Multi-layer composite transmission layer, perovskite solar module and preparation method of perovskite solar module

Abstract

The invention relates to a multi-layer composite transmission layer which comprises a blocking transition layer, a transition layer, a hole transmission layer and a buffer layer which are sequentially stacked in the light incidence direction, the blocking transition layer is prepared by doping an element R in a fluorine-doped tin oxide material to replace an element F, and the proportion range of the element R replacing the element F is 1%-100%. The R element is at least one element of W, Nb, Ni, Al and Si, the transition layer is prepared from NixAySizSnmOn or CuxAySizSnmOn, and x < gt >, y < gt >, y < gt >, y < gt >, y < gt >, y < gt > and y < gt >; 0, ygt; zgt is equal to 0; mgt = 0, mgt; ngt is equal to 0; 0, A is aluminum or boron, the preparation material of the hole transport layer is any one of NiOx, CuxO and CuSCN, and the preparation material of the buffer layer is NiaEbNcOd or CuaEbNcOd, where, egt; 0, bgt; cgt = 0; 0, dgt; e is any one of Al, B, Si, Zn, Co and Zr. The invention further discloses a perovskite solar module using the multi-layer composite transmission layer and a preparation method of the perovskite solar module. The perovskite solar module provided by the invention has the characteristics of high conversion efficiency and good long-term photo-thermal stability.

Description

Technical Field

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

[0002] The common device structures of perovskite solar modules include positive structure and inverted structure, wherein the positive structure refers to at least including, starting from the light incident surface, the following: transparent conductive layer, electron transport layer, perovskite active layer, hole transport layer and back electrode, and the inverted structure refers to at least including, starting from the light incident surface, the following: transparent conductive layer, hole transport layer, perovskite active layer, electron transport layer and back electrode. In the available reports, the highest conversion efficiency of perovskite solar modules with inverted structure is slightly lower than that of perovskite solar modules with positive structure, but the comprehensive stability of inverted structure is better than that of positive structure. It is generally believed that the main reason for the low conversion efficiency of inverted structure is that the energy band of the first interface formed by the transparent conductive layer and the hole transport layer is not matched, and the second interface formed by the hole transport layer and the perovskite active layer has many interface defects.

[0003] 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 The first type of material is easy to obtain and low in cost, but its good hole transport performance comes from the defects of the material itself. It often requires a higher defect density to obtain better hole transport performance. However, a higher defect density will make the photothermal stability of the second interface between the hole transport layer and the perovskite active layer worse, 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. The second type of material generally requires a longer synthesis path, has better hole transport performance, and is easier to obtain an inversion device with high conversion efficiency. Its biggest shortcoming is that the polymer material itself has poor photostability and is prone to decomposition under long-term outdoor light conditions, resulting in rapid performance decay of the inversion device. The third type of material can further improve the conversion efficiency of the inversion device on the basis of the second type of material, but similar to the second type of material, due to the use of organic matter, the stability is poor under long-term light. In order to solve these problems, there are also reports on the use of a composite structure of an inorganic hole transport layer and an organic hole transport layer or a method of passivating an inorganic hole transport layer. However, the use of a composite structure of an inorganic hole transport layer and an organic hole transport layer is an indicator-free solution, because under long-term light, the organic layer will still decompose, causing the effect of this composite structure to disappear. The passivation of the inorganic hole transport layer is often a stopgap measure in exchange for improved stability at the expense of conversion efficiency.

[0004] In addition, common transparent conductive layer materials such as fluorine-doped tin oxide (FTO) often contain a high concentration of F element doping. These F elements are at risk of migrating into the perovskite material during long-term use, causing it to degrade, making the perovskite solar module unstable and reducing its service life.

[0005] In addition, the existing hole transport layer is generally made of inorganic oxides. The hole transport layer of inorganic oxides has the following problems: 1) The structure formed by inorganic oxides may be too dense, and hole conduction may encounter some problems; 2) Inorganic nanocrystals are prone to agglomeration during long-term use due to charge imbalance caused by surface defects. Once agglomerated, it will affect the stability of the material; 3) There are a large number of disordered dangling bonds on the surface of the inorganic interface, some of which will react with the perovskite material. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a multi-layer composite transmission layer and a perovskite solar module and a preparation method thereof. The use of the multi-layer composite transmission layer not only greatly improves the light stability of the perovskite solar module, but also improves the conversion efficiency of the perovskite solar module. On the other hand, a coupling agent is doped in the preparation material of the multi-layer composite transmission layer to improve the conduction performance and stability of the hole transport layer made of inorganic oxide materials, so that the manufactured perovskite solar module has the characteristics of high conversion efficiency and good stability.

[0007] The present invention is implemented by providing a first multi-layer composite transmission layer, comprising a blocking transition layer, a transition layer, a hole transmission layer and a buffer layer stacked in sequence according to the light incident direction, wherein the preparation material of the blocking transition layer is a fluorine-doped tin oxide material doped with an R element to replace the F element, the proportion of the R element replacing the F element ranges from 1% to 100%, the R element is at least one element selected from W, Nb, Ni, Al and Si, 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.

[0008] The present invention is implemented in this way, and also provides a second multi-layer composite transmission layer, including a blocking transition layer, a transition layer, a hole transmission layer and a buffer layer stacked in sequence according to the light incident direction, wherein the preparation material of the blocking transition layer is a fluorine-doped tin oxide material doped with an R element to replace the F element, the proportion of the R element replacing the F element ranges from 1% to 100%, the R element is at least one element selected from W, Nb, Ni, Al and Si, 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 , Cux 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 doped in the preparation material of at least one of the blocking transition layer, the transition layer, and the buffer layer to obtain a corresponding array blocking transition layer and / or array transition layer and / or array buffer layer containing a coupling agent, and the film of the blocking transition layer and / or 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, wherein the openings connect 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; and the length of the opening is 10nm to 200nm.

[0009] The present invention is implemented in this way, and also provides a first 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 stacked in sequence, and a first multi-layer composite transport layer as described above is arranged between the transparent conductive layer and the perovskite light absorbing layer, the blocking transition layer of the multi-layer composite transport layer is in contact with the transparent conductive layer, and the buffer layer thereof is in contact with the perovskite light absorbing layer.

[0010] The present invention is implemented in this way, and also provides a second 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 stacked in sequence, and a second multi-layer composite transport layer as described above is arranged between the transparent conductive layer and the perovskite light absorbing layer, the blocking transition layer of the multi-layer composite transport layer is in contact with the transparent conductive layer, and the buffer layer thereof is in contact with the perovskite light absorbing layer.

[0011] The present invention is implemented in this way, and also provides a method for preparing the first perovskite solar module as described above, comprising the following steps:

[0012] Step 1, cleaning and UV-ozone treating the transparent conductive layer;

[0013] Step 2: Prepare a barrier 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 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 any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method.

[0014] Step 3: prepare a transition layer on the barrier transition 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 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.

[0015] Step 4: 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;

[0016] Step 5: 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 ALD device, a chemical vapor deposition CVD device, a magnetron sputtering device, an electron beam evaporation device, and a thermal evaporation device to prepare a 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.

[0017] Step 6: 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 module is completed.

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

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

[0020] Step II, using a gas phase method or a liquid phase method to prepare a blocking transition layer on the transparent conductive layer, 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 blocking 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.

[0021] Step III, 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 barrier transition layer, and annealing and drying to obtain the array transition layer;

[0022] Step IV, preparing 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 preparing a hole transport layer by any one of a doctor blade coating, a slit coating, and a spray coating process;

[0023] Step V, 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 device ALD, a chemical vapor deposition device CVD, a magnetron sputtering device, an electron beam evaporation device, and a thermal evaporation device to prepare a 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.

[0024] Step VI: 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 module is completed.

[0025] The present invention is implemented in this way, and also provides a method for preparing the second perovskite solar module as described above, comprising the following steps:

[0026] Step 1, cleaning and UV-ozone treating the transparent conductive layer;

[0027] Step 2: Prepare a blocking 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 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 blocking 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.

[0028] Step 3, using a gas phase method or a liquid phase method to prepare a transition layer on the barrier transition layer, 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 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.

[0029] Step 4: preparing 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 preparing a hole transport layer by any one of a solution blade coating, a slit coating, and a spray coating process;

[0030] Step 5, 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, and annealing and drying to obtain the array buffer layer;

[0031] Step 6: 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 module is completed.

[0032] The present invention is implemented in this way, and also provides a method for preparing the second perovskite solar module as described above, comprising the following steps:

[0033] Step A, cleaning and UV-ozone treating the transparent conductive layer;

[0034] Step B, mixing the coupling agent with the material solution for preparing the blocking transition layer to obtain a third composite precursor solution, subjecting the third composite precursor solution to UV light treatment or high temperature treatment, and then coating the treated third composite precursor solution on the surface of the transparent conductive layer, and annealing and drying to obtain the array blocking transition layer;

[0035] Step C, preparing a transition layer on the barrier transition 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 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;

[0036] Step D, preparing 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 preparing a hole transport layer by any one of solution blade coating, slit coating, and spraying;

[0037] Step E: 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. 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.

[0038] Step F: 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 module is completed.

[0039] Compared with the prior art, the first multi-layer composite transmission layer and perovskite solar module and the preparation method thereof of the present invention, the multi-layer composite transmission layer comprises a blocking transition layer, a transition layer, a hole transmission layer and a buffer layer stacked in sequence according to the light incident direction. The preparation material of the blocking transition layer is to dope R element in fluorine-doped tin oxide material to replace F element, the ratio of R element replacing F element ranges from 1% to 100%, R element is at least one element of W, Nb, Ni, Al, Si, 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. The perovskite solar module of the present invention uses the multi-layer composite transport layer, retaining the high defect density and high hole mobility of the hole transport material, so that the perovskite solar module including the multi-layer composite transport layer has the characteristics of high conversion efficiency and good long-term light and heat stability.

[0040] On the other hand, compared with the prior art, the second multi-layer composite transmission layer and perovskite solar module and the preparation method thereof of the present invention, the multi-layer composite transmission layer comprises a blocking transition layer, a transition layer, a hole transmission layer and a buffer layer stacked in sequence according to the light incident direction. The preparation material of the blocking transition layer is to dope the R element in the fluorine-doped tin oxide material to replace the F element, the ratio of the R element replacing the F element ranges from 1% to 100%, the R element is at least one element of W, Nb, Ni, Al, Si, and the preparation material of the transition layer is Ni x A y Si z Sn m O n Cu x A ySi 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 doped in the preparation material of at least one of the barrier transition layer, the transition layer, and the buffer layer to obtain a corresponding array barrier transition layer and / or array transition layer and / or array buffer layer containing a coupling agent. The film of the barrier transition layer and / or transition layer and / or buffer layer doped with a coupling agent contains a plurality of discretely arranged array molecular groups containing a coupling agent and an opening separating two adjacent molecular groups, and the opening connects 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 A schematic plan view of the internal structure of a preferred embodiment of the first perovskite solar cell module of the present invention;

[0042] Figure 2 is a schematic plan view of a first internal structure of a second perovskite solar module of the present invention;

[0043] Figure 3 is a schematic plan view of a second internal structure of a second perovskite solar module of the present invention;

[0044] Figure 4 is a schematic plan view of a third internal structure of the second perovskite solar module of the present invention;

[0045] Figure 5 for Figure 3 Schematic diagram of the multilayer composite transport layer of the second internal structure of the second perovskite solar module

[0046] Figure 6 A schematic diagram comparing conversion efficiency curves of the perovskite solar module prepared in Example 1 of the present invention and the perovskite solar module prepared in Comparative Example 1;

[0047] Figure 7 A schematic diagram comparing conversion efficiency curves of the perovskite solar module prepared in Example 1 of the present invention and the perovskite solar modules of Comparative Examples 2 to 3;

[0048] Figure 8 A comparison diagram of light aging of the perovskite solar module prepared in Example 1 of the present invention and the perovskite solar modules of Comparative Examples 1 to 3;

[0049] Fig. 9 A schematic diagram comparing conversion efficiency curves of the perovskite solar module prepared in Example 3 of the present invention and the perovskite solar modules of Comparative Examples 1, 4 and 5;

[0050] Fig.10 Schematic diagram comparing aging curves of the perovskite solar module prepared in Example 3 of the present invention and the perovskite solar modules of Comparative Examples 1, 4 and 5. DETAILED DESCRIPTION

[0051] 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 in conjunction with 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.

[0052] Please refer to Figure 1 As shown, a preferred embodiment of the first multi-layer composite transmission layer of the present invention comprises a blocking transition layer 1, a transition layer 2, a hole transport layer 3 and a buffer layer 4 stacked in sequence according to the light incident direction. The preparation material of the blocking transition layer 1 is a fluorine-doped tin oxide material doped with an R element to replace the 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 W, Nb, Ni, Al and Si. The preparation material of the transition layer 2 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 (Al) or boron (B), and the material for preparing the transition layer 2 contains at least one element of A, Si, and Sn. The material for preparing the hole transport layer 3 is NiO x , Cu x O, CuSCN. The buffer layer 4 is made of Ni a Eb 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.

[0053] Please also refer to Figures 2 to 4 As shown, a preferred embodiment of the second multi-layer composite transmission layer of the present invention comprises a blocking transition layer 1, a transition layer 2, a hole transport layer 3 and a buffer layer 4 stacked in sequence according to the light incident direction. The preparation material of the blocking transition layer 1 is to dope R element in the fluorine-doped tin oxide material to replace F element, and the ratio of R element replacing F element ranges from 1% to 100%, and R element is at least one element selected from W, Nb, Ni, Al and Si. The preparation material of the transition layer 2 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, and the material for preparing the transition layer 2 contains at least one element among A, Si, and Sn. The material for preparing the hole transport layer 3 is NiO x , Cu x O, CuSCN. The buffer layer 4 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.

[0054] A coupling agent is doped in the preparation material of at least one of the barrier transition layer 1, the transition layer 2, and the 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 film of the barrier transition layer 1 and / or the transition layer 2 and / or the buffer layer 4 doped with a coupling agent contains a plurality of discretely arranged array molecular groups 11 containing a coupling agent and an opening 10 separating two adjacent molecular groups, and the opening 10 connects 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.

[0055] Specifically, 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 barrier transition layer 1 and / or the transition layer 2 and / or the buffer layer 3, and the concentration of the nanoparticle suspension is 0.1-10 wt.%.

[0056] Specifically, the length of the opening 10 is 10 nm to 200 nm.

[0057] Specifically, in the first multilayer composite transport layer and the second multilayer composite transport layer of the present invention, the thickness of the blocking transition layer 1 is 1nm to 30nm, the thickness of the transition layer 2 is 0.2nm to 30nm, the thickness of the hole transport layer 3 is 1nm to 100nm, and the thickness of the buffer layer 4 is 0.2nm to 50nm.

[0058] Please refer to Figure 1 As shown, the present invention also discloses a first perovskite solar module, the internal structure of which includes a transparent conductive layer 6, a perovskite light absorbing layer 7, an electron transport layer 8 and a back electrode 9 stacked in sequence. The first multi-layer composite transport layer 5 as described above is arranged between the transparent conductive layer 6 and the perovskite light absorbing layer 7. The blocking transition layer 1 of the multi-layer composite transport layer 5 is in contact with the transparent conductive layer 6, and the buffer layer 4 thereof is in contact with the perovskite light absorbing layer 7. The transition layer 2 and the hole transport layer 3 of the multi-layer composite transport layer 5 are arranged between the blocking transition layer 1 and the buffer layer 4, the transition layer 2 is in contact with the blocking transition layer 1, and the hole transport layer 3 is in contact with the buffer layer 4.

[0059] Please refer to Figures 2 to 4As shown, the present invention also discloses a second perovskite solar module, the internal structure of which includes a transparent conductive layer 6, a perovskite light absorbing layer 7, an electron transport layer 8 and a back electrode 9 stacked in sequence. The second multi-layer composite transport layer 5 as described above is arranged between the transparent conductive layer 6 and the perovskite light absorbing layer 7. The blocking transition layer 1 of the multi-layer composite transport layer 5 is in contact with the transparent conductive layer 6, and the buffer layer 4 thereof is in contact with the perovskite light absorbing layer 7. The transition layer 2 and the hole transport layer 3 of the multi-layer composite transport layer 5 are arranged between the blocking transition layer 1 and the buffer layer 4, the transition layer 2 is in contact with the blocking transition layer 1, and the hole transport layer 3 is in contact with the buffer layer 4.

[0060] In the first perovskite solar module and the second perovskite solar module of the present invention, the molecular formula of the material for preparing the perovskite light-absorbing layer 7 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 anions selected from the group consisting of iodine, bromine, chlorine, astatine, thiocyanate, and acetate.

[0061] The multi-layer composite transmission layer of the second perovskite solar module of the present invention has the following characteristics:

[0062] 1. 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.

[0063] 2. Inorganic nanocrystals tend to aggregate during long-term use due to charge imbalance caused by surface defects. Once aggregated, it will affect the stability of the material. The bonding and dispersing effects of the coupling agent avoid this phenomenon and improve the stability of the material and device.

[0064] 3. There are a large number of disordered dangling bonds on the surface of the inorganic interface. The use of coupling agents can also passivate 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.

[0065] Please refer to Figure 1 As shown, the present invention also discloses a method for preparing the first perovskite solar module as described above, comprising the following steps:

[0066] Step 1: Clean and treat the transparent conductive layer 6 with ultraviolet ozone.

[0067] Step 2: Prepare a blocking transition layer 1 on the transparent conductive layer 6 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 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.

[0068] Step three, prepare the transition layer 2 on the blocking transition layer 1 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 transition layer. The liquid phase method is any one of the processing methods including a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method.

[0069] Step 4: Prepare a hole transport layer 3 on the surface of the transition layer 2 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 3 by any one of a solution blade coating, a slit coating, and a spray coating process.

[0070] Step 5: Prepare a buffer layer 4 on the surface of the hole transport layer 3 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 a 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.

[0071] Step 6: Prepare the perovskite light absorbing layer 7, the electron transport layer 8 and the back electrode 9 in sequence on the surface of the buffer layer 4 until the preparation of the perovskite solar cell module is completed.

[0072] Please refer to Figure 2 As shown, the present invention also discloses a method for preparing the second perovskite solar module as described above, comprising the following steps:

[0073] Step I: cleaning and treating the transparent conductive layer 6 with ultraviolet ozone.

[0074] Step II, using a gas phase method or a liquid phase method to prepare a blocking transition layer 1 on the transparent conductive layer 6, 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 blocking transition layer 1, 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.

[0075] Step III: Mix the coupling agent with the material solution for preparing the transition layer 2 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 barrier transition layer 1, and obtain the array transition layer 2 after annealing and drying.

[0076] Step IV: prepare the hole transport layer 3 on the surface of the transition layer 2 using any one of ALD equipment, chemical vapor deposition CVD equipment, magnetron sputtering equipment, electron beam evaporation equipment, and thermal evaporation equipment, or prepare the hole transport layer 3 by any one of solution blade coating, slit coating, and spraying.

[0077] Step V, prepare the buffer layer 4 on the surface of the hole transport layer 3 using a gas phase method or a liquid phase method. The gas phase method is to use any one of atomic layer deposition equipment ALD, chemical vapor deposition equipment CVD, magnetron sputtering equipment, electron beam evaporation equipment, and thermal evaporation equipment to prepare the transition layer 4. 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 VI: sequentially prepare a perovskite light absorbing layer 7, an electron transport layer 8 and a back electrode 9 on the surface of the buffer layer 4 until the preparation of the perovskite solar cell module is completed.

[0079] Please refer to Figure 3 As shown, the present invention also discloses a method for preparing the second perovskite solar module as described above, comprising the following steps:

[0080] Step 1: Clean and treat the transparent conductive layer 6 with ultraviolet ozone.

[0081] Step 2: Prepare a blocking transition layer 1 on the transparent conductive layer 6 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 blocking 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.

[0082] Step 3: Prepare the transition layer 2 on the blocking transition layer 1 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 transition layer 2. The liquid phase method is any one of the processing methods including a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method.

[0083] Step 4: Prepare a hole transport layer 3 on the surface of the transition layer 2 using any one of ALD equipment, chemical vapor deposition CVD equipment, magnetron sputtering equipment, electron beam evaporation equipment, and thermal evaporation equipment, or prepare the hole transport layer 3 by any one of solution blade coating, slit coating, and spraying.

[0084] Step 5: Mix the coupling agent with the material solution for preparing the buffer layer 4 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 3, and obtain the array buffer layer 4 after annealing and drying.

[0085] Step 6: sequentially prepare a perovskite light absorbing layer 7, an electron transport layer 8 and a back electrode 9 on the surface of the buffer layer 4 until the preparation of the perovskite solar cell module is completed.

[0086] Please refer to Figure 4 As shown, the present invention also discloses a method for preparing the second perovskite solar module as described above, comprising the following steps:

[0087] Step A: cleaning and treating the transparent conductive layer 6 with ultraviolet ozone.

[0088] Step B: Mix the coupling agent with the material solution for preparing the blocking transition layer 1 to obtain a third composite precursor solution, subject the third composite precursor solution to UV light treatment or high temperature treatment, and then coat the treated third composite precursor solution on the surface of the transparent conductive layer 6, and anneal and dry to obtain the array blocking transition layer 1.

[0089] Step C, using a gas phase method or a liquid phase method to prepare a transition layer 2 on the blocking transition layer 1, 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 transition layer 2, 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.

[0090] Step D: prepare the hole transport layer 3 on the surface of the transition layer 2 using any one of ALD equipment, chemical vapor deposition CVD equipment, magnetron sputtering equipment, electron beam evaporation equipment, and thermal evaporation equipment, or prepare the hole transport layer 3 by any one of solution blade coating, slit coating, and spraying.

[0091] Step E: prepare a buffer layer 4 on the surface of the hole transport layer 3 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 4. 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.

[0092] Step F: sequentially prepare a perovskite light absorbing layer 7, an electron transport layer 8 and a back electrode 9 on the surface of the buffer layer 4 until the preparation of the perovskite solar cell module is completed.

[0093] Specifically, the conditions of the UV light treatment are: the light wavelength range is 265nm to 365nm, and the light treatment time is 5min to 60min. The conditions of the high temperature treatment are: the heating temperature range is 50 to 100°C, and the heating treatment time is 5min to 60min.

[0094] The perovskite solar module structure and the preparation method thereof of the present invention are further described below through specific examples.

[0095] Example 1

[0096] Please refer to Figure 1 As shown, an embodiment of the method for preparing the first perovskite solar module of the present invention comprises the following steps:

[0097] Step 11: The glass on which the FTO transparent conductive layer 6 has been prepared is cleaned with detergent, deionized water, acetone, and isopropanol ultrasonically for 30 minutes each, then dried with N2 and treated with UV O-zone for 10 minutes.

[0098] Step 12: Prepare Al-doped tin oxide by chemical vapor deposition, with the Al doping ratio being 5-10%, to obtain a barrier transition layer 1.

[0099] Step 13: Using magnetron sputtering equipment to prepare a transition layer 2 with a thickness of 0.2 nm to 30 nm on the surface of the barrier transition layer 1. The structural formula of the material of the transition layer 2 is Ni 0.15 Al 0.05 Sn 0.8 O 1.825 .

[0100] Step 14: Spin-coat a 0.15M nickel acetylacetonate ethanol solution on the surface of the transition layer 2 at 4000R for 30s, and then burn at 400°C for 30min to prepare a nickel oxide hole transport layer 3.

[0101] Step 15: Prepare the buffer layer 4 by solution combustion method. The structural formula of the buffer layer 4 material is NiN 0.3 O 0.7 , 29 mg of NiNO3·6H2O and 3 mg of urea solution were dissolved in 1 ml of deionized water, stirred, and a 0.2 nm to 50 nm thick buffer layer 4 thin film was prepared on the surface of the nickel oxide hole transport layer 3 by spraying, and heated at 400°C for 30 min in N2 atmosphere and at 200°C for 10 min in air.

[0102] Step 16: Prepare the perovskite light absorbing layer 7 on the surface of the buffer layer 4 using a one-step solution method.

[0103] Step 17: sequentially coating an electron transport layer 8 (PCBM) and a barrier layer (BCP) on the surface of the perovskite light absorbing layer 7.

[0104] Step 18: Prepare a back electrode 9 (Ag) on ​​the surface of the electron transport layer 8 and the barrier layer until the preparation of the perovskite solar cell module is completed.

[0105] Example 2

[0106] Please refer to Figure 1 As shown, an embodiment of the method for preparing the second perovskite solar module of the present invention comprises the following steps:

[0107] Step 21, the glass on which the FTO transparent conductive layer 6 has been prepared is cleaned with detergent, deionized water, acetone, and isopropanol ultrasonically for 30 minutes each, then dried with N2 and treated with UV O-zone for 10 minutes.

[0108] Step 22: Prepare Nb-doped tin oxide by magnetron sputtering, with the doping ratio of Nb being 3-8%, to obtain a barrier transition layer 1.

[0109] Step 23: Prepare a transition layer 2 with a thickness of 0.2 nm to 30 nm on the surface of the barrier transition layer 1 by using a mixed solution method. The structural formula of the material of the transition layer 2 is Cu 0.05 Al 0.2 Sn 0.75 O 1.85 , dissolve 1.4 mg of CuCl2, 5.4 mg of AlCl3, and 28.5 mg of SnCl2 in 1 ml of deionized water, stir and set aside, use a doctor blade method to prepare a 0.2 nm to 30 nm thick transition layer 2 film on the surface of the blocking transition layer 1, and heat it at 500°C in air for 1 hour to obtain the required transition layer 2.

[0110] Step 24: Use a magnetron sputtering device Cu on the surface of the transition layer 2 x O hole transport layer 3.

[0111] Step 25: In Cu x The buffer layer 4 is prepared on the surface of the hole transport layer 3 by magnetron sputtering. The structural formula of the buffer layer 4 material is Cu 0.4 Al 0.6 O 1.1 .

[0112] Step 26: Prepare the perovskite light absorbing layer 7 on the surface of the buffer layer 4 using a one-step solution method.

[0113] Step 27: sequentially coating an electron transport layer 8 (C60) and a barrier layer (zirconium acetylacetonate) on the surface of the perovskite light absorbing layer 7.

[0114] Step 28: Prepare a back electrode 9 (Ag) on ​​the surface of the electron transport layer 8 and the barrier layer until the preparation of the perovskite solar cell module is completed.

[0115] The multi-layer composite transmission layer of the first perovskite solar module of the present invention has the following characteristics:

[0116] 1. Commonly used transparent conductive layers, such as FTO, are n-type doped. After the present invention introduces p-type doping such as Al, B, Si into the transition layer, a doping concentration gradient and energy level transition are formed between the transparent conductive layer and the hole transport layer. In addition, the buffer layer replaces organic matter with nitrogen-containing inorganic matter, which has good light and heat stability, passivates the surface defects of the hole transport layer, and improves the stability of the second interface between the hole transport layer and the perovskite light absorption layer.

[0117] 2. The perovskite solar module of the present invention uses a multi-layer composite transmission layer, which greatly improves the light stability of the perovskite solar module. x As the hole transport layer, Ni is mainly composed of Ni 2+ 、Ni 3+ And a small amount of Ni 4+ In the form of 3+ Can improve carrier transport, but Ni 3+ The presence of high-priced Ni also causes Ni photocatalysis, affecting the light stability of perovskite solar panels. The transition layer proposed by the present invention allows the hole transport material to transition to the perovskite material, while controlling the Ni in the transition layer. 3+ As well as the proportion of high-priced Ni, the light stability of perovskite solar modules is greatly improved.

[0118] 3. Commonly used transparent conductive layers such as FTO have a high concentration of fluorine doping. During the long-term use of perovskite solar modules, fluorine ions may migrate to the active layer of the perovskite solar modules. The barrier transition layer of the present invention can effectively inhibit this migration and improve the light stability of the perovskite solar modules.

[0119] Please refer to Figure 6 As shown in FIG. 1 , the conversion efficiency curve of the perovskite solar module (i.e., a composite structure of four hole transport layers) prepared in Example 1 of the present invention is shown, and the conversion efficiency curve of the comparative example 1 is the conversion efficiency curve of the existing perovskite solar module (i.e., a single hole transport layer) containing a single hole transport layer. Figure 6 It can be seen that the open circuit voltage of the composite structure including the four-layer hole transport layer of the present invention is significantly improved, and its open circuit voltage reaches 1.16V, while the open circuit voltage of the single-layer hole transport layer is 1.014V.

[0120] Please refer to Figure 7 As shown, the conversion efficiency curve of the perovskite solar module prepared in Example 1 of the present invention (i.e., a composite structure of four hole transport layers), and the conversion efficiency curve of Comparative Example 2 is a perovskite solar module having a composite hole transport layer structure including a blocking transition layer, a transition layer and a hole transport layer (i.e., a blocking transition layer / transition layer / hole transport layer). The open circuit voltage of Comparative Example 2 reaches 1.07V, and the short circuit current and fill factor of the single hole transport layer in Comparative Example 1 are significantly improved. The difference between Comparative Example 2 and Example 1 is that Comparative Example 2 does not have a buffer layer. Comparative Example 3 is a conversion efficiency curve of a perovskite solar module having a composite hole transport layer structure of a hole transport layer and a buffer layer (i.e., a hole transport layer / buffer layer). From Figure 7 It can be seen that the open circuit voltage of comparative example 3 is significantly improved to 1.11V, but the short circuit current and fill factor are not good. Compared with the above structures, the four-layer hole transport composite structure of Example 1 of the present invention is significantly improved in open circuit voltage, short circuit current and fill factor, with Voc reaching 1.16V and Jsc increased to 23mA / cm 2 , FF increased to more than 80% and the efficiency reached 21.49%.

[0121] Please refer to Figure 8 As shown, the light aging test curve of the perovskite solar module prepared in Example 1 of the present invention (i.e., a 4-layer hole transport composite structure), Comparative Example 1 is the light aging test curve of the existing perovskite solar module containing a single hole transport layer (i.e., a single hole transport layer), Comparative Example 2 is the light aging test curve of a perovskite solar module with a composite hole transport layer structure including a blocking transition layer, a transition layer and a hole transport layer (i.e., a blocking transition layer / transition layer / hole transport layer), and Comparative Example 3 is the light aging test curve of a perovskite solar module with a composite hole transport layer structure of a hole transport layer and a buffer layer (i.e., a hole transport layer / buffer layer). Figure 8 It can be seen that the light stability of Comparative Examples 2 and 3 is significantly improved, and the light stability of Example 1 of the present invention is greatly improved compared with the stability of Comparative Examples 1 to 3, and there is no attenuation after light aging for nearly 5000 hours.

[0122] Example 3

[0123] Please refer to Figure 2 As shown, an embodiment of the method for preparing the second perovskite solar module of the present invention comprises the following steps:

[0124] Step 31, the glass on which the FTO transparent conductive layer 6 has been prepared is cleaned with detergent, deionized water, acetone, and isopropanol ultrasonically for 30 minutes each, then dried with N2 and treated with UV O-zone for 10 minutes.

[0125] Step 32: Prepare Al-doped tin oxide by chemical vapor deposition, where the Al doping ratio is 5-10%, to obtain a barrier transition layer 1 with a thickness of 1 nm to 30 nm.

[0126] Step 33, mix 3-aminopropyltriethoxysilane with Al2O3 and SnO2 nanoparticles (10wt%, 100nm) suspension in IPA at a volume ratio of 1%, stir and mix, and irradiate under a 365nm UV lamp for 10 minutes for use; use a doctor blade method to apply the mixed suspension on the blocking transition layer 1, and after the wet film is heated and annealed, form an array transition layer 2 with a thickness of 0.2nm to 30nm.

[0127] Step 34: Spin-coat a 0.15M nickel acetylacetonate ethanol solution on the surface of the transition layer 2 at 4000R for 30s, and then burn at 400°C for 30min to prepare a nickel oxide hole transport layer 3 with a thickness of 1nm to 100nm.

[0128] Step 35: Prepare the buffer layer 4 by solution combustion method. The structural formula of the buffer layer 4 material is NiN 0.3 O 0.7 , 29 mg of NiNO3·6H2O and 3 mg of urea solution were dissolved in 1 ml of deionized water, stirred, and a 0.2 nm to 50 nm thick buffer layer 4 thin film was prepared on the surface of the nickel oxide hole transport layer 3 by spraying, and heated at 400°C for 30 min in N2 atmosphere and at 200°C for 10 min in air.

[0129] Step 36: Prepare the perovskite light absorbing layer 7 on the surface of the buffer layer 4 using a one-step solution method.

[0130] Step 37: sequentially coat the electron transport layer 8 (PCBM) and the barrier layer (BCP) on the surface of the perovskite light absorbing layer 7.

[0131] Step 38: Prepare a back electrode 9 (Ag) on ​​the surface of the electron transport layer 8 until the preparation of the perovskite solar module is completed.

[0132] Example 4

[0133] Please also refer to Figure 3 and Figure 5 As shown, another embodiment of the method for preparing the second perovskite solar module of the present invention comprises the following steps:

[0134] Step 41, the glass on which the FTO transparent conductive layer 6 has been prepared is cleaned with detergent, deionized water, acetone, and isopropanol ultrasonically for 30 minutes each, then dried with N2 and treated with UV O-zone for 10 minutes.

[0135] Step 42: Prepare Nb-doped tin oxide by magnetron sputtering, with the doping ratio of Nb being 3-8%, to obtain a barrier transition layer 1.

[0136] Step 43: Prepare a transition layer 2 with a thickness of 1 nm to 100 nm on the surface of the barrier transition layer 1 by using a mixed solution method. The structural formula of the material of the transition layer 2 is Cu 0.05 Al 0.2 Sn 0.75 O 1.85 , dissolve 1.4 mg of CuCl2, 5.4 mg of AlCl3, and 28.5 mg of SnCl2 in 1 ml of deionized water, stir and set aside, use a doctor blade method to prepare a 1 nm to 80 nm thick transition layer 2 film on the surface of the blocking transition layer 1, heat it at 500°C in air for 1 hour to obtain the required transition layer 2.

[0137] Step 44: Use a magnetron sputtering device Cu on the surface of the transition layer 2 x O hole transport layer 3.

[0138] Step 45: Vinyltriethoxysilane and Cu x O and SiO2 nanoparticles (10wt%, 80nm) suspension were mixed in deionized water at a volume ratio of 3%, and the mixed solution was heated and stirred at 80-100°C for 30min for use; the mixed suspension was coated on Cu by a doctor blade method. x On the hole transport layer 3, an array buffer layer 4 containing openings 10 is obtained after annealing.

[0139] Step 46: Prepare the perovskite light absorbing layer 7 on the surface of the buffer layer 4 using a one-step solution method.

[0140] Step 47: sequentially coating the electron transport layer 8 (C60) and the barrier layer (zirconium acetylacetonate) on the surface of the perovskite light absorbing layer 7.

[0141] Step 48: Prepare a back electrode 9 (Ag) on ​​the surface of the electron transport layer 8 until the preparation of the perovskite solar module is completed.

[0142] The multi-layer composite transmission layer of the second perovskite solar module of the present invention has the following characteristics:

[0143] 1. Commonly used transparent conductive layers, such as FTO, are n-type doped. After the present invention introduces p-type doping such as Al, B, Si into the transition layer, a doping concentration gradient and energy level transition are formed between the transparent conductive layer and the hole transport layer. In addition, the buffer layer replaces organic matter with nitrogen-containing inorganic matter, which has good light and heat stability, passivates the surface defects of the hole transport layer, and improves the stability of the second interface between the hole transport layer and the perovskite light absorption layer.

[0144] 2. The perovskite solar module of the present invention uses a multi-layer composite transmission layer, which greatly improves the light stability of the perovskite solar module. x As the hole transport layer, Ni is mainly composed of Ni 2+ 、Ni 3+ And a small amount of Ni 4+ In the form of 3+ Can improve carrier transport, but Ni 3+ The presence of high-priced Ni also causes Ni photocatalysis, affecting the light stability of perovskite solar panels. The transition layer proposed by the present invention allows the hole transport material to transition to the perovskite material, while controlling the Ni in the transition layer. 3+ As well as the proportion of high-priced Ni, the light stability of perovskite solar modules is greatly improved.

[0145] 3. Commonly used transparent conductive layers such as FTO have a high concentration of fluorine doping. During the long-term use of perovskite solar modules, the fluorine element may migrate to the active layer of the perovskite solar module. The barrier transition layer of the present invention can effectively inhibit this migration and improve the light stability of the perovskite solar module.

[0146] 4. 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 absorbing layer and the hole transport layer, and does not affect the carrier transport.

[0147] 5. Inorganic nanocrystals tend to aggregate during long-term use due to charge imbalance caused by surface defects. Once aggregated, it will affect the stability of the material. The bonding and dispersion effects of the coupling agent avoid this phenomenon and improve the stability of the material and device.

[0148] 6. There are a large number of disordered dangling bonds on the surface of the inorganic interface. The use of coupling agents can also passivate 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.

[0149] Please refer to Fig. 9As shown, the conversion efficiency curve of the perovskite solar module prepared in Example 3 of the present invention (i.e., the hole transport layer is a 4-layer composite structure / includes an array-like transition layer), Comparative Example 1 is the conversion efficiency curve of the existing perovskite solar module containing a single-layer hole transport layer (i.e., a single-layer hole transport layer), Comparative Example 4 is the conversion efficiency curve of the perovskite solar module containing a blocking transition layer, an array-like transition layer and a hole transport layer (i.e., a blocking transition layer / array-like transition layer / hole transport layer), and Comparative Example 5 is the conversion efficiency curve of the perovskite solar module containing a hole transport layer and an array-like buffer layer (i.e., a hole transport layer / array-like transition layer). The difference between Comparative Example 4 and Example 3 is that Comparative Example 4 does not contain a buffer layer. The difference between Comparative Example 5 and Example 4 is that Comparative Example 5 does not contain a blocking transition layer and an array-like transition layer. By Fig. 9 It can be seen that the efficiency of the perovskite solar module device in Comparative Examples 4 and 5 is greatly improved compared with that in Comparative Example 1, and the open circuit voltage and short circuit current of the perovskite solar module in Example 3 are greatly improved compared with those in Comparative Examples 1, 4 and 5. The open circuit voltage of Example 3 reaches 1.15V and the FF reaches 80.44%. Figure 7 and Fig. 9 By comparison, it can be seen that the efficiency of the perovskite solar cell device prepared by the four-layer composite structure including the array structure is also better than that of the four-layer composite structure without the array, and the short-circuit current is increased from 23.02mA / cm 2 Significantly increased to 24.46mA / cm 2 The conversion efficiency increased from 21.49% to 22.61%, and the conversion efficiency increased by about 5.2%.

[0150] Please refer to Fig.10 As shown, the light aging test curve of the perovskite solar module prepared in Example 3 of the present invention (i.e., the hole transport layer is a 4-layer composite structure / including an array-like transition layer), Comparative Example 1 is the light aging test curve of the existing perovskite solar module 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 the perovskite solar module containing a blocking transition layer, an array-like transition layer and a hole transport layer (i.e., a blocking transition layer / array-like transition layer / hole transport layer), and Comparative Example 5 is the light aging test curve of the perovskite solar module containing a hole transport layer and an array-like buffer layer (i.e., a hole transport layer / array-like transition layer). The difference between Comparative Example 4 and Example 3 is that Comparative Example 4 does not contain a buffer layer. The difference between Comparative Example 5 and Example 4 is that Comparative Example 5 does not contain a blocking transition layer and an array-like transition layer. From Fig.10 It can be seen that the light stability of the perovskite solar module of Example 3 of the present invention is greatly improved compared with the perovskite solar modules of Comparative Examples 1, 4 and 5, and the light aging of Example 3 is more than 5000h without attenuation. Figure 8 and Fig.10 The light stability of the perovskite solar cell device prepared with a four-layer composite structure including an array structure is slightly better than that of the four-layer composite structure without an array. The conversion efficiency of solar cells of both structures has not declined after 5000 hours of light aging.

[0151] 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 protection scope of the present invention.

Claims

1. A multi-layer composite transmission layer, characterized in that: The invention comprises a blocking transition layer, a transition layer, a hole transport layer and a buffer layer which are sequentially stacked in the direction of light incidence, wherein the material for preparing the blocking transition layer is a fluorine-doped tin oxide material doped with an R element to replace an F element, the proportion of the R element replacing the F element is in the range of 1% to 100%, the R element is at least one element selected from W, Nb, Ni, Al and Si, and the material for preparing 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 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.

2. A multi-layer composite transmission layer, characterized in that: The invention comprises a blocking transition layer, a transition layer, a hole transport layer and a buffer layer which are sequentially stacked in the direction of light incidence, wherein the material for preparing the blocking transition layer is a fluorine-doped tin oxide material doped with an R element to replace an F element, the proportion of the R element replacing the F element is in the range of 1% to 100%, the R element is at least one element selected from W, Nb, Ni, Al and Si, and the material for preparing 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 doped in the preparation material of at least one of the blocking transition layer, the transition layer, and the buffer layer to obtain a corresponding array blocking transition layer and / or array transition layer and / or array buffer layer containing a coupling agent, and the film of the blocking transition layer and / or 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, wherein the openings connect 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; and the length of the opening is 10nm to 200nm.

3. The multi-layer 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 barrier transition layer and / or transition layer and / or buffer layer, and the concentration of the nanoparticle suspension is 0.1-10wt.%.

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

5. A perovskite solar module, wherein the internal structure of the perovskite solar module 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 multilayer composite transmission layer according to claim 1 is arranged between the transparent conductive layer and the perovskite light absorbing layer, the barrier transition layer of the multilayer 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.

6. A perovskite solar module, wherein the internal structure of the perovskite solar module 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 multilayer composite transmission layer as claimed in claim 2 is arranged between the transparent conductive layer and the perovskite light absorbing layer, the barrier transition layer of the multilayer 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 method for preparing a perovskite solar module as claimed in claim 5, characterized in that: The steps include: Step 1, cleaning and UV-ozone treating the transparent conductive layer; Step 2: Prepare a barrier 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 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 any one of a mixed solution method, a hydrothermal method, a chemical bath method, and an in-situ doping method. Step 3: prepare a transition layer on the barrier transition 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 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 4: 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 5: 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 a 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 6: 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 module is completed.

8. A method for preparing a perovskite solar module according to claim 6, characterized in that: The steps include: Step I: cleaning and UV-ozone treating the transparent conductive layer; Step II, using a gas phase method or a liquid phase method to prepare a blocking transition layer on the transparent conductive layer, 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 blocking 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. Step III, 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 barrier transition layer, and annealing and drying to obtain the array transition layer; Step IV, preparing 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 preparing a hole transport layer by any one of a solution blade coating, a slit coating, and a spray coating process; Step V, 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 device ALD, a chemical vapor deposition device CVD, a magnetron sputtering device, an electron beam evaporation device, and a thermal evaporation device to prepare a 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. Step VI: 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 module is completed.

9. A method for preparing a perovskite solar module 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 blocking 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 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 blocking 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, using a gas phase method or a liquid phase method to prepare a transition layer on the barrier transition layer, 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 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. Step 4: preparing 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 preparing a hole transport layer by any one of a solution blade coating, a slit coating, and a spray coating process; Step 5, 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, and annealing and drying to obtain the array buffer layer; Step 6: 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 module is completed.

10. A method for preparing a perovskite solar module according to claim 6, characterized in that: The steps include: Step A, cleaning and UV-ozone treating the transparent conductive layer; Step B, mixing the coupling agent with the material solution for preparing the blocking transition layer to obtain a third composite precursor solution, subjecting the third composite precursor solution to UV light treatment or high temperature treatment, and then coating the treated third composite precursor solution on the surface of the transparent conductive layer, and annealing and drying to obtain the array blocking transition layer; Step C, preparing a transition layer on the barrier transition 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 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; Step D, preparing 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 preparing a hole transport layer by any one of solution blade coating, slit coating, and spraying; Step E: 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. 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 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 module is completed.

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