阅读说明：本技术 具有双层钙钛矿光活性层的太阳能电池的制备方法及结构 (Preparation method and structure of solar cell with double-layer perovskite photoactive layer ) 是由 朱卫东 张泽阳 张春福 郝跃 于 2021-01-22 设计创作，主要内容包括：本发明涉及一种具有双层钙钛矿光活性层的太阳能电池的制备方法及结构,本制备方法包括：对第一FTO衬底预处理得到第二FTO衬底；在第二FTO衬底的部分上表面旋涂TiO-(2)溶液得到TiO-(2)电子传输层；在TiO-(2)电子传输层的上表面旋涂PbBr-(2)溶液得到PbBr-(2)层；在PbBr-(2)层的上表面旋涂PMMA溶液得到PMMA超薄隔阻层；在PMMA超薄隔阻层的上表面旋涂PbCl-(2)溶液得到第一基底；对第一基底进行加热得到第二基底；在第二基底的上表面旋涂CsBr溶液得到第三基底；在第三基底的上表面淀积碳浆得到阳极碳电极,以制备具有双层钙钛矿光活性层的太阳能电池。本太阳能电池中的CsPbBr-(3)层和CsPbBrCl-(2)层具有不同的禁带宽度,可提高钙钛矿太阳能电池的光电转换效率,极大的抑制了光生载流子间的复合,有利于载流子的提取和传输。(The invention relates to a preparation method and a structure of a solar cell with a double-layer perovskite photoactive layer, wherein the preparation method comprises the following steps: preprocessing the first FTO substrate to obtain a second FTO substrate; spin coating TiO on a portion of the upper surface of the second FTO substrate 2 Solution to obtain TiO 2 An electron transport layer; in TiO 2 The upper surface of the electron transport layer is coated with PbBr by spin coating 2 Obtaining PbBr from the solution 2 A layer; in PbBr 2 Spin-coating PMMA solution on the upper surface of the layer to obtain a PMMA ultrathin barrier layer; spin coating PbCl on the upper surface of PMMA ultrathin barrier layer 2 Obtaining a first substrate from the solution; heating the first substrate to obtain a second substrate; spin coating CsBr solution on the upper surface of the second substrateObtaining a third substrate; and depositing carbon slurry on the upper surface of the third substrate to obtain an anode carbon electrode so as to prepare the solar cell with the double-layer perovskite photoactive layer. CsPbBr in solar cell 3 Layer and CsPbBrCl 2 The layers have different forbidden band widths, can improve the photoelectric conversion efficiency of the perovskite solar cell, greatly inhibits the recombination between photon-generated carriers, and is beneficial to the extraction and transmission of the carriers.)

1. A method of fabricating a solar cell having a double-layer perovskite photoactive layer, comprising:

preprocessing the first FTO substrate (1) to obtain a second FTO substrate (2);

spin coating TiO on part of the upper surface of the second FTO substrate (2)₂Solution to obtain TiO₂An electron transport layer (3);

in the TiO₂The upper surface of the electron transport layer (3) is coated with PbBr by spin coating₂Obtaining PbBr from the solution₂A layer (4);

in the PbBr₂Spin-coating a PMMA solution on the upper surface of the layer (4) to obtain a PMMA ultrathin barrier layer (5);

coating PbCl on the upper surface of the PMMA ultrathin barrier layer (5) in a spin coating manner₂Obtaining a first base (7) by using the solution, wherein the second FTO substrate (2) and the TiO are sequentially laminated on the first base (7) from bottom to top₂An electron transport layer (3) and the PbBr₂Layer (4), the PMMA ultrathin barrier layer (5) and PbCl₂Layer (6);

heating the first substrate (7) to obtain a second substrate (8), wherein the second substrate (8) is formed by sequentially stacking the second FTO substrate (2) and the TiO from bottom to top₂An electron transport layer (3) and the PbBr₂Layer (4) and the PbCl₂Layer (6);

spin-coating a CsBr solution on the upper surface of the second base (8) to obtain a third base (9), wherein the third base (9) is formed by sequentially stacking the second FTO substrate (2) and the TiO from bottom to top₂Electron transport layer (3), CsPbBr₃Layer (11) andCsPbBrCl₂a layer (12);

and depositing carbon slurry on the upper surface of the third substrate (9) to obtain an anode carbon electrode (10) so as to prepare the solar cell with the double-layer perovskite photoactive layer.

2. The method for the preparation of a solar cell with a double-layer perovskite photoactive layer according to claim 1, characterized in that a cathode electrode is provided on the upper surface of the remaining part of the second FTO substrate (2).

3. Method for the preparation of a solar cell with a double-layer perovskite photoactive layer according to claim 1, characterized in that heating the first substrate (7) results in a second substrate (8) comprising:

and heating the first substrate (7) to ensure that the PMMA ultrathin barrier layer (5) is decomposed and evaporated with heat so as to prepare the second substrate (8).

4. The method for preparing a solar cell with a double-layer perovskite photoactive layer according to claim 3, characterized in that the first substrate (7) is heated with a high-temperature hot stage at a temperature of 280 ℃ to 300 ℃.

5. The method for preparing a solar cell with a bilayer perovskite photoactive layer according to claim 1, wherein spin-coating a CsBr solution on the upper surface of the second substrate (8) to obtain a third substrate (9) comprises:

spin-coating CsBr solution on the upper surface of the second substrate (8) to enable the PbBr to be₂Reacting the layer (4) with the CsBr solution to obtain the CsPbBr₃Layer (11), the PbCl₂Reacting the layer (6) with the CsBr solution to obtain the CsPbBrCl₂Layer (12) to prepare said third substrate (9).

6. The method of claim 1, wherein the CsPbBr is added to the double perovskite photoactive layer₃The thickness of the layer (11) is in the range of 300 to 350 nm.

7. The method of claim 1, wherein the CsPbBrCl is present in the solar cell comprising a double perovskite photoactive layer₂The thickness of the layer (12) is in the range of 50 to 150 nm.

8. The preparation method of the solar cell with the double-layer perovskite photoactive layer according to claim 1, wherein the spin coating dosage of the CsBr solution is 80-150 μ L.

9. A solar cell structure having a double-layer perovskite photoactive layer, which is prepared by the method for preparing a solar cell having a double-layer perovskite photoactive layer according to any one of claims 1 to 8, comprising:

a second FTO substrate (2);

TiO₂the electron transmission layer (3) is arranged on the upper surface of the second FTO substrate (2);

CsPbBr₃a layer (11) arranged on the TiO₂An upper surface of the electron transport layer (3);

CsPbBrCl₂a layer (12) disposed on the CsPbBr₃An upper surface of the layer (11);

an anodic carbon electrode (10) disposed on the CsPbBrCl₂The upper surface of the layer (12).

Technical Field

The invention belongs to the technical field of perovskite solar cells, and particularly relates to a preparation method and a structure of a solar cell with a double-layer perovskite photoactive layer.

Background

The perovskite solar cell uses perovskite type organic metal halide semiconductor as a light absorption material, and belongs to the third generation solar cell. The organic metal halide perovskite has the advantages of being obvious, and has a plurality of excellent optical and electrical properties such as adjustable band gap, long carrier diffusion length, high mobility, low defect density and the like, so that the perovskite solar cell has the efficiency equivalent to that of a silicon-based solar cell, and in addition, the organic metal halide perovskite becomes a hotspot in the research field of optoelectronic devices in recent years due to the potential advantages of high photoelectric conversion efficiency, simple preparation process, low cost and the like.

At present, organic-inorganic hybrid lead-halogen perovskites contain volatile and hydrophilic organic cation components, so that the perovskite compounds are easy to decompose and degrade under high-temperature, high-humidity or continuous illumination conditions. Therefore, under extreme conditions such as high temperature, high humidity or continuous illumination, the problem of poor reliability of organic-inorganic hybrid lead-halogen perovskite solar cells is difficult to avoid, and on the other hand, most perovskite photovoltaic devices comprise an organic charge transport layer and a metal electrode, and the former has the problem of poor stability. In addition, atoms in the metal electrode of the device tend to diffuse to the organic-inorganic hybrid lead-halogen perovskite film/charge transport layer interface to chemically react with halogen in the film, further aggravating the degradation of the device.

However, the carbon-based CsPbBr3-xClx inorganic perovskite solar cell completely avoids the use of organic-inorganic hybrid lead-halogen perovskite materials with poor stability, organic charge transport materials and metal electrodes, so that the solar cell becomes one of important ways for overcoming the reliability problem of perovskite photovoltaic devices. The carbon-based CsPbBr3-xClx inorganic perovskite photoactive layer is usually prepared by adopting a one-step solution spin coating method or a two-step spin coating method, but the spectrum utilization range of a single-layer photoactive layer is limited, the photoelectric conversion efficiency of a device is limited, the photogenerated current is reduced, the interface energy levels of the photoactive layer and a carbon electrode are not matched, more defects are formed at the interface, the extraction and transmission of carriers are limited, the recombination of photogenerated carriers is easily caused, and the stability of the perovskite on water and oxygen is also influenced to a certain extent by more defects, so that the performance of the perovskite is seriously degraded.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a preparation method and a structure of a solar cell with a double-layer perovskite photoactive layer. The technical problem to be solved by the invention is realized by the following technical scheme:

one embodiment of the present invention provides a method of fabricating a solar cell having a double-layered perovskite photoactive layer, comprising:

preprocessing the first FTO substrate to obtain a second FTO substrate;

spin coating TiO on part of the upper surface of the second FTO substrate₂Solution to obtain TiO₂An electron transport layer;

in the TiO₂The upper surface of the electron transport layer is coated with PbBr by spin coating₂Obtaining PbBr from the solution₂A layer;

in the PbBr₂Spin-coating PMMA solution on the upper surface of the layer to obtain a PMMA ultrathin barrier layer;

spin coating PbCl on the upper surface of the PMMA ultrathin barrier layer₂Obtaining a first base by using the solution, wherein the first base is formed by sequentially laminating the second FTO substrate and the TiO from bottom to top₂An electron transport layer, the PbBr₂Layer, the PMMA ultra-thin barrier layer and PbCl₂Layer composition;

heating the first substrate to obtain a second substrate, wherein the second substrate is sequentially stacked from bottom to top on the second FTO substrateTiO₂An electron transport layer, the PbBr₂Layer and the PbCl₂Layer composition;

spin-coating CsBr solution on the upper surface of the second substrate to obtain a third substrate, wherein the third substrate is formed by sequentially laminating the second FTO substrate and the TiO from bottom to top₂Electron transport layer, CsPbBr₃Layer and CsPbBrCl₂Layer composition;

and depositing carbon slurry on the upper surface of the third substrate to obtain an anode carbon electrode so as to prepare the solar cell with the double-layer perovskite photoactive layer.

In one embodiment of the present invention, a cathode electrode is disposed on the upper surface of the remaining portion of the second FTO substrate.

In one embodiment of the present invention, heating the first substrate to obtain a second substrate comprises:

and heating the first substrate to ensure that the PMMA ultrathin barrier layer is decomposed and evaporated with heat so as to prepare the second substrate.

In one embodiment of the invention, the first substrate is heated using a high temperature heat block having a temperature of 280 ℃ to 300 ℃.

In one embodiment of the present invention, spin-coating a CsBr solution on a top surface of the second substrate to obtain a third substrate, includes:

spin-coating CsBr solution on the upper surface of the second substrate to enable the PbBr to be₂Reacting the layer with the CsBr solution to obtain CsPbBr₃Layer of said PbCl₂Reacting the layer with the CsBr solution to obtain the CsPbBrCl₂A layer to prepare the third substrate.

In one embodiment of the invention, the CsPbBr is₃The thickness of the layer is 300-350 nm.

In one embodiment of the invention, the CsPbBrCl is₂The thickness of the layer is 50-150 nm.

In one embodiment of the invention, the spin coating dose of the CsBr solution is 80-150 μ L.

One embodiment of the present invention provides a solar cell structure having a double-layer perovskite photoactive layer, comprising:

a second FTO substrate;

TiO₂the electron transmission layer is arranged on the upper surface of the second FTO substrate;

CsPbBr₃a layer provided on the TiO₂An upper surface of the electron transport layer;

CsPbBrCl₂a layer disposed on the CsPbBr₃An upper surface of the layer;

an anode carbon electrode disposed on the CsPbBrCl₂The upper surface of the layer.

Compared with the prior art, the invention has the beneficial effects that:

the application discloses a preparation method and a structure of a solar cell with a double-layer perovskite photoactive layer₂Electron transport layer, CsPbBr₃Layer, CsPbBrCl₂Layer and anode carbon electrode on TiO₂Sequentially generating PbBr on the upper surface of the electron transport layer₂Layer, PMMA ultra-thin barrier layer and PbCl₂Layer, then to the FTO/TiO formed₂/PbBr₂/PMMA/PbCl₂Heating the substrate, spin-coating CsBr solution to obtain a third substrate, and finally, coating CsPbBr in the third substrate₃Layer and CsPbBrCl₂The layer is a double-layer perovskite photoactive layer, has different forbidden bandwidth, improves the photoelectric conversion efficiency of the perovskite solar cell, further increases the photoproduction current, and promotes the energy level matching degree of the interface of the perovskite photoactive layer and the anode carbon electrode. Meanwhile, CsPbBrCl₂The material of the layer has the function of passivating the interface defects, and the recombination among photon-generated carriers is greatly inhibited; CsPbBrCl₂The band gap of the layer is wide, so that the extraction and transmission of carriers are facilitated; CsPbBrCl₂The material of the layer has good stability in a room temperature environment, the influence of water-oxygen erosion on the perovskite solar cell in the environment can be reduced, and the performance and the stability of the perovskite solar cell are improved.

Drawings

Fig. 1 is a flow chart of a method for manufacturing a solar cell having a double-layer perovskite photoactive layer according to an embodiment of the present invention;

FIGS. 2a to 2i are schematic diagrams illustrating a process for manufacturing a solar cell having a double-layer perovskite photoactive layer according to an embodiment of the present invention;

fig. 3 is a structural diagram of a solar cell having a double-layer perovskite photoactive layer according to an embodiment of the present invention.

Detailed Description

The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.

In the present embodiment, the terms "upper", "lower", "left" and "right" indicate the positional relationship when the solar cell structure of the double-layer perovskite photoactive layer is in the illustrated state, "long" indicates the lateral dimension when the solar cell structure of the double-layer perovskite photoactive layer is in the illustrated state, and "deep" indicates the longitudinal dimension when the solar cell structure of the double-layer perovskite photoactive layer is in the illustrated state.

Example one

Referring to fig. 1 and fig. 2a to 2i, fig. 1 is a flow chart of a method for manufacturing a solar cell having a double-layer perovskite photoactive layer according to an embodiment of the present invention, and fig. 2a to 2i are schematic diagrams of a process for manufacturing a solar cell having a double-layer perovskite photoactive layer according to an embodiment of the present invention. The embodiment discloses a preparation method of a solar cell with a double-layer perovskite photoactive layer, which comprises the following steps:

step 1, preprocessing a first FTO substrate 1 to obtain a second FTO substrate 2.

Specifically, the first FTO substrate 1 is sequentially placed into a Decon-90 aqueous solution, deionized water, acetone and absolute ethyl alcohol for ultrasonic cleaning, and the cleaning time is 15-20 min. Then placing the first FTO substrate 1 which is subjected to ultrasonic cleaning into a UV-zone for UV-O₃Treating to obtain a second FTO substrate 2, UV-O₃The treatment time is 15-30 min.

Step 2, coating TiO on part of the upper surface of the second FTO substrate 2 in a spin coating mode₂Solution to obtain TiO₂An electron transport layer 3.

Specifically, 80. mu.L of TiO was mixed by a spin coater₂The solution was spin coated on a portion of the upper surface of the second FTO substrate 2 at a spin coater speed of 3000rpm for 30 seconds, and then placed in a muffle furnace at 500 ℃ and annealed in an air atmosphere for 1 hour. The size of the spin coater may be, for example, TP 200.

Step 3, in TiO₂The upper surface of the electron transmission layer 3 is coated with PbBr by spin coating₂Obtaining PbBr from the solution₂And (4) a layer.

In particular, the second FTO substrate 2 and TiO that have been prepared₂Electron transport layer 3 composition FTO/TiO₂Substrate, FTO/TiO₂The substrate was placed in a glove box N₂In the environment, 85 μ L of PbBr was mixed using a spin coater₂The solution is coated on FTO/TiO by spinning₂Upper surface of the substrate, PbBr₂The concentration of the solution is 367mg/mL, the rotating speed of a spin coater is 2000rpm, the spin coating time is 30s, and then PbBr is spin-coated₂FTO/TiO of solution₂The substrate is placed on a 90 ℃ hot bench to be annealed for 30min to obtain PbBr₂And (4) a layer.

PbBr₂The preparation method of the solution comprises the following steps: proportionally mixing 367mg of PbBr₂Dissolving the solid in 1mL dimethylformamide solution, stirring at a temperature of less than 90 deg.C until PbBr is added₂The solid was completely dissolved.

Step 4, in PbBr₂And spin-coating a PMMA solution on the upper surface of the layer 4 to obtain the PMMA ultrathin barrier layer 5.

Specifically, 50. mu.L of PMMA solution was spin coated onto PbBr using a spin coater₂The upper surface of layer 4 was spin coated at 4000rpm for 30s and the spin coater was then coated with FTO/TiO₂/PbBr₂The substrate is placed at room temperature to obtain the PMMA ultrathin barrier layer 5, and the room temperature is 25 ℃.

The preparation method of the PMMA solution comprises the following steps: dissolving PMMA powder with the mass of 1mg in a chlorobenzene solution with the volume of 1mL according to a proportion, and stirring the mixture under a normal-temperature environment until the PMMA powder is completely dissolved.

Step 5, spin coating PbCl on the upper surface of the PMMA ultrathin barrier layer 5₂Obtaining a first base 7 from the solution, and sequentially laminating a second FTO substrate 2 and TiO on the first base 7 from bottom to top₂Electron transport layer 3, PbBr₂Layer 4, PMMA ultra-thin barrier layer 5 and PbCl₂Layer 6.

Specifically, 85. mu.L of PbCl was mixed using a spin coater₂The solution is spin-coated on the upper surface of the PMMA ultrathin barrier layer 5, the rotating speed of a spin coater is 4000rpm, the spin-coating time is 30s, and then the PbCl is spin-coated₂FTO/TiO of solution₂/PbBr₂Placing the PMMA substrate on a 90 ℃ hot bench for annealing for 30min to obtain PbCl₂And (6) a layer.

PbCl₂The preparation method of the solution comprises the following steps: proportionally mixing PbCl with mass of 27.8mg₂The solid is dissolved in dimethylformamide solution with the volume of 1mL, and stirred under the normal temperature environment until the solid is completely dissolved.

Step 6, heating the first substrate 7 to obtain a second substrate 8, wherein the second substrate 8 is formed by sequentially laminating a second FTO substrate 2 and TiO from bottom to top₂Electron transport layer 3, PbBr₂Layer 4 and PbCl₂Layer 6.

Further, the first substrate 7 is heated to evaporate the PMMA ultra-thin barrier layer 5 by thermal decomposition to prepare a second substrate 8.

Specifically, the first substrate 7 is heated by a high temperature hot stage at a temperature of 280 ℃ to 300 ℃, preferably at a temperature of 280 ℃ for 3 min.

Step 7, spin-coating CsBr solution on the upper surface of the second substrate 8 to obtain a third substrate 9, and sequentially laminating the third substrate 9 and the second FTO substrate 2 and the TiO from bottom to top₂Electron transport layer 3, CsPbBr₃Layer 11 and CsPbBrCl₂Layer 12.

Further, CsBr solution is spin-coated on the upper surface of the second substrate 8 to make PbBr₂Reacting the layer 4 with CsBr solution to obtain CsPbBr₃Layer 11, PbCl₂The layer 6 reacts with CsBr solution to obtain CsPbBrCl₂Layer 12 to prepare the third substrate 9.

Specifically, the second substrate 8 was placed in an air room temperature environment, and 110 μ L of the CsBr solution was spin-coated on the upper surface of the second substrate 8 using a spin coater at 2000rpm for 30 seconds. Then, the second substrate 8 on which the CsBr solution was spin-coated was placed on a 250 ℃ hot stage and annealed for 5min to obtain a third substrate 9.

And 8, depositing carbon slurry on the upper surface of the third substrate 9 to obtain an anode carbon electrode 10 so as to prepare the solar cell with the double-layer perovskite photoactive layer.

Specifically, the third substrate 9 is placed in a room temperature environment, conductive carbon paste is deposited on the upper surface of the third substrate 9 by using a screen printing method, and then the third substrate is placed on a hot stage at 120 ℃ for annealing for 15min to obtain the carbon electrode 10, wherein the carbon electrode 10 is used as an anode of the solar cell of the present application.

In summary, this example discloses a method for fabricating a solar cell with a double-layered perovskite photoactive layer by applying a chemical solution to TiO₂Sequentially generating PbBr on the upper surface of the electron transport layer₂Layer, PMMA ultra-thin barrier layer and PbCl₂Heating the formed first substrate 7, spin-coating CsBr solution to obtain the third substrate 9 CsPbBr₃Layer and CsPbBrCl₂The layer is a double-layer perovskite light active layer with different forbidden band widths, different solar spectrums absorbed by different band gaps, CsPbBr₃Layer and CsPbBrCl₂The spectrum utilization range can be widened to the bilayer structure on layer, utilizes the perovskite solar cell of wide band gap to absorb the light of short wavelength, utilizes the perovskite solar cell of narrow band gap to absorb the light of long wavelength, and very big limit becomes the electric energy with light energy, has improved perovskite solar cell's photoelectric conversion efficiency, and then increases the photoproduction current, promotes the energy level matching degree of light active layer and positive pole carbon electrode interface. CsPbBrCl₂The material of the layer has the function of passivating the interface defects, and the recombination among photon-generated carriers is greatly inhibited; CsPbBrCl₂The band gap of the layer is wide, so that the extraction and transmission of carriers are facilitated; CsPbBrCl₂The material of the layer has good stability in a room temperature environment, the influence of water-oxygen erosion on the perovskite solar cell in the environment can be reduced, and the performance and the stability of the perovskite solar cell are improved.

Example two

Referring to fig. 3, fig. 3 is a structural diagram of a solar cell having a double-layer perovskite photoactive layer according to an embodiment of the present invention. The embodiment discloses a solar cell structure with a double-layer perovskite photoactive layer, which comprises:

a second FTO substrate 2;

TiO₂an electron transport layer 3 disposed on the upper surface of the second FTO substrate 2;

CsPbBr₃layer 11 on TiO₂The upper surface of the electron transport layer 3;

CsPbBrCl₂a layer 12 disposed on CsPbBr₃The upper surface of layer 11;

an anode carbon electrode 10 disposed on CsPbBrCl₂The upper surface of layer 12.

In the embodiment, the second FTO substrate 2 is prepared by placing the first FTO substrate 1 into Decon-90 aqueous solution, deionized water, acetone and absolute ethyl alcohol in sequence for ultrasonic cleaning, and then placing into UV-zone for UV-O₃And (4) processing to obtain the product. The first FTO substrate 1 is specifically an FTO/Glass substrate, and the thickness of the second FTO substrate 2 is 1.5 mm-2.5 mm.

TiO₂The electron transport layer 3 is formed by spin coating TiO on the upper surface of the second FTO substrate 2₂Obtained from solution, TiO₂The thickness of the electron transport layer 3 is 50nm to 80 nm.

Further, in TiO₂The upper surface of the electron transmission layer 3 is coated with PbBr by spin coating₂Obtaining PbBr from the solution₂Layer 4 followed by PbBr₂Spin coating PMMA solution on the upper surface of the layer 4 to obtain a PMMA ultrathin barrier layer 5, wherein the thickness of the PMMA ultrathin barrier layer 5 is 10-50 nm, and spin coating PbCl on the upper surface of the PMMA ultrathin barrier layer 5₂Obtaining PbCl from the solution₂Layer 6, then FTO/TiO₂/PbBr₂/PMMA/PbCl₂The substrate 7 is placed on a high-temperature heating table to be heated so that PMMA is decomposed and evaporated with heat to obtain FTO/TiO₂/PbBr₂/PbCl₂Substrate 8 in FTO/TiO₂/PbBr₂/PbCl₂Spin coating CsBr solution, PbBr on the upper surface of the substrate 8₂Reacting the layer 4 with CsBr solution to obtain CsPbBr₃Layer 11, CsPbBr₃The thickness of the layer 11 is 300nm to 350nm, PbCl₂The layer 6 reacts with CsBr solution to obtain CsPbBrCl₂Layer 12, CsPbBrCl₂Thickness of layer 12The degree is 50 nm-150 nm, and finally the third substrate 9 is obtained.

Depositing carbon slurry on the upper surface of the third substrate 9 to obtain the anode carbon electrode 10, wherein the thickness of the anode carbon electrode 10 is 5-10 μm, and the area is 0.09cm²。

In summary, the structure of the solar cell includes the second FTO substrate, the TiO substrate₂Electron transport layer, CsPbBr₃Layer, CsPbBrCl₂Layer and anode carbon electrode on TiO₂Sequentially generating PbBr on the upper surface of the electron transport layer₂Layer, PMMA ultra-thin barrier layer and PbCl₂Heating the formed first substrate 7, spin-coating CsBr solution to obtain a third substrate 9 CsPbBr₃Layer and CsPbBrCl₂The layer is a double-layer perovskite photoactive layer, has different forbidden bandwidth, improves the photoelectric conversion efficiency of the perovskite solar cell, further increases the photoproduction current, and promotes the energy level matching degree of the interface of the perovskite photoactive layer and the anode carbon electrode. Meanwhile, CsPbBrCl₂The material of the layer has the function of passivating the interface defects, and the recombination among photon-generated carriers is greatly inhibited; CsPbBrCl₂The band gap of the layer is wide, so that the extraction and transmission of carriers are facilitated; CsPbBrCl₂The material of the layer has good stability in a room temperature environment, the influence of water-oxygen erosion on the perovskite solar cell in the environment can be reduced, and the performance and the stability of the perovskite solar cell are improved.

EXAMPLE III

Referring to fig. 1 and fig. 2a to 2i, fig. 1 is a flow chart of a method for manufacturing a solar cell having a double-layer perovskite photoactive layer according to an embodiment of the present invention, and fig. 2a to 2i are schematic diagrams of a process for manufacturing a solar cell having a double-layer perovskite photoactive layer according to an embodiment of the present invention.

The embodiment discloses a preparation method of a solar cell with a double-layer perovskite photoactive layer, which comprises the following steps:

step 1, preprocessing a first FTO substrate 1 to obtain a second FTO substrate 2.

Specifically, a first FTO substrate 1 is sequentially placed into a Decon-90 aqueous solution, deionized water, acetone and anhydrousUltrasonic cleaning is carried out in ethanol, and the cleaning time is 15 min. Then placing the first FTO substrate 1 which is subjected to ultrasonic cleaning into a UV-zone for UV-O₃Treating to obtain a second FTO substrate 2, UV-O₃The treatment time is 15-30 min.

Step 2, coating TiO on part of the upper surface of the second FTO substrate 2 in a spin coating mode₂Solution to obtain TiO₂An electron transport layer 3.

Specifically, 80. mu.L of TiO was mixed by a spin coater₂The solution was spin coated on a portion of the upper surface of the second FTO substrate 2 at a spin coater speed of 3000rpm for 30 seconds, and then placed in a muffle furnace at 500 ℃ and annealed in an air atmosphere for 1 hour.

Step 3, in TiO₂The upper surface of the electron transmission layer 3 is coated with PbBr by spin coating₂Obtaining PbBr from the solution₂And (4) a layer.

In particular, the second FTO substrate 2 and TiO that have been prepared₂Electron transport layer 3 composition FTO/TiO₂Substrate, FTO/TiO₂The substrate was placed in a glove box N₂In the environment, 85 μ L of PbBr was mixed using a spin coater₂The solution is coated on FTO/TiO by spinning₂Upper surface of the substrate, PbBr₂The concentration of the solution is 367mg/mL, the rotating speed of a spin coater is 2000rpm, the spin coating time is 30s, and then PbBr is spin-coated₂FTO/TiO of solution₂The substrate is placed on a 90 ℃ hot bench to be annealed for 30min to obtain PbBr₂And (4) a layer.

Step 4, in PbBr₂And spin-coating a PMMA solution on the upper surface of the layer 4 to obtain the PMMA ultrathin barrier layer 5.

Specifically, 50. mu.L of PMMA solution was spin coated onto PbBr using a spin coater₂The density of PMMA solution on the upper surface of the layer 4 is 1mg/mL, the rotating speed of a spin coater is 4000rpm, the spin coating time is 30s, and then FTO/TiO₂/PbBr₂The substrate is placed at room temperature to obtain the PMMA ultrathin barrier layer 5, and the room temperature is 25 ℃.

Step 5, spin coating PbCl on the upper surface of the PMMA ultrathin barrier layer 5₂Obtaining a first base 7 from the solution, and sequentially laminating a second FTO substrate 2 and TiO on the first base 7 from bottom to top₂Electron transport layer 3, PbBr₂Layer 4, PMMA ultra-thin barrier layer 5 and PbCl₂Group of layers 6And (4) obtaining.

Specifically, 85. mu.L of PbCl was mixed using a spin coater₂Solution is coated on the upper surface of the PMMA ultrathin barrier layer 5 in a spinning way, and PbCl is added₂The concentration of the solution was 27.8mg/mL, the rotation speed of the spin coater was 4000rpm, the coating time was 30s, and then PbCl was spin-coated₂FTO/TiO of solution₂/PbBr₂Placing the PMMA substrate on a 90 ℃ hot bench for annealing for 30min to obtain PbCl₂And (6) a layer.

Step 6, heating the first substrate 7 to obtain a second substrate 8, wherein the second substrate 8 is formed by sequentially laminating a second FTO substrate 2 and TiO from bottom to top₂Electron transport layer 3, PbBr₂Layer 4 and PbCl₂Layer 6.

Further, the first substrate 7 is heated to evaporate the PMMA ultra-thin barrier layer 5 by thermal decomposition to prepare a second substrate 8.

Specifically, the first substrate 7 was heated by a high temperature stage at 280 ℃ for 3 min.

Step 7, spin-coating CsBr solution on the upper surface of the second substrate 8 to obtain a third substrate 9, and sequentially laminating the third substrate 9 and the second FTO substrate 2 and the TiO from bottom to top₂Electron transport layer 3, CsPbBr₃Layer 11 and CsPbBrCl₂Layer 12.

Further, CsBr solution is spin-coated on the upper surface of the second substrate 8 to make PbBr₂Reacting the layer 4 with CsBr solution to obtain CsPbBr₃Layer 11, PbCl₂The layer 6 reacts with CsBr solution to obtain CsPbBrCl₂Layer 12 to prepare the third substrate 9.

Specifically, the second substrate 8 was placed in an air room temperature environment, and 110 μ L of the CsBr solution was spin-coated on the upper surface of the second substrate 8 using a spin coater, the concentration of the CsBr solution was 250mg/mL, the rotation speed of the spin coater was 2000rpm, and the spin coating time was 30 s. Then, the second substrate 8 on which the CsBr solution was spin-coated was placed on a 250 ℃ hot stage and annealed for 5min to obtain a third substrate 9.

And 8, depositing carbon slurry on the upper surface of the third substrate 9 to obtain an anode carbon electrode 10 so as to prepare the solar cell with the double-layer perovskite photoactive layer.

Specifically, the third substrate 9 is placed in a room temperature environment, conductive carbon paste is deposited on the upper surface of the third substrate 9 by using a screen printing method, and then the third substrate is placed on a hot stage at 120 ℃ for annealing for 15min to obtain the carbon electrode 10, wherein the carbon electrode 10 is used as an anode of the solar cell of the present application.

Example four

Referring to fig. 1 and fig. 2a to 2i, fig. 1 is a flow chart of a method for manufacturing a solar cell having a double-layer perovskite photoactive layer according to an embodiment of the present invention, and fig. 2a to 2i are schematic diagrams of a process for manufacturing a solar cell having a double-layer perovskite photoactive layer according to an embodiment of the present invention.

The embodiment discloses a preparation method of a solar cell with a double-layer perovskite photoactive layer, which comprises the following steps:

step 1, preprocessing a first FTO substrate 1 to obtain a second FTO substrate 2.

Specifically, the first FTO substrate 1 is sequentially placed into a Decon-90 aqueous solution, deionized water, acetone and absolute ethyl alcohol for ultrasonic cleaning, and the cleaning time is 15 min. Then placing the first FTO substrate 1 which is subjected to ultrasonic cleaning into a UV-zone for UV-O₃Treating to obtain a second FTO substrate 2, UV-O₃The treatment time is 15-30 min.

Step 2, coating TiO on part of the upper surface of the second FTO substrate 2 in a spin coating mode₂Solution to obtain TiO₂An electron transport layer 3.

Specifically, 80. mu.L of TiO was mixed by a spin coater₂The solution was spin coated on a portion of the upper surface of the second FTO substrate 2 at a spin coater speed of 3000rpm for 30 seconds, and then placed in a muffle furnace at 500 ℃ and annealed in an air atmosphere for 1 hour.

Step 3, in TiO₂The upper surface of the electron transmission layer 3 is coated with PbBr by spin coating₂Obtaining PbBr from the solution₂And (4) a layer.

In particular, the second FTO substrate 2 and TiO that have been prepared₂Electron transport layer 3 composition FTO/TiO₂Substrate, FTO/TiO₂The substrate was placed in a glove box N₂In the environment, 85 μ L of PbBr was mixed using a spin coater₂The solution is coated on FTO/TiO by spinning₂Upper surface of the substrate, PbBr₂The concentration of the solution is 367mg/mL, the rotating speed of a spin coater is 2000rpm, the spin coating time is 30s, and then PbBr is spin-coated₂FTO/TiO of solution₂The substrate is placed on a 90 ℃ hot bench to be annealed for 30min to obtain PbBr₂And (4) a layer.

Step 4, in PbBr₂And spin-coating a PMMA solution on the upper surface of the layer 4 to obtain the PMMA ultrathin barrier layer 5.

Specifically, 50. mu.L of PMMA solution was spin coated onto PbBr using a spin coater₂The density of PMMA solution on the upper surface of the layer 4 is 2.5mg/mL, the rotating speed of a spin coater is 4000rpm, the spin coating time is 30s, and then FTO/TiO₂/PbBr₂The substrate is placed at room temperature to obtain the PMMA ultrathin barrier layer 5, and the room temperature is 25 ℃.

Step 5, spin coating PbCl on the upper surface of the PMMA ultrathin barrier layer 5₂Obtaining a first base 7 from the solution, and sequentially laminating a second FTO substrate 2 and TiO on the first base 7 from bottom to top₂Electron transport layer 3, PbBr₂Layer 4, PMMA ultra-thin barrier layer 5 and PbCl₂Layer 6.

Specifically, 85. mu.L of PbCl was mixed using a spin coater₂Solution is coated on the upper surface of the PMMA ultrathin barrier layer 5 in a spinning way, and PbCl is added₂The concentration of the solution was 27.8mg/mL, the rotation speed of the spin coater was 4000rpm, the coating time was 30s, and then PbCl was spin-coated₂FTO/TiO of solution₂/PbBr₂Placing the PMMA substrate on a 90 ℃ hot bench for annealing for 30min to obtain PbCl₂And (6) a layer.

Step 6, heating the first substrate 7 to obtain a second substrate 8, wherein the second substrate 8 is formed by sequentially laminating a second FTO substrate 2 and TiO from bottom to top₂Electron transport layer 3, PbBr₂Layer 4 and PbCl₂Layer 6.

Further, the first substrate 7 is heated to evaporate the PMMA ultra-thin barrier layer 5 by thermal decomposition to prepare a second substrate 8.

Specifically, the first substrate 7 was heated by a high temperature stage at 280 ℃ for 3 min.

Step 7, spin-coating CsBr solution on the upper surface of the second substrate 8 to obtain a third substrate 9, wherein the third substrate 9 is coated from bottom to topA second FTO substrate 2 and TiO laminated in sequence₂Electron transport layer 3, CsPbBr₃Layer 11 and CsPbBrCl₂Layer 12.

Further, CsBr solution is spin-coated on the upper surface of the second substrate 8 to make PbBr₂Reacting the layer 4 with CsBr solution to obtain CsPbBr₃Layer 11, PbCl₂The layer 6 reacts with CsBr solution to obtain CsPbBrCl₂Layer 12 to prepare the third substrate 9.

Specifically, the second substrate 8 was placed in an air room temperature environment, and 150 μ L of the CsBr solution was spin-coated on the upper surface of the second substrate 8 using a spin coater, the concentration of the CsBr solution was 250mg/mL, the rotation speed of the spin coater was 2000rpm, and the spin coating time was 30 s. Then, the second substrate 8 on which the CsBr solution was spin-coated was placed on a 200 ℃ hot stage and annealed for 5min to obtain a third substrate 9.

And 8, depositing carbon slurry on the upper surface of the third substrate 9 to obtain the anode carbon electrode 10.

Specifically, the third substrate 9 is placed in a room temperature environment, conductive carbon paste is deposited on the upper surface of the third substrate 9 by using a screen printing method, and then the third substrate is placed on a hot stage at 120 ℃ for annealing for 15min to obtain the carbon electrode 10, wherein the carbon electrode 10 is used as an anode of the solar cell of the present application.

EXAMPLE five

Referring to fig. 1 and fig. 2a to 2i, fig. 1 is a flow chart of a method for manufacturing a solar cell having a double-layer perovskite photoactive layer according to an embodiment of the present invention, and fig. 2a to 2i are schematic diagrams of a process for manufacturing a solar cell having a double-layer perovskite photoactive layer according to an embodiment of the present invention.

The embodiment discloses a preparation method of a solar cell with a double-layer perovskite photoactive layer, which comprises the following steps:

step 1, preprocessing a first FTO substrate 1 to obtain a second FTO substrate 2.

Specifically, the first FTO substrate 1 is sequentially placed into a Decon-90 aqueous solution, deionized water, acetone and absolute ethyl alcohol for ultrasonic cleaning, and the cleaning time is 15 min. Then placing the first FTO substrate 1 which is subjected to ultrasonic cleaning into a UV-zone for UV-O₃Is processed to obtain the secondFTO substrate 2, UV-O₃The treatment time is 15-30 min.

Step 2, coating TiO on part of the upper surface of the second FTO substrate 2 in a spin coating mode₂Solution to obtain TiO₂An electron transport layer 3.

Specifically, 80. mu.L of TiO was mixed by a spin coater₂The solution was spin coated on a portion of the upper surface of the second FTO substrate 2 at a spin coater speed of 3000rpm for 30 seconds, and then placed in a muffle furnace at 500 ℃ and annealed in an air atmosphere for 1 hour.

Step 3, in TiO₂The upper surface of the electron transmission layer 3 is coated with PbBr by spin coating₂Obtaining PbBr from the solution₂And (4) a layer.

In particular, the second FTO substrate 2 and TiO that have been prepared₂Electron transport layer 3 composition FTO/TiO₂Substrate, FTO/TiO₂The substrate was placed in a glove box N₂In the environment, 85 μ L of PbBr was mixed using a spin coater₂The solution is coated on FTO/TiO by spinning₂Upper surface of the substrate, PbBr₂The concentration of the solution is 367mg/mL, the rotating speed of a spin coater is 2000rpm, the spin coating time is 30s, and then PbBr is spin-coated₂FTO/TiO of solution₂The substrate is placed on a 90 ℃ hot bench to be annealed for 30min to obtain PbBr₂And (4) a layer.

Step 4, in PbBr₂And spin-coating a PMMA solution on the upper surface of the layer 4 to obtain the PMMA ultrathin barrier layer 5.

Specifically, 50. mu.L of PMMA solution was spin coated onto PbBr using a spin coater₂The density of PMMA solution on the upper surface of the layer 4 is 5mg/mL, the rotating speed of a spin coater is 4000rpm, the spin coating time is 30s, and then FTO/TiO₂/PbBr₂The substrate is placed at room temperature to obtain the PMMA ultrathin barrier layer 5, and the room temperature is 25 ℃.

Step 5, spin coating PbCl on the upper surface of the PMMA ultrathin barrier layer 5₂Obtaining a first base 7 from the solution, and sequentially laminating a second FTO substrate 2 and TiO on the first base 7 from bottom to top₂Electron transport layer 3, PbBr₂Layer 4, PMMA ultra-thin barrier layer 5 and PbCl₂Layer 6.

Specifically, 85. mu.L of PbCl was mixed using a spin coater₂Solution is coated on the upper surface of the PMMA ultrathin barrier layer 5 in a spinning way, and PbCl is added₂The concentration of the solution was 27.8mg/mL, the rotation speed of the spin coater was 4000rpm, the coating time was 30s, and then PbCl was spin-coated₂FTO/TiO of solution₂/PbBr₂Placing the PMMA substrate on a 90 ℃ hot bench for annealing for 30min to obtain PbCl₂And (6) a layer.

Step 6, heating the first substrate 7 to obtain a second substrate 8, wherein the second substrate 8 is formed by sequentially laminating a second FTO substrate 2 and TiO from bottom to top₂Electron transport layer 3, PbBr₂Layer 4 and PbCl₂Layer 6.

Further, the first substrate 7 is heated to evaporate the PMMA ultra-thin barrier layer 5 by thermal decomposition to prepare a second substrate 8.

Specifically, the first substrate 7 was heated by a high temperature stage at 280 ℃ for 3 min.

Step 7, spin-coating CsBr solution on the upper surface of the second substrate 8 to obtain a third substrate 9, and sequentially laminating the third substrate 9 and the second FTO substrate 2 and the TiO from bottom to top₂Electron transport layer 3, CsPbBr₃Layer 11 and CsPbBrCl₂Layer 12.

Further, CsBr solution is spin-coated on the upper surface of the second substrate 8 to make PbBr₂Reacting the layer 4 with CsBr solution to obtain CsPbBr₃Layer 11, PbCl₂The layer 6 reacts with CsBr solution to obtain CsPbBrCl₂Layer 12 to prepare the third substrate 9.

Specifically, the second substrate 8 was placed in an air room temperature environment, and 80 μ L of the CsBr solution was spin-coated on the upper surface of the second substrate 8 using a spin coater, the concentration of the CsBr solution was 250mg/mL, the rotation speed of the spin coater was 2000rpm, and the spin coating time was 30 s.

Specifically, the second substrate 8 on which the CsBr solution was spin-coated was placed on a 300 ℃ hot stage and annealed for 5min to obtain a third substrate 9.

And 8, depositing carbon slurry on the upper surface of the third substrate 9 to obtain the anode carbon electrode 10.

Specifically, the third substrate 9 is placed in a room temperature environment, conductive carbon paste is deposited on the upper surface of the third substrate 9 by using a screen printing method, and then the third substrate is placed on a hot stage at 120 ℃ for annealing for 15min to obtain the carbon electrode 10, wherein the carbon electrode 10 is used as an anode of the solar cell of the present application.

The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.