CN113380950B - Back contact perovskite solar cell and preparation method thereof - Google Patents
Back contact perovskite solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention provides a back contact perovskite solar cell and a preparation method thereof, wherein the solar cell comprises a substrate, positive electrodes and negative electrodes are alternately arranged on the upper side of the substrate at intervals, a hole transmission layer is arranged on the upper side of the positive electrode, an electron transmission layer is arranged on the upper side of the negative electrode, a perovskite layer is arranged on the upper sides of the hole transmission layer and the electron transmission layer, an encapsulation adhesive layer is arranged on the upper side of the perovskite layer, and a transparent cover plate is arranged on the upper side of the encapsulation adhesive layer. The invention can increase the area response of the solar cell for absorbing light and increase the short-circuit current of the cell because the light incident surface of the cell is not blocked by the electrode structure, thereby effectively improving the photoelectric conversion efficiency of the solar cell. Meanwhile, as the electrode part and the perovskite layer are distributed on the two sides of the device, secondary repair and recycling of the battery are facilitated, and maintenance and use cost of the battery is greatly reduced.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a back contact perovskite solar cell and a preparation method thereof.
Background
In recent years, perovskite solar cells have been significantly advanced stepwise, and photoelectric conversion efficiency has been improved to 20% or more. More importantly, the perovskite material is rich in element reserves and low in cost, and can be processed by a solution method, so that the cost of the solar cell is reduced, and the electricity generation cost lower than that of the traditional energy source is hopeful to be truly realized. However, due to the poor stability of the perovskite material, the perovskite solar cell needs to strictly control the contact of the perovskite material with water vapor in the preparation and use processes. The associated isolation measures undoubtedly increase the manufacturing and operating costs of the battery. In addition, the perovskite solar cell with the existing vertical sandwich structure is characterized in that the perovskite layer is usually clamped between the electron transport layer and the hole transport layer, once the perovskite layer is damaged in the use process, the perovskite layer is difficult to repair and recycle, the possibility of environmental pollution is increased, and the maintenance cost of the cell in the use process is greatly increased. Therefore, improvements in the structure and fabrication process of existing perovskite solar cells are urgently needed.
Disclosure of Invention
According to the back contact perovskite solar cell and the preparation method thereof, as the light incident surface of the cell is not blocked by the electrode structure, the area response of the solar cell for absorbing light can be increased, the short-circuit current of the cell is increased, and the photoelectric conversion efficiency of the solar cell is further effectively improved. Meanwhile, as the electrode part and the perovskite layer are distributed on the two sides of the device, secondary repair and recycling of the battery are facilitated, and maintenance and use cost of the battery is greatly reduced.
The technical scheme of the invention is realized as follows: the utility model provides a back contact perovskite solar cell, includes the substrate, and the upside of substrate is provided with positive electrode and negative electrode at alternate interval, and the upside of positive electrode is provided with the hole transport layer, and the upside of negative electrode is provided with electron transport layer, and the upside of hole transport layer and electron transport layer is provided with the perovskite layer, and the upside of perovskite layer is provided with the encapsulation glue film, and the upside of encapsulation glue film is provided with transparent apron.
Further, the thicknesses of the positive electrode and the negative electrode are 50-800nm, and the interval between adjacent positive electrode and negative electrode is 20-100nm.
Further, the thicknesses of the positive electrode and the negative electrode are 100-300nm, and the interval between adjacent positive electrode and negative electrode is 30-50nm.
Further, the thickness of the hole transport layer is 10-100nm, and the thickness of the electron transport layer is 10-100nm.
Further, the thickness of the hole transport layer is 20-50nm, and the thickness of the electron transport layer is 20-80nm.
Further, the thickness of the perovskite layer is 100-1000nm.
Further, the thickness of the perovskite layer is 200-500nm.
Further, the positive electrode or negative electrode is one or more of Ag, al, au, ni, ti, cu.
Further, the hole transport layer is one or more of NiO x、NiMgO、MoOx, spiro-OMeTAD and P3HT, PTAA, PCPDTBT.
Further, the electron transport layer is one or more of ZnO, tiO 2 and PCBM.
Further, the perovskite layer is one or more of CsPbI 3、FAPbI3、MAPbI3.
Further, the substrate is one or more of glass, plastic, metal and ceramic.
A method for preparing a back contact perovskite solar cell, comprising the steps of:
s1) preparing a first metal electrode film on the upper side of a substrate;
S2) preparing a hole transport layer on the upper side of the first metal electrode film;
S3) preparing a grid-shaped interval shielding layer on the surface of the hole transport layer through spin coating, photoresist exposure and development;
S4) changing the first metal electrode film and the hole transport layer into grid shapes through acid corrosion, wherein the rest first metal electrode film is a positive electrode;
S5) preparing a second metal electrode film and an electron transport layer on the upper side of the substrate;
s6) removing the interval shielding layer, the second metal electrode film and the electron transmission layer on the upper side of the interval shielding layer through a photoresist removing process, wherein the remaining second metal electrode film on the substrate is a negative electrode;
s7) spin coating photoresist on the surfaces of the hole transport layer and the electron transport layer;
s8) removing the photoresist at the interface of the hole transmission layer and the electron transmission layer by exposing and developing the photoresist in the step S7);
s9) removing materials at the interfaces of the hole transport layer and the electron transport layer and materials at the interfaces of the positive electrode and the negative electrode through acid corrosion to form insulation of the hole transport layer and the electron transport layer and insulation of the positive electrode and the negative electrode;
S10) removing photoresist on the hole transport layer and the electron transport layer;
s11) preparing a perovskite layer on the upper sides of the hole transport layer and the electron transport layer;
S12) coating packaging adhesive on the upper side of the perovskite layer to form a packaging adhesive layer; and covering a transparent cover plate on the packaging adhesive layer, and sealing the battery.
Further, the first metal electrode film and the second metal electrode film are prepared by magnetron sputtering, thermal evaporation or ion plating.
Further, the hole transport layer is prepared by spin coating or magnetron sputtering.
Further, the electron transport layer is prepared by spin coating or magnetron sputtering.
Further, the width and shape of the hole transport layer and the electron transport layer need to be modulated according to the perovskite layer.
The invention has the beneficial effects that:
The back contact perovskite solar cell structure has the following advantages: firstly, the front surface is free of electrodes, and as the electrodes are free of shielding, compared with a traditional perovskite battery with a vertical sandwich structure, the area response of the solar battery for absorbing light can be increased, and the battery can absorb more incident light, so that higher photo-generated current is generated, and the improvement of the photoelectric conversion efficiency of the battery is facilitated; secondly, because the electrode part with better stability and the perovskite layer with relatively poorer stability are distributed on the two sides of the device, the secondary repair and recycling of the device are facilitated under the condition that the perovskite layer is damaged, and the maintenance and use cost of the battery is greatly reduced; finally, because the relatively complex electrode process is concentrated in the front section, the relatively simple perovskite and packaging process is concentrated in the rear section, thereby being beneficial to the management and control and adjustment of the process, ensuring the stability of the battery quality and improving the battery performance.
In addition, the photocarriers reach the alternately distributed hole transport layers and electron transport layers by lateral transport, and thus there is a relatively high requirement on the diffusion length of the carriers. The carrier diffusion length of single crystal lead halide perovskite exceeds 30 μm, and under low injection conditions, the charge diffusion length of majority carriers reaches 320 μm even. More importantly, the polycrystalline thin film perovskite can reach a diffusion length of 70 mu m, so that the perovskite material has a relatively large diffusion length, is beneficial to improving the extraction efficiency of photo-generated carriers, and is very suitable for preparing the back contact solar cell.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method of making the present invention;
Fig. 2 is a schematic diagram of the structure of the back pattern one of the solar cell of embodiment 1;
fig. 3 is a schematic structural diagram of a second back pattern of the solar cell of embodiment 1;
Fig. 4 is a schematic diagram of the structure of the back pattern one of the solar cell of embodiment 2;
fig. 5 is a schematic diagram of the structure of a second pattern on the back surface of the solar cell of example 2.
A substrate 1, a first metal electrode film 2, a hole transport layer 3, a spacing shielding layer 4, a positive electrode 5, a second metal electrode film 6, an electron transport layer 7, a negative electrode 8, a photoresist 9, a perovskite layer 10, an encapsulation adhesive layer 11 and a transparent cover plate 12.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1:
the glass substrate 1 is washed by ultrasonic in acetone, absolute ethyl alcohol and deionized water for 10 minutes, and then dried by nitrogen for standby.
As shown in fig. 1, a method for preparing a back contact perovskite solar cell comprises the following steps:
s1) preparing a first metal electrode film 2 on the upper side of a substrate 1;
An Ag film having a thickness of 200nm was prepared on the substrate 1 by a vacuum evaporation method. Wherein, the evaporation heating current is 80A, the substrate temperature is 80 ℃, the evaporation speed is 1nm/s, and the pressure of vacuum evaporation is 2.0X10 -4 Pa.
S2) preparing a hole transport layer 3 on the upper side of the first metal electrode film 2;
And preparing a NiO x film with the thickness of 50nm on the surface of the Ag film by magnetron sputtering. The purity of the NiO target is 99.999%, the temperature of the substrate 1 is 250 ℃, the sputtering power is 150W, the oxygen argon flow ratio is 0.05, and the sputtering pressure is 0.8Pa.
S3) preparing a grid-shaped interval shielding layer 4 on the surface of the hole transport layer 3 through spin coating, photoresist exposure and development;
And preparing a spacing shielding layer 4 on the surface of the NiO x film by spin coating, photoresist, exposure and development. Wherein the width of the shielding part is 150 μm, and the interval width is 100 μm.
S4) changing the first metal electrode film 2 and the hole transport layer 3 into grid shapes through hydrochloric acid corrosion, wherein the rest of the first metal electrode film 2 is a positive electrode 5;
And (3) removing the NiO x film and the Ag film in the non-shielding part by corroding the NiO x film and the Ag film for 3 minutes through dilute hydrochloric acid with the concentration of 20%, so that the NiO x film and the Ag film are changed into grid shapes.
S5) preparing a second metal electrode film 6 and an electron transport layer 7 on the upper side of the substrate 1;
On the upper surface of the NiO x film, the Ag film is evaporated by vacuum and the ZnO film is prepared by magnetron sputtering. Wherein, when the Ag film is evaporated, the evaporation heating current is 80A, the substrate temperature is 80 ℃, the evaporation speed is 1nm/s, and the vacuum evaporation pressure is 2.0X10 -4 Pa. When the ZnO film is sputtered, the purity of the ZnO target is 99.999%, the temperature of the substrate 1 is 150 ℃, the sputtering power is 200W, the oxygen argon flow ratio is 0.15, and the sputtering pressure is 1.5Pa.
S6) removing the interval shielding layer 4, the second metal electrode film 6 and the electron transport layer 7 on the upper side of the interval shielding layer 4 through a photoresist removing process, wherein the second metal electrode film 6 remained on the substrate 1 is a negative electrode 8;
And removing the excessive Ag film and ZnO film on the upper surface of the NiO x film through a photoresist removing process to form a grid-shaped NiO x hole transport layer 3 and a ZnO electron transport layer 7.
S7) spin-coating photoresist 9 on the surfaces of the hole transport layer 3 and the electron transport layer 7;
photoresist 9 is spin-coated and cured on the surfaces of the hole transport layer 3 and the electron transport layer 7.
S8) removing the photoresist at the interface of the hole transmission layer 3 and the electron transmission layer 7 by exposing and developing the photoresist 9 in the step S7);
And removing the photoresist at the interface of the NiO x hole transport layer 3 and the ZnO electron transport layer 7 by exposing and developing the photoresist 9, wherein the photoresist removing width is 50nm.
S9) removing the material at the interface of the hole transport layer 3 and the electron transport layer 7 and the material at the interface of the positive electrode 5 and the negative electrode 8 by corrosion with hydrochloric acid to form insulation of the hole transport layer 3 and the electron transport layer 7 and insulation of the positive electrode 5 and the negative electrode 8;
the material at the interface of the NiO x hole transport layer 3 and the ZnO electron transport layer 7 is removed by etching in dilute hydrochloric acid with a concentration of 20% for 3 minutes, forming a lateral insulation of the hole transport layer 3 and the electron transport layer 7.
S10) removing the photoresist 9 on the hole transport layer 3 and the electron transport layer 7;
s11) preparing a perovskite layer 10 on the upper sides of the hole transport layer 3 and the electron transport layer 7;
CsPbI 3 perovskite light-absorbing layer with thickness of 200nm is prepared on the surfaces of the NiO x hole-transporting layer 3 and the ZnO electron-transporting layer 7 by knife coating.
S12) coating packaging adhesive on the upper side of the perovskite layer 10 to form a packaging adhesive layer 11; covering a transparent cover plate 12 on the packaging adhesive layer 11, and realizing battery sealing;
and (3) dropwise adding UV light-cured glue on the upper surface of the perovskite layer 10. Finally, a glass sheet is covered on the UV light curing agent, then the curing of the UV light curing adhesive is realized through the irradiation of UV light, and the sealing of the battery is realized.
Finally, the back side of the back contact perovskite solar cell is shown in fig. 2 or 3. As shown in fig. 2, all positive electrodes 5 are led out in a connected mode, and all negative electrodes 8 are led out in a connected mode; as shown in fig. 3, adjacent positive electrodes 5 are connected and led out to form a plurality of positive electrode lead-out terminals, and adjacent negative electrodes 8 are connected and led out to form a plurality of negative electrode lead-out terminals.
Example 2:
The PE substrate 1 is washed by ultrasonic in absolute ethyl alcohol and deionized water for 10 minutes, and then dried by nitrogen for standby.
As shown in fig. 1, a method for preparing a back contact perovskite solar cell comprises the following steps:
s1) preparing a first metal electrode film 2 on the upper side of a substrate 1;
An Al film having a thickness of 300nm was prepared on PE substrate 1 by magnetron sputtering. When the Al film is sputtered, the purity of the Al target is 99.999%, the temperature of the substrate 1 is 100 ℃, the sputtering power is 100W, and the sputtering pressure is 2.5Pa.
S2) preparing a hole transport layer 3 on the upper side of the first metal electrode film 2;
NiMgO film with thickness of 100nm was prepared on the surface of the Al film by spin coating NiMgO nm.
S3) preparing a grid-shaped interval shielding layer 4 on the surface of the hole transport layer 3 through spin coating, photoresist exposure and development;
And preparing a spacing shielding layer 4 on the surface of the NiMgO film by spin coating, photoresist, exposure and development. Wherein the width of the shielding part is 200 μm, and the interval width is 150 μm.
S4) forming the first metal electrode film 2 and the hole transport layer 3 into a grid shape by acid etching, the remaining first metal electrode film 2 being the positive electrode 5;
And removing NiMgO thin films and Al thin films at the non-shielding parts by corrosion and cleaning with dilute hydrochloric acid with the concentration of 20%, so that the NiMgO thin films and the Al thin films are changed into grid shapes.
S5) preparing a second metal electrode film 6 and an electron transport layer 7 on the upper side of the substrate 1 (including the upper side of the substrate 1 other than the positive electrode 5 and the upper side of the spacer shielding layer 4);
And sequentially preparing an Al film and a TiO 2 film with the thicknesses of 300nm and 100nm on the upper surface of the NiMgO film by magnetron sputtering. When the Al film is sputtered, the purity of the Al target is 99.999%, the temperature of the substrate 1 is 100 ℃, the sputtering power is 100W, and the sputtering pressure is 2.5Pa. When the TiO 2 film is sputtered, the purity of the TiO 2 target material is 99.999%, the temperature of the substrate 1 is 200 ℃, the sputtering power is 200W, and the sputtering pressure is 1.5Pa.
S6) removing the interval shielding layer 4, the second metal electrode film 6 and the electron transport layer 7 on the upper side of the interval shielding layer 4 through a photoresist removing process, wherein the second metal electrode film 6 remained on the substrate 1 is a negative electrode 8;
and removing redundant Al films and TiO 2 films on the upper surface of the NiMgO films through a photoresist removing process to form a grid-shaped NiMgO hole transport layer 3 and a TiO 2 electron transport layer 7.
S7) spin-coating photoresist 9 on the surfaces of the hole transport layer 3 and the electron transport layer 7;
photoresist 9 is spin-coated and cured on the surfaces of the hole transport layer 3 and the electron transport layer 7.
S8) removing the photoresist at the interface of the hole transmission layer 3 and the electron transmission layer 7 by exposing and developing the photoresist 9 in the step S7);
And removing the photoresist at the interface of the NiMgO hole transport layer 3 and the TiO 2 electron transport layer 7 by exposing and developing the photoresist 9, wherein the photoresist removing width is 30nm.
S9) removing the material at the interface of the hole transport layer 3 and the electron transport layer 7 and the material at the interface of the positive electrode 5 and the negative electrode 8 by acid etching to form insulation of the hole transport layer 3 and the electron transport layer 7 and insulation of the positive electrode 5 and the negative electrode 8;
the material at the interface of NiMgO hole transport layer 3 and TiO 2 electron transport layer 7 is removed by etching with dilute hydrochloric acid at a concentration of 20% to form lateral insulation of hole transport layer 3 and electron transport layer 7.
S10) removing the photoresist 9 on the hole transport layer 3 and the electron transport layer 7;
s11) preparing a perovskite layer 10 on the upper sides of the hole transport layer 3 and the electron transport layer 7;
On the surfaces of NiMgO hole transport layer 3 and TiO 2 electron transport layer 7, FAPbI 3 perovskite light-absorbing layer with thickness of 200nm was prepared by spin coating.
S12) coating packaging adhesive on the upper side of the perovskite layer 10 to form a packaging adhesive layer 11; a transparent cover plate 12 is covered on the encapsulation adhesive layer 11, and battery sealing is realized.
An EVA packaging adhesive film is paved on the upper surface of the perovskite layer 10, a PMMA cover plate is covered on the EVA packaging adhesive film, and then the battery is sealed through an EVA curing process.
The back side pattern of the final back contact perovskite solar cell is shown in fig. 4 or 5 by the design of the electrode pattern. As shown in fig. 4, all positive electrodes 5 are led out in a connected mode, and all negative electrodes 8 are led out in a connected mode; as shown in fig. 5, adjacent positive electrodes 5 are connected and led out to form a plurality of positive electrode lead-out terminals, and adjacent negative electrodes 8 are connected and led out to form a plurality of negative electrode lead-out terminals.
In the present invention, the positive electrode or the negative electrode may also be one of Au, ni, ti, cu, or a multi-layer composite formed of a plurality of materials, such as a Ni layer on an Au layer, or the like. The hole transport layer may also be one of MoO x, spiro-OMeTAD, P3HT, PTAA, PCPDTBT, or a multi-layer composite formed by multiple materials, such as a composite of a Spiro-OMeTAD film on a MoO x film. The electron transport layer is PCBM or multi-layer composite of ZnO, tiO 2 and PCBM, such as composite TiO 2 on ZnO film; the perovskite layer may also be MAPbI 3, or a multi-layer composite formed from multiple materials, such as FAPbI 3 on a CsPbI 3 film.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. A back contact perovskite solar cell comprising a substrate characterized in that: positive electrodes and negative electrodes are alternately and alternately arranged on the upper side of the substrate, a hole transmission layer is arranged on the upper side of the positive electrode, an electron transmission layer is arranged on the upper side of the negative electrode, a perovskite layer is arranged on the upper sides of the hole transmission layer and the electron transmission layer, a packaging adhesive layer is arranged on the upper side of the perovskite layer, and a transparent cover plate is arranged on the upper side of the packaging adhesive layer;
the preparation method of the back contact perovskite solar cell is characterized by comprising the following steps of:
s1) preparing a first metal electrode film on the upper side of a substrate;
S2) preparing a hole transport layer on the upper side of the first metal electrode film;
S3) preparing a grid-shaped interval shielding layer on the surface of the hole transport layer through spin coating, photoresist exposure and development;
S4) changing the first metal electrode film and the hole transport layer into grid shapes through acid corrosion, wherein the rest first metal electrode film is a positive electrode;
S5) preparing a second metal electrode film and an electron transport layer on the upper side of the substrate;
s6) removing the interval shielding layer, the second metal electrode film and the electron transmission layer on the upper side of the interval shielding layer through a photoresist removing process, wherein the remaining second metal electrode film on the substrate is a negative electrode;
s7) spin coating photoresist on the surfaces of the hole transport layer and the electron transport layer;
s8) removing the photoresist at the interface of the hole transmission layer and the electron transmission layer by exposing and developing the photoresist in the step S7);
s9) removing materials at the interfaces of the hole transport layer and the electron transport layer and materials at the interfaces of the positive electrode and the negative electrode through acid corrosion to form insulation of the hole transport layer and the electron transport layer and insulation of the positive electrode and the negative electrode;
S10) removing photoresist on the hole transport layer and the electron transport layer;
s11) preparing a perovskite layer on the upper sides of the hole transport layer and the electron transport layer;
s12) coating packaging adhesive on the upper side of the perovskite layer to form a packaging adhesive layer; covering a transparent cover plate on the packaging adhesive layer, and sealing the battery;
The thickness of the positive electrode and the negative electrode is 50-800nm, and the interval between the adjacent positive electrode and the adjacent negative electrode is 20-100nm;
The thickness of the hole transport layer is 10-100nm, the thickness of the electron transport layer is 10-100nm, and the thickness of the perovskite layer is 100-1000nm;
The perovskite layer is one or more of CsPbI 3、FAPbI3、MAPbI3.
2. A back contact perovskite solar cell according to claim 1, wherein: the positive electrode or negative electrode is one or more of Ag, al, au, ni, ti, cu.
3. A back contact perovskite solar cell according to claim 1, wherein: the hole transport layer is one or more of NiO x、NiMgO、MoOx, spiro-OMeTAD and P3HT, PTAA, PCPDTBT.
4. A back contact perovskite solar cell according to claim 1, wherein: the electron transport layer is one or more of ZnO, tiO 2 and PCBM.
5. The back contact perovskite solar cell of claim 1, wherein the first metal electrode film and the second metal electrode film are prepared by magnetron sputtering, thermal evaporation or ion plating.
6. The back contact perovskite solar cell of claim 1, wherein the hole transport layer and the electron transport layer are fabricated using spin coating or magnetron sputtering.
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