Ni 3+ The presence of high-valent Ni also causes Ni photocatalysis, affecting the light stability of perovskite solar cells. The transition layer proposed by the present invention allows the hole transport material to transition to the perovskite material, while controlling the Ni content in the transition layer. 3+ As well as the proportion of high-priced Ni, the light stability of perovskite solar cells is greatly improved.

[0128] Please refer to Figure 5, which shows the conversion efficiency curve of the perovskite solar cell prepared in Example 1 of the present invention (i.e., a three-layer composite structure). Comparative Example 1 shows the conversion efficiency curve of a conventional perovskite solar cell containing a single hole transport layer (i.e., a single hole transport layer). As shown in Figure 5, the open-circuit voltage of the perovskite solar cell containing the composite transport layer of the present invention is significantly improved. The open-circuit voltage of the single hole transport layer is 1.014V, while the voltage of the three-layer composite structure reaches 1.136V.

[0129] Referring to Figure 6, Comparative Example 2 shows the conversion efficiency curve for a perovskite solar cell with a double-layer structure comprising a transition layer and a hole transport layer (i.e., transition layer + hole transport layer), while Comparative Example 3 shows the conversion efficiency curve for a perovskite solar cell with a double-layer structure comprising a hole transport layer and a buffer layer (i.e., hole transport layer + buffer layer). As can be seen in Figure 6, Example 1 significantly improves Jsc and Voc compared to Comparative Example 2, significantly improves FF compared to Comparative Example 3, and further improves Voc, achieving an efficiency of 19.64%.

[0130] Please refer to Figure 7, which shows the aging test curves of the perovskite solar cell (i.e., a three-layer composite structure) prepared in Example 1 of the present invention, the aging test curves of the perovskite solar cell of Comparative Example 1 (i.e., a single-layer hole transport layer), the aging test curves of the perovskite solar cell of Comparative Example 2 (i.e., a double-layer structure of a transition layer + a hole transport layer), and the aging test curves of the perovskite solar cell of Comparative Example 3 (i.e., a double-layer structure of a hole transport layer + a buffer layer). As can be seen from Figure 7, the light aging stability of the perovskite solar cells of Comparative Examples 2 and 3 is improved compared to that of Comparative Example 1. The perovskite solar cell of Example 1 of the present invention decays less than 5% after 3500 hours of light aging, which is significantly better than the test results of the perovskite solar cells of Comparative Examples 1 to 3.

[0131] Example 5

[0132] Referring again to FIG. 2 , an embodiment of a method for preparing a second perovskite solar cell according to the present invention includes the following steps:

[0133] Step 51: The glass on which the FTO transparent conductive layer 5 is prepared is cleaned with detergent, deionized water, acetone, and isopropyl alcohol ultrasonically for 30 minutes each, then blown dry with N2 and treated in a UV O-zone for 10 minutes.

[0134] Step 52: 3-aminopropyltriethoxysilane is mixed with a suspension of Al2O3 and SnO2 nanoparticles (10 wt%, 100 nm) in IPA at a volume ratio of 1%, stirred and mixed, and then irradiated under a 365 nm UV lamp for 10 minutes for use; the mixed suspension is coated on the FTO transparent conductive layer 5 by a doctor blade method, and the wet film is heated and annealed to form an array transition layer 1 containing an opening 10.

[0135] Step 53: Spin-coat a 0.15M nickel acetylacetonate ethanol solution on the surface of the transition layer 1 at 4000R for 30s, and then burn at 400°C for 30min to prepare a nickel oxide hole transport layer 2 with a thickness of 1nm to 100nm.

[0136] Step 54: Prepare the buffer layer 3 by solution combustion method. The structural formula of the buffer layer 3 material is NiN0.3 O 0.7 29 mg of NiNO3·6H2O and 3 mg of urea were dissolved in 1 ml of deionized water, stirred, and a 0.2 nm to 50 nm thick buffer layer 3 film was prepared on the surface of the nickel oxide hole transport layer 2 by spray coating. The film was heated at 400°C for 30 min in a N2 atmosphere and at 200°C for 10 min in air.

[0137] Step 55 : Prepare the perovskite light absorbing layer 6 on the surface of the buffer layer 3 using a one-step solution method.

[0138] Step 56: sequentially coating an electron transport layer 7 (PCBM) and a barrier layer (BCP) on the surface of the perovskite light absorbing layer 6.

[0139] Step 57: Prepare a back electrode 8 (Ag) on ​​the surface of the electron transport layer 7 and the barrier layer until the preparation of the perovskite solar cell is completed.

[0140] Example 6

[0141] Referring to FIG. 3 and FIG. 8 , another embodiment of the second method for preparing a perovskite solar cell according to the present invention includes the following steps:

[0142] Step 61: The glass on which the FTO transparent conductive layer 5 is prepared is cleaned with detergent, deionized water, acetone, and isopropyl alcohol ultrasonically for 30 minutes each, then blown dry with N2 and treated in a UV O-zone for 10 minutes.

[0143] Step 62: Prepare a transition layer 1 with a thickness of 0.2 nm to 30 nm on the surface of the transparent conductive layer 5 of FTO by using a mixed solution method. The structural formula of the material of the transition layer 1 is Cu 0.05 Al 0.2 Sn 0.75 O 1.85 1.4 mg of CuCl2, 5.4 mg of AlCl3, and 28.5 mg of SnCl2 were dissolved in 1 ml of deionized water, stirred and set aside. A transition layer 1 film was prepared on the surface of the transparent conductive layer 5 of FTO by a doctor blade method, and heated at 500°C in air for 1 hour to obtain the required transition layer 1.

[0144] Step 63: Use magnetron sputtering equipment to prepare a Cu layer with a thickness of 1 nm to 100 nm on the surface of the transition layer 1. x O hole transport layer 2.

[0145] Step 64: Vinyltriethoxysilane and Cu xO and SiO2 nanoparticles (10wt%, 80nm) suspension were mixed in deionized water at a volume ratio of 1%, and the mixed solution was heated and stirred at 80-100℃ for 30min for use; the mixed suspension was coated on Cu by doctor blade method. x On the hole transport layer 2, an array buffer layer 3 containing openings 10 is obtained after annealing.

[0146] Step 65 : Prepare the perovskite light absorbing layer 6 on the surface of the buffer layer 3 using a one-step solution method.

[0147] Step 66: sequentially coating an electron transport layer 7 (C60) and a barrier layer (zirconium acetylacetonate) on the surface of the perovskite light absorbing layer 6.

[0148] Step 67: Prepare a back electrode 8 (Ag) on ​​the surface of the electron transport layer 7 and the barrier layer until the preparation of the perovskite solar cell is completed.

[0149] The composite transport layer of the second perovskite solar cell of the present invention also has the following characteristics:

[0150] 1. Conventional transparent conductive layers, such as FTO, are n-type doped. This invention introduces p-type dopants such as Al, B, and Si 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 matter with nitrogen-containing inorganics, which have excellent photothermal stability and passivate surface defects in the hole transport layer, improving the stability of the second interface between the hole transport layer and the perovskite light-absorbing layer.

[0151] 2. The perovskite solar cell of the present invention has greatly improved the light stability of the perovskite solar cell due to the use of a composite transmission layer. x As the hole transport layer, Ni is mainly composed of Ni 2+ 、Ni 3+ and a small amount of Ni 4+ exists in the form of 3+ Can improve carrier transport, but Ni 3+ The presence of high-valent Ni also causes Ni photocatalysis, affecting the light stability of perovskite solar cells. The transition layer proposed by the present invention allows the hole transport material to transition to the perovskite material, while controlling the Ni content in the transition layer. 3+ As well as the proportion of high-priced Ni, the light stability of perovskite solar cells is greatly improved.

[0152] 3. When coating, the nanoparticles simply form openings, which solves the problem of the inorganic oxide layer structure being too dense, eliminates the influence of the thickness of the transition layer and the buffer layer on the electrical tunneling, reduces the non-radiative recombination between the interface of the perovskite light absorption layer and the hole transport layer, and does not affect the carrier transport.

[0153] 4. Inorganic nanocrystals tend to aggregate over long periods of time due to charge imbalance caused by surface defects. Once aggregated, this can affect material stability. The bonding and dispersing effects of coupling agents prevent this phenomenon, improving material and device stability.

[0154] 5. There are a large number of disordered dangling bonds on the surface of the inorganic interface. The use of coupling agents can also play a role in passivating the dangling bonds on the surface of the inorganic material, thereby inhibiting the photocatalytic reaction at the interface between the inorganic material and the perovskite, and further improving the stability.

[0155] Please refer to Figure 9, which shows the conversion efficiency curve of the perovskite solar cell (i.e., a three-layer structure / including an array transition layer) prepared in Example 5 of the present invention. Comparative Example 1 is the conversion efficiency curve of an existing perovskite solar cell containing a single hole transport layer (i.e., a single hole transport layer). Comparative Example 4 is the conversion efficiency curve of a perovskite solar cell containing an array transition layer and a hole transport layer (i.e., an array transition layer / hole transport layer). Comparative Example 3 is the conversion efficiency curve of a perovskite solar cell containing a hole transport layer and a buffer layer (i.e., a hole transport layer / buffer layer). The difference between Comparative Example 4 and Example 6 is that Comparative Example 4 does not contain a buffer layer. The difference between Comparative Example 3 and Example 6 is that Comparative Example 3 does not contain a transition layer and the buffer layer is not in an array shape. As can be seen from Figure 9, the open circuit voltage and fill factor of the three-layer hole transport composite structure containing Example 5 of the present invention are significantly improved compared to Comparative Examples 1, 4, and 3. The open circuit voltage of the perovskite solar cell of Example 5 of the present invention reaches 1.147V and the FF reaches 79.23%. At the same time, it can be seen from the comparison between Figure 9 and Figure 5 that the efficiency of the perovskite solar cell device prepared by the three-layer composite structure including the array structure is also better than the three-layer composite structure without the array. The open circuit voltage is increased from 1.136V to 1.147V, the fill factor is significantly improved from 76.62% to 79.23%, and the conversion efficiency is increased from 19.64% to 20.34%, and the conversion efficiency is increased by about 3.6%.

[0156] Please refer to Figure 10, which shows the light aging test curve of the perovskite solar cell (i.e., a three-layer structure / containing an array-shaped transition layer) prepared in Example 5 of the present invention. Comparative Example 1 is the light aging test curve of the existing perovskite solar cell containing a single-layer hole transport layer (i.e., a single-layer hole transport layer). Comparative Example 4 is the light aging test curve of a perovskite solar cell containing an array transition layer and a hole transport layer (i.e., an array transition layer / hole transport layer). Comparative Example 3 is the light aging test curve of a perovskite solar cell containing a hole transport layer and a buffer layer (i.e., a hole transport layer / buffer layer). The light stability of Comparative Examples 4 and 5 is significantly improved compared to that of Comparative Example 1, but the aging test results of the perovskite solar cell prepared in Example 5 of the present invention are significantly better than those of Comparative Examples 1, 4, and 3. The light stability is greatly improved, with no attenuation after 2000 hours of light aging and less than 3% attenuation after 3500 hours. At the same time, comparing Figure 7 and Figure 10, the light stability of the perovskite solar cell device prepared by the three-layer composite structure including the array structure is also better than the three-layer composite structure without the array, and the attenuation after 3500 hours is reduced from about 5% to less than 3%.

[0157] 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 in the scope of protection of the present invention.

Claims

1. A composite transmission layer, characterized in that: It includes a transition layer, a hole transport layer and a buffer layer stacked in sequence according to the light incident direction, and the preparation material of the transition layer is Ni x A y Si z Sn m O n Cu x A y Si z Sn m O n , wherein x>0, y>=0, z>=0, m>=0, n>0, A is aluminum or boron, the material for preparing the transition layer contains at least one element of A, Si, Sn, and the material for preparing the hole transport layer is NiO x , Cu x O, CuSCN, the buffer layer is made of Ni a E b N c O d 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.

2. A composite transmission layer, characterized in that: It includes a transition layer, a hole transport layer and a buffer layer stacked in sequence according to the light incident direction, and the preparation material of the transition layer is Ni x A y Si z Sn m O n Cu x A y Si z Sn m O n , wherein x>0, y>=0, z>=0, m>=0, n>0, A is aluminum or boron, the material for preparing the transition layer contains at least one element of A, Si, Sn, and the material for preparing the hole transport layer is NiO x , Cu x O, CuSCN, the buffer layer is made of Ni a E b N c O d 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; a coupling agent is also added to the preparation material of the transition layer and / or the buffer layer to obtain a corresponding array transition layer and / or array buffer layer containing a coupling agent, and the film made of the transition layer and / or buffer layer doped with a coupling agent contains a plurality of discretely arranged array molecular clusters containing a coupling agent and openings separating two adjacent molecular clusters, each opening respectively connects the upper and lower surfaces of the film, and the coupling agent is any one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a phosphate coupling agent, and a borate coupling agent.

3. The composite transmission layer according to claim 2, characterized in that The coupling agent is added in an amount of 0.5-5% of the volume of the nanoparticle suspension to be added to prepare the transition layer and / or buffer layer, and the concentration of the nanoparticle suspension is 0.1-10 wt.%.

4. The composite transmission layer according to claim 2, characterized in that The length of the opening is 10 nm to 200 nm.

5. The composite transmission layer according to claim 1 or 2, characterized in that: The thickness of the transition layer is 0.2nm-30nm, the thickness of the hole transport layer is 1nm-100nm, and the thickness of the buffer layer is 0.2nm-50nm.

6. A perovskite solar cell, wherein the internal structure of the perovskite solar cell comprises a transparent conductive layer, a perovskite light absorbing layer, an electron transport layer and a back electrode stacked in sequence, characterized in that: The composite transmission layer according to claim 1 is arranged between the transparent conductive layer and the perovskite light absorbing layer, the transition layer of the composite transmission layer is in contact with the transparent conductive layer, and the buffer layer thereof is in contact with the perovskite light absorbing layer.

7. A perovskite solar cell, wherein the internal structure of the perovskite solar cell comprises a transparent conductive layer, a perovskite light absorbing layer, an electron transport layer and a back electrode stacked in sequence, characterized in that: The composite transmission layer as claimed in claim 2 is arranged between the transparent conductive layer and the perovskite light absorbing layer, the transition layer of the composite transmission layer is in contact with the transparent conductive layer, and the buffer layer thereof is in contact with the perovskite light absorbing layer.

8. A method for preparing a perovskite solar cell according to claim 6, characterized in that: The steps include: Step 1, cleaning and UV-ozone treating the transparent conductive layer; Step 2: Prepare a transition layer on the transparent conductive layer using a gas phase method or a liquid phase method. The gas phase method is to use any one of an atomic layer deposition device ALD, a chemical vapor deposition device CVD, a magnetron sputtering device, an electron beam evaporation device, and a thermal evaporation device to prepare the transition layer. 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: prepare a hole transport layer on the surface of the transition layer using any one of an atomic layer deposition device ALD, a chemical vapor deposition device CVD, a magnetron sputtering device, an electron beam evaporation device, and a thermal evaporation device, or prepare a hole transport layer by any one of a solution blade coating, a slit coating, and a spray coating process; Step 4: prepare a buffer layer on the surface of the hole transport layer using a gas phase method or a liquid phase method. The gas phase method is to use any one of an atomic layer deposition device ALD, a chemical vapor deposition device CVD, a magnetron sputtering device, an electron beam evaporation device, and a thermal evaporation device to prepare the buffer layer. The liquid phase method is to use any one of a mixed solution method, a hydrothermal method, a chemical bath, and an in-situ doping method to prepare the buffer layer. Step 5: Prepare a perovskite light absorbing layer, an electron transport layer and a back electrode in sequence on the surface of the buffer layer until the preparation of the perovskite solar cell is completed.

9. A method for preparing a perovskite solar cell according to claim 7, characterized in that: The steps include: Step I: cleaning and UV-ozone treating the transparent conductive layer; Step II, mixing the coupling agent with the material solution for preparing the transition layer to obtain a first composite precursor solution, subjecting the first composite precursor solution to UV light treatment or high temperature treatment, and then coating the treated first composite precursor solution on the surface of the transparent conductive layer, and annealing and drying to obtain an array transition layer; Step III, preparing a hole transport layer on the surface of the array 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 preparing a hole transport layer by any one of a solution blade coating, a slit coating, and a spray coating process; Step IV, preparing a buffer layer on the surface of the hole transport layer using a gas phase method or a liquid phase method, the gas phase method is to use 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 to prepare the buffer 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. Step V: sequentially prepare a perovskite light absorbing layer, an electron transport layer and a back electrode on the surface of the buffer layer until the preparation of the perovskite solar cell is completed.

10. A method for preparing a perovskite solar cell according to claim 7, characterized in that: The steps include: Step 1, cleaning and UV-ozone treating the transparent conductive layer; Step 2: Prepare a transition layer on the transparent conductive layer using a gas phase method or a liquid phase method. The gas phase method uses atomic layer deposition ALD. The transition layer is prepared by any one of equipment, chemical vapor deposition CVD equipment, magnetron sputtering equipment, electron beam evaporation equipment, and thermal evaporation equipment; the liquid phase method is any one of the processing methods of mixed solution method, hydrothermal method, chemical bath method, and in-situ doping method; Step 3: prepare 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 prepare a hole transport layer by any one of a solution blade coating, a slit coating, and a spray coating process; Step 4: Mix the coupling agent with the material solution for preparing the buffer layer to obtain a second composite precursor solution, subject the second composite precursor solution to UV light treatment or high temperature treatment, and then apply the treated second composite precursor solution on the surface of the hole transport layer, and anneal and dry to obtain the array buffer layer; Step 5: sequentially prepare a perovskite light absorbing layer, an electron transport layer and a back electrode on the surface of the array buffer layer until the preparation of the perovskite solar cell is completed.

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