CN110931657A - Flexible composite substrate for perovskite thin-film solar cell and preparation method thereof - Google Patents

Flexible composite substrate for perovskite thin-film solar cell and preparation method thereof Download PDF

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CN110931657A
CN110931657A CN201911243706.XA CN201911243706A CN110931657A CN 110931657 A CN110931657 A CN 110931657A CN 201911243706 A CN201911243706 A CN 201911243706A CN 110931657 A CN110931657 A CN 110931657A
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barrier layer
inorganic
coating
substrate
water
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王亚丽
王佳
侯丽新
刘贤豪
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CHINA LUCKY GROUP Corp
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Abstract

The invention provides a flexible composite substrate for a perovskite thin-film solar cell and a preparation method thereof. The problem that the existing PET, PEN and other base materials are poor in weather resistance is solved, and the water-oxygen barrier layer can also prevent water vapor and oxygen in the environment from corroding the perovskite battery, so that the requirement of long-term use of the outdoor damp-heat environment of the battery is met. The invention breaks through the preparation technology of the ultrathin high-barrier layer, integrates the barrier layer, the ultrathin base material and the transparent electrode into a whole, reduces the use of a layer of packaging film, reduces the surface density of the battery, simplifies the traditional sandwich type battery packaging process, only needs one-side pressing process, reduces the side leakage risk of the device and improves the long-term stability of the device.

Description

Flexible composite substrate for perovskite thin-film solar cell and preparation method thereof
Technical Field
The invention relates to the technical field of solar cells, in particular to preparation of a substrate for a perovskite thin-film solar cell.
Background
The photoelectric conversion efficiency of the perovskite solar cell rapidly increased from 3.8% to 23.7% in 2009, which is comparable to the efficiency of commercial solar cells. The inexpensive raw materials and simple fabrication process have led to perovskite cells receiving unprecedented attention over the past five years. The flexible substrate replaces a glass rigid substrate, so that the battery has the advantages of high efficiency, light weight, flexibility, impact resistance, convenience in carrying and the like, and can be applied to a plurality of fields of military and civil. With the rapid development of the near space detection field, aircrafts such as airships, unmanned aerial vehicles and the like are widely applied. There is an urgent need for light, curved and high mass-specific power flexible solar cells that can be laid on the surface of airships and unmanned aerial vehicles as power supplies.
Although the preparation technology of the flexible perovskite solar cell is continuously broken through, the flexible perovskite solar cell is extremely sensitive to humidity, temperature and illumination to generate decomposition due to the problems of ion migration, material and interface defects and the like, the long-term stability is poor, and how to obtain the flexible perovskite solar cell with high efficiency, high mass specific power and long service life is still a technical challenge.
The existing flexible perovskite battery mostly adopts plastic with a transparent electrode as a substrate, and then a perovskite battery device is deposited on the substrate, wherein the plastic is mostly made of polymer materials such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), Polydimethylsiloxane (PDMS) and the like. Due to the limitations of temperature resistance, barrier property and weather resistance of the plastic substrate, the preparation temperature of the battery generally cannot exceed 150 ℃, which presents great challenges to the preparation process; the substrate materials do not have the barrier effect, and cannot prevent water and oxygen in the air from entering the interior of the perovskite battery, so that the device is decomposed; under the conditions of long-term ultraviolet illumination, high temperature and the like, the substrate material can be decomposed, and the requirements of outdoor long-term application are difficult to meet; the thickness of the substrate is usually 100-175 μm, which results in higher areal density of the device and can not meet the requirements of low areal density and high mass specific power of future aerospace vehicles.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a flexible composite substrate for a perovskite thin-film solar cell, which has multiple characteristics and functions of ultraviolet cut-off, weather resistance, blocking, inclusion of a transparent conductive film and the like, overcomes the technical problems of poor temperature resistance, poor environmental adaptability, incapability of blocking water and oxygen and the like of the conventional plastic substrate, can effectively enhance the long-term working stability of a flexible perovskite cell device, and can meet the requirements of the civil field and the space application field.
It is another object of the present invention to provide a method for preparing such a flexible composite substrate.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a flexible composite substrate for a perovskite thin-film solar cell is provided with an inorganic nano coating, a base material, a water-oxygen barrier layer and a transparent conductive film from bottom to top in sequence;
the inorganic nano coating is inorganic oxide SiO2Or Al2O3Is formed by coating nano silica sol or nano alumina sol; the solid content of the sol is 10-30 wt%, and the sol is water or glycol.
The flexible composite substrate for the perovskite thin-film solar cell is characterized in that the base material is selected from one of Polyimide (PI), tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF) or ethylene-vinylidene fluoride copolymer (ECTFE), and the light transmittance of the base material is more than 80%, preferably more than 90%; the thickness of the substrate is 10 to 150. mu.m, preferably 30 to 75 μm.
The flexible composite substrate for the perovskite thin-film solar cell is characterized In that the water-oxygen barrier layer is an inorganic barrier layer or comprises one or more organic barrier layer/inorganic barrier layer paired layers, wherein the inorganic barrier layer comprises metal oxide or nitride, and the metal is selected from at least one of Al, Si, Zr, Ti, Hf, Ta, In, Sn and Zn; the thickness of the inorganic barrier layer is 10-600nm, preferably 100-300 nm; the organic barrier layer is polyacrylic resin containing silicon element and has a thickness of0.5-20 μm, preferably 0.8-2 μm; the water-oxygen barrier layer has a water vapor permeability WVTR < 10-4g/m2/day。
The flexible composite substrate for the perovskite thin-film solar cell is characterized in that the transparent electrode is one or more selected from Indium Tin Oxide (ITO), Ag/ITO/Ag, Ag/AZO/Ag, silver nanowires (AgNws), silver or copper metal grids, carbon nanotubes or graphite; the square resistance of the surface is 10-40 omega/□; the light transmittance is more than 80 percent.
The thickness of the inorganic nano coating layer of the flexible composite substrate for the perovskite thin-film solar cell is 10-200nm, preferably 50-100 μm; the coating hardness is 3H-6H.
A method for preparing the flexible composite substrate for the perovskite thin-film solar cell comprises the following steps:
(1) treating the outer surface of the flexible substrate, and then coating an inorganic nano coating;
(2) treating the inner surface of the flexible substrate, and then coating an organic barrier layer;
(3) depositing an inorganic barrier layer on the surface of the organic barrier layer coated in the step (2), and finishing the preparation of the water-oxygen barrier layer after depositing one or more organic/inorganic pair layers;
(4) and (4) depositing a transparent conductive film on the surface of the water-oxygen barrier layer in the step (3) to finish the preparation of the flexible composite substrate.
Advantageous effects
Compared with the prior art, the invention has the following beneficial effects:
(1) the flexible composite substrate for the perovskite solar cell integrates multiple functions of water and oxygen barrier, transparent electrodes and weather resistance. The base material has excellent weather resistance, and the problem of poor weather resistance of the existing base materials such as PET, PEN and the like is solved; the water-oxygen barrier layer can also prevent the corrosion of water vapor and oxygen in the environment to the perovskite battery, and the long-term use requirement of the outdoor damp-heat environment of the battery is met.
(2) According to the flexible composite substrate for the perovskite solar cell, the barrier layer, the base material and the transparent electrode are integrated, the use of a layer of high-barrier packaging film can be reduced, the surface density of the cell is reduced, the traditional sandwich type cell packaging process can be simplified, only one side pressing process is needed in the packaging process, and the side leakage risk around the device is reduced.
(3) According to the flexible composite substrate for the perovskite solar cell, the outer surface is protected by the inorganic nano coating material, so that the strength, hardness and wear resistance of the substrate are enhanced, the processability of the ultrathin substrate is improved, and the preparation technology of the water-oxygen barrier layer of the ultrathin substrate is broken through.
Drawings
FIG. 1 is a schematic cross-sectional view of a flexible composite substrate;
in the drawings, the reference numerals denote: 1. base material, 2 inorganic nano coating, 3 organic barrier layer, 4 inorganic barrier layer and 5 transparent electrode
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments. It should be noted that these examples are only for explaining the present invention, and are not intended to limit other embodiments of the present invention.
The flexible composite substrate is provided with an inorganic nano coating, a base material, a water-oxygen barrier layer and a transparent conductive film from bottom to top in sequence.
The inorganic nano coating is inorganic oxide SiO2Or Al2O3It is made up by coating nano silica sol or nano alumina sol. The inorganic nano coating can prevent the deformation of a thinner base material under the action of plasma deposition or high temperature, improve the processing performance of the base material, and improve the strength, hardness and wear resistance of the base material, thereby realizing the preparation of the ultrathin high-performance water-oxygen barrier layer. The thickness of the coating is 10-200nm, preferably 50-100 μm, the light transmittance of the composite substrate is influenced when the thickness of the coating is more than 200nm, the coating is less than 10nm, the function of enhancing the hardness and the wear resistance of the base material cannot be realized, and the hardness of the finally obtained coating is 3H-6H. The solid content of the sol is 10-30 wt%, the sol is water or glycol, and some additives can be added into the sol to improve the film forming property of the silica sol and the alumina sol and the adhesive force between the silica sol and the base material.
The substrate comprises one of Polyimide (PI), tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF) and ethylene-vinylidene fluoride copolymer (ECTFE). The flexible substrate has excellent weather resistance, and is a basic requirement for ensuring long-term outdoor use of the device. And the common PET and PEN base materials have poor weather resistance, and the materials can be degraded, yellowed and cracked after being used for a long time in illumination, so that the requirements of special fields such as space environment and the like can not be met, and the application field of the flexible perovskite battery is limited. Meanwhile, the thermal deformation temperatures of the PET and PEN base materials are low, so that the annealing temperature and the film forming quality of the perovskite light absorption layer are limited, and the further improvement of the photoelectric conversion efficiency and the stability of the flexible PSC is influenced. The thickness of the substrate is 10 to 150 μm, preferably 30 to 75 μm; substrate thickness > 150 μm results in a large degree of surface area of the battery, and substrate thickness < 10 μm results in no processability of the substrate; the higher the light transmittance of the base material is, the more sunlight can be absorbed by the cell, thereby improving the conversion efficiency of the cell.
The flexible base material adopted by the invention can meet the long-term outdoor high-low temperature use requirement, and has excellent chemical corrosion resistance and excellent irradiation resistance. When the annealing temperature of the perovskite battery is higher than 135 ℃, the base material is not deformed, so that the perovskite thin film with high quality and more stable crystalline phase is obtained.
The water-oxygen barrier layer is an inorganic barrier layer or comprises one or more organic barrier layer/inorganic barrier layer pairs, wherein the inorganic barrier layer comprises metal oxide or nitride, and the metal can be at least one selected from Al, Si, Zr, Ti, Hf, Ta, In, Sn and Zn. The thickness of the inorganic barrier layer is 10-600nm, preferably 100-300 nm. The inorganic barrier layer is too thin, the barrier property is not good, and the brittleness of the too thick film is increased, so that the cracking phenomenon is easy to generate. The organic barrier layer is polyacrylic resin containing silicon element, and has a thickness of 0.5-20 μm, preferably 0.8-2 μm. The organic barrier layer is too thin to cover the defects of the inorganic barrier layer, and the adhesion is not good if it is too thick. The organic barrier layer has the function of flattening the substrate under the inorganic barrier layer, and can cover up the defects of the inorganic barrier layer and play a role in protection when being placed above the inorganic barrier layer. The water vapor permeability of the water oxygen barrier layer requires WVTR < 10-4g/m2Can meet the requirement of the perovskite battery on waterThe level of oxygen barrier required.
The transparent electrode can be selected from one or more of Indium Tin Oxide (ITO), Ag/ITO/Ag, Ag/AZO/Ag, silver nanowires (AgNws), silver or copper metal grids, carbon nanotubes or graphite. The square resistance of the surface is 10-40 omega/□; the light transmittance is more than 80 percent. The lower the square resistance of the transparent electrode, the better, the square resistance is increased, and the photoelectric conversion efficiency of the cell is reduced; but lower sheet resistance generally means lower light transmittance. Therefore, an optimum balance between sheet resistance and light transmittance is required, typically greater than 80%. The adoption of the high-temperature resistant base material is beneficial to annealing and crystallization of the ITO transparent electrode at higher temperature, and the square resistance of the ITO transparent electrode is reduced.
The invention also provides a preparation method of the flexible perovskite thin film solar cell, which comprises the following steps:
(1) adopting UV-O on the outer surface of the flexible substrate3、O2Plasma or Plasma treatment followed by a wet coating process to deposit the inorganic nanocoating. Wet coating processes include, but are not limited to, microgravure coating, slot coating, roll coating, spray coating, knife coating, or screen printing.
(2) And (3) treating the inner surface of the substrate in the same way as the step (1). Depositing an organic barrier layer on the inner surface, depositing an inorganic barrier layer on the surface of the organic barrier layer, and finishing the preparation of the water-oxygen barrier layer after depositing one or more paired layers. The flexible substrate can be a substrate or a substrate/planarization layer, and the planarization layer can reduce the surface roughness of the substrate, so that the performance of the water-oxygen barrier layer is improved. The flexible substrate may be surface treated by plasma or ultraviolet ozone to improve surface interface properties. The organic barrier layer can be prepared by wet coating, ink-jet printing, screen printing, vacuum evaporation polymerization, and the inorganic barrier layer is formed on the surface of the organic barrier layer by Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), Plasma Enhanced Chemical Vapor Deposition (PECVD) or Atomic Layer Deposition (ALD). To obtain a higher barrier property, it is often possible to prepare one or more organic barrier layer/inorganic barrier layer pairs.
(2) And (3) depositing a transparent electrode on the surface of the water oxygen barrier layer in the step (1), and etching to form a required electrode pattern. The transparent electrode can be prepared by wet coating (such as AgNWs and carbon nano tubes) and magnetron sputtering (such as ITO, Ag/ITO/Ag, Ag/AZO/Ag and the like), after the preparation is finished, a proper process is selected to etch the required electrode pattern according to the device pattern design and the characteristics of the transparent electrode, and the etching process can be selected from extreme lithography and photoresist process.
The flexible composite substrate for the perovskite solar cell has the advantages of flexibility, light weight, ultrathin property, barrier property, weather resistance, inclusion of a transparent conductive film and the like, has excellent weather resistance and long-term stability, can be widely applied to perovskite cells with various structures, and meets the requirements of the perovskite solar cell on the substrate and packaging.
The present invention will be described in further detail with reference to the following examples, but the practice of the present invention is not limited to the following examples.
Example 1
Step one, preparing a water-oxygen barrier layer:
taking a 50 mu m ETFE film as a base material and adopting O2Plasma treatment of the outer surface of the substrate, micro-gravure coating with 20% by weight of SiO2Hydrosol to obtain 50nm SiO2An inorganic nanocoating. Then, the inner surface of the base material is treated by plasma, a planarization layer is coated, and SiN is deposited by PECVD equipmentxAn inorganic barrier layer having a thickness of 150 nm; then coating an organic silicon modified polyacrylate organic barrier layer in vacuum with the thickness of 10 mu m; depositing 150nm thick SiN again by PECVD equipmentxAnd (4) an inorganic barrier layer, so as to finish the preparation of the water-oxygen barrier layer. WVTR of 1X 10-5g/m2/day。
Step two, preparing a transparent electrode:
on the surface of the water-oxygen barrier layer prepared in the first step, an ITO transparent conductive film with the thickness of 180nm is prepared by magnetron sputtering, the sheet resistance is 10 omega/□, and the light transmittance is 84%. And (5) laser etching to obtain a required pattern, and finishing the preparation of the flexible composite substrate. The flexible composite substrate structure is shown in fig. 1.
Step three, preparing an electron transport layer:
SnO with the concentration of 3 wt% is coated on the surface of a transparent electrode of a flexible composite substrate in a spin coating manner2The water solution is rotated at 1500rpm for 30 s. Drying at 150 deg.C for 30min to obtain a thickness of 25 nm.
Fourthly, preparing a perovskite light absorption layer:
under the protection of nitrogen, a perovskite light absorption layer is prepared on the surface of the electron transport layer through a two-step method. The spin-coating liquid in the first step is PbI2: PbBr2The molar ratio of the mixed solution to the mixed solution is 80:20, the solvent is DMF and DMSO mixed solution, the volume ratio is 90:10, and the solution concentration is 1.3M. The spin speed of the first step was 1500rpm for 30s, and then dried at 70 ℃. The spin-coating liquid in the second step is a mixed liquid of FAI, MABr and MACl with the mass ratio of 10:1:1, the solvent is IPA, and the concentration of the solution is 72 mg/ml. And the spin coating rotation speed of the second step is 1300rpm, the time is 30s, and the perovskite light absorption layer with the thickness of 600nm is obtained by annealing at 150 ℃ for 15 min.
Step five, preparing a hole transport layer:
under the protection of nitrogen, preparing a hole transport layer on the perovskite light absorption layer by adopting a spin coating method, adding 7.5 mu l of Li-TFSI/acetonitrile (170mg/1ml) and 4 mu l of tBP (tert-butyl phosphate) into a PTAA (Mn ═ 18,000g/mol) toluene solution with the concentration of 10mg/ml, dissolving to prepare a solution, and spin-coating the solution on the surface of the perovskite light absorption layer at the rotating speed of 3000rpm for 30s to obtain the hole transport layer with the thickness of 150 nm.
Sixthly, preparing a counter electrode:
preparing a counter electrode on the surface of the hole transport layer by thermal evaporation at 5 × 10-4Under Pa vacuum degree, gold with a thickness of 80nm was vacuum-evaporated to form a counter electrode.
Seventh, preparing the adhesive layer
And coating a UV (ultraviolet) curing solvent-free adhesive on the surface of the metal electrode to form an adhesive layer, wherein the thickness of the adhesive layer is 1 mu m.
Eighth, compounding the high barrier film
An ETFE substrate high-barrier film (WVTR is 5 multiplied by 10) is adopted by a lamination composite device-4g/m2/day) is compounded with the glue layer of the seventh step and then cured. Curing conditions were 200W UV lamp for 1 min. The high barrier film has the structure of base material, organic barrier layer, inorganic barrier layer and organicThe barrier layer, the preparation method and the material of the barrier layer are the same as the first step.
The device structure of the flexible perovskite thin-film solar cell prepared by the method is as follows: flexible composite substrate (ETFE/water oxygen barrier layer/ITO)/SnO2/(FAPbI3)x(MAPbBr3)1-xPTAA/Au/adhesive layer/high-barrier film with effective area of 0.16cm2The photoelectric conversion efficiency data are shown in Table 1, the test conditions are AM1.5G spectrum and the illumination intensity is 1000W/m2The I-V curves were tested using a model Keithly2400 digital Source Meter using an AAA-grade solar simulator (model XES-502S + ELS155, SAN-EI, Japan). The photostability tester was also a solar simulator (model XES-502S + ELS155, SAN-EI, Japan), with a spectral distribution AM1.5G, at a temperature of 25 ℃. The damp-heat aging is carried out in an aging oven with the temperature of 65 ℃ and the humidity of 85 percent. The time for the conversion efficiency of the light and humid heat aging test to decay to 80% of the initial value (T80) is shown in table 1.
Example 2
Step one, preparing a water-oxygen barrier layer:
using a 125 mu mUV cut-off transparent PVDF film as a base material, carrying out external surface treatment by corona, and coating 25 wt% of Al in a slit2O3Hydrosol to obtain 100nm Al2O3An inorganic nanocoating. Treating the inner surface of the substrate by adopting plasma, coating a planarization layer, and then depositing SiO by adopting PECVD equipmentxCyAn inorganic barrier layer having a thickness of 200 nm; then coating an organic silicon modified polyacrylate organic barrier layer with the thickness of 2 mu m; depositing SiO with the thickness of 200nm again by adopting PECVD equipmentxCyAnd (4) an inorganic barrier layer, so as to finish the preparation of the water-oxygen barrier layer. WVTR of 1X 10-4g/m2/day。
Step two, preparing a transparent electrode:
on the surface of the water-oxygen barrier layer prepared in the first step, a 100nm silver nanowire AgNWs transparent conductive film is prepared in a wet coating mode, the sheet resistance is 35 omega/□, and the light transmittance is 85%. And chemically etching to form a required pattern to finish the preparation of the flexible composite substrate.
The third to seventh steps are the same as in example 1;
eighth, compounding the high barrier film
A125 mu m PVDF substrate high-barrier film (WVTR is 1 multiplied by 10) is adopted by a lamination composite device-4g/m2/day) is compounded with the glue layer of the seventh step and then cured. Curing conditions were 200W UV lamp for 1 min. The structure of the high barrier film is base material/organic barrier layer/inorganic barrier layer/organic barrier layer, and the preparation method and material of the barrier layer are the same as those in the first step.
The photoelectric conversion efficiency and aging test data of the flexible perovskite thin-film solar cell prepared by the method are shown in table 1, and the test conditions are the same as those of example 1.
Example 3
Step one, preparing a water-oxygen barrier layer:
using a 50 mu mUV cut-off type transparent PI film as a base material, carrying out external surface treatment by corona, and coating 25 wt% of Al in a slit2O3Hydrosol to obtain 100nm Al2O3An inorganic nanocoating. Treating the inner surface of the substrate by plasma, and then depositing Al by using an ALD device2O3Inorganic barrier layer with thickness of 50 nm. WVTR of 1X 10-5g/m2/day。
Step two, preparing a transparent electrode:
on the surface of the water-oxygen barrier layer prepared in the first step, an Ag/ITO/Ag transparent conductive film with the thickness of 150nm is prepared in a magnetron sputtering mode, the sheet resistance is 20 omega/□, and the light transmittance is 86%. And chemically etching to form a required pattern to finish the preparation of the flexible composite substrate.
The third to seventh steps are the same as in example 1;
eighth, compounding the high barrier film
A50 μm thick PI substrate high barrier film (WVTR of 1X 10) was laminated using a lamination equipment-5g/m2And/day) is compounded with the glue layer in the seventh step to obtain the flexible perovskite thin film solar cell. The structure of the high-barrier film is a substrate/inorganic barrier layer, and the preparation method and the material of the barrier layer are the same as those in the first step.
The photoelectric conversion efficiency and aging test data of the device of the flexible perovskite thin-film solar cell prepared by the method are shown in table 1, and the test conditions are the same as those of example 1.
Example 4
Step one, preparing a water-oxygen barrier layer:
using a 125 mu mUV cut-off transparent ECTFE film as a substrate and adopting O2Plasma treatment of the outer surface of the substrate, micro-gravure coating with 23 wt% SiO2Hydrosol to obtain 80nm SiO2An inorganic nanocoating. Treating the inner surface of the substrate by plasma, and then depositing Al by using an ALD device2O3An inorganic barrier layer having a thickness of 50 nm; then, printing an organic silicon modified polyacrylate organic barrier layer by ink jet, wherein the thickness of the organic silicon modified polyacrylate organic barrier layer is 15 mu m; then, Al with the thickness of 50nm is deposited by adopting an ALD device2O3And (4) an inorganic barrier layer, so as to finish the preparation of the water-oxygen barrier layer. WVTR of 2X 10-6g/m2/day。
Step two, preparing a transparent electrode:
on the surface of the water-oxygen barrier layer prepared in the first step, a 100nm thick silver nanowire AgNWs transparent conducting layer is prepared in a wet coating mode, the sheet resistance is 35 omega/□, and the light transmittance is 85%. And chemically etching to form a required pattern to finish the preparation of the flexible composite substrate.
The third to seventh steps are the same as in example 1;
eighth, compounding the high barrier film
The ECTFE substrate high barrier film (WVTR of 2X 10) is prepared by adopting a lamination composite device-6g/m2And/day) is compounded with the glue layer in the seventh step to obtain the flexible perovskite thin film solar cell. The structure of the high barrier film is base material/organic barrier layer/inorganic barrier layer/organic barrier layer, and the preparation method and material of the barrier layer are the same as those in the first step.
The photoelectric conversion efficiency and aging test data of the flexible perovskite thin-film solar cell prepared by the method are shown in table 1, and the test conditions are the same as those of example 1.
Example 5
Step one, preparing a water-oxygen barrier layer:
using 50 mu m ETFE film as a base material, carrying out external surface treatment by corona, and coating 25 wt% Al on a strip seam2O3Hydrosol to obtain 100nm Al2O3An inorganic nanocoating. Treating the inner surface of the substrate by adopting plasma, coating a planarization layer, and then depositing SiN by adopting PECVD equipmentxAn inorganic barrier layer having a thickness of 150 nm; then coating an organic silicon modified polyacrylate organic barrier layer in vacuum with the thickness of 10 mu m; depositing 150nm thick SiN again by PECVD equipmentxAnd (4) an inorganic barrier layer, so as to finish the preparation of the water-oxygen barrier layer. WVTR of 1X 10-5g/m2/day。
Step two, preparing a transparent electrode:
on the surface of the water-oxygen barrier layer prepared in the first step, an ITO transparent conductive film with the thickness of 180nm is prepared by magnetron sputtering, the sheet resistance is 10 omega/□, and the light transmittance is 84%. And (5) laser etching to obtain a required pattern, and finishing the preparation of the flexible composite substrate.
Step three, preparing a hole transport layer:
adopting magnetron sputtering NiO on the surface of the transparent electrode of the flexible composite substratexLayer, thickness 15 nm.
Fourthly, preparing a perovskite light absorption layer:
under the protection of nitrogen, a perovskite light absorption layer is prepared on the surface of the hole transport layer through a two-step method. The spin-coating liquid in the first step is PbI2: PbBr2The molar ratio of the mixed solution to the mixed solution is 80:20, the solvent is DMF and DMSO mixed solution, the volume ratio is 90:10, and the solution concentration is 1.3M. In the first step, slot-die slit coating and drying treatment are adopted. The spin-coating liquid in the second step is a mixed liquid of FAI, MABr and MACl with the mass ratio of 12:1.5:1.5, the solvent is IPA, and the concentration of the solution is 80 mg/ml. And in the second step, after slot-die slit coating, annealing at 105 ℃ for 90min to obtain a perovskite light absorption layer with the thickness of 600 nm.
Fifthly, preparing an electron transport layer:
under the protection of nitrogen, preparing an electron transport layer, PC, on the perovskite light absorption layer by slot-die coating61BM chlorobenzene solution with a concentration of 20mg/ml, a rotation speed of 1000rpm, a time of 30s and a thickness of 60 nm. Then at PC61BM surface vacuum evaporation of 20nm BCP and 8nm C60And finishing the preparation of the electron transport layer.
Sixthly, preparing a counter electrode:
in the electronic transmissionThe surface of the layer is provided with a counter electrode prepared by an electron beam thermal evaporation method at 5 multiplied by 10-4And (5) carrying out vacuum evaporation on a copper electrode with the thickness of 80nm under the Pa vacuum degree.
Seventh, preparing the adhesive layer
And coating a UV (ultraviolet) curing solvent-free adhesive on the surface of the metal electrode to form an adhesive layer. The adhesive is an epoxy resin adhesive containing 3 wt% of CaO, and the thickness of the adhesive layer is 1 μm.
Eighth, compounding the high barrier film
An ETFE substrate high-barrier film (WVTR is 5 multiplied by 10) is adopted by a lamination composite device-4g/m2/day) is compounded with the glue layer of the seventh step and then cured. Curing conditions were 200W UV lamp for 1 min. The structure of the high barrier film is base material/organic barrier layer/inorganic barrier layer/organic barrier layer, and the preparation method and material of the barrier layer are the same as those in the first step.
The device structure of the flexible perovskite thin-film solar cell prepared by the method is as follows: flexible composite substrate (ETFE/water oxygen barrier layer/ITO)/NiOx/(FAPbI3)x(MAPbBr3)1-x/PC61BM/BCP/C60Cu, adhesive layer, and high barrier film with effective area of 0.16cm2The photoelectric conversion efficiency and the aging test data are shown in Table 2, and the test conditions are the same as those in example 1.
Example 6
Step one, preparing a water-oxygen barrier layer:
using a 125 mu mUV cut-off type transparent PVDF film as a base material, treating the outer surface of the base material by corona, and coating 20 wt% SiO on a micro-concave plate2Hydrosol to obtain 50nm SiO2An inorganic nanocoating. Treating the inner surface of the substrate by adopting plasma, coating a planarization layer, and then depositing SiO by adopting PECVD equipmentxCyAn inorganic barrier layer having a thickness of 200 nm; then coating an organic silicon modified polyacrylate organic barrier layer with the thickness of 2 mu m; depositing SiO with the thickness of 200nm again by adopting PECVD equipmentxCyAnd (4) an inorganic barrier layer, so as to finish the preparation of the water-oxygen barrier layer. WVTR of 1X 10-4g/m2/day。
Step two, preparing a transparent electrode:
on the surface of the water-oxygen barrier layer prepared in the first step, a 100nm thick silver nanowire AgNWs transparent conductive film is prepared in a wet coating mode, the sheet resistance is 35 omega/□, and the light transmittance is 85%. And chemically etching to form a required pattern to finish the preparation of the flexible composite substrate.
The third to seventh steps were the same as in example 5;
eighth, compounding the high barrier film
A125 mu m PVDF substrate high-barrier film (WVTR is 1 multiplied by 10) is adopted by a lamination composite device-4g/m2/day) is compounded with the glue layer of the seventh step and then cured. Curing conditions were 200W UV lamp for 1 min. The structure of the high barrier film is base material/organic barrier layer/inorganic barrier layer/organic barrier layer, and the preparation method and material of the barrier layer are the same as those in the first step.
The photoelectric conversion efficiency and aging test data of the flexible perovskite thin-film solar cell prepared by the method are shown in table 2, and the test conditions are the same as those of example 1.
Example 7
Step one, preparing a water-oxygen barrier layer:
using a 50 mu mUV cut-off transparent PI film as a base material, carrying out external surface treatment by corona, and coating 30 wt% Al in a slit2O3Hydrosol to obtain 200nm Al2O3An inorganic nanocoating. Treating the inner surface of the substrate by plasma, and then depositing Al by using an ALD device2O3Inorganic barrier layer with thickness of 50 nm. WVTR of 1X 10-5g/m2/day。
Step two, preparing a transparent electrode:
on the surface of the water-oxygen barrier layer prepared in the first step, an Ag/ITO/Ag transparent conductive film with the thickness of 150nm is prepared in a magnetron sputtering mode, the sheet resistance is 20 omega/□, and the light transmittance is 86%. And chemically etching to form a required pattern to finish the preparation of the flexible composite substrate.
The third to seventh steps were the same as in example 5;
eighth, compounding the high barrier film
A50 μm thick PI substrate high barrier film (WVTR of 1X 10) was laminated using a lamination equipment-5g/m2/daAnd y) compounding with the glue layer in the seventh step to obtain the flexible perovskite thin film solar cell. The structure of the high-barrier film is a substrate/inorganic barrier layer, and the preparation method and the material of the barrier layer are the same as those in the first step.
The photoelectric conversion efficiency and aging test data of the flexible perovskite thin-film solar cell prepared by the method are shown in table 2, and the test conditions are the same as those of example 1.
Example 8
Step one, preparing a water-oxygen barrier layer:
using a 125 mu mUV cut-off transparent ECTFE film as a substrate and adopting O2Plasma treatment of the outer surface of the substrate, micro-gravure coating with 30% by weight of SiO2Hydrosol to obtain 150nm SiO2An inorganic nanocoating. Treating the inner surface of the substrate by plasma, and then depositing Al by using an ALD device2O3An inorganic barrier layer having a thickness of 50 nm; then, printing an organic silicon modified polyacrylate organic barrier layer by ink jet, wherein the thickness of the organic silicon modified polyacrylate organic barrier layer is 15 mu m; then, Al with the thickness of 50nm is deposited by adopting an ALD device2O3And (4) an inorganic barrier layer, so as to finish the preparation of the water-oxygen barrier layer. WVTR of 2X 10-6g/m2/day。
Step two, preparing a transparent electrode:
on the surface of the water-oxygen barrier layer prepared in the first step, a 100nm thick silver nanowire AgNWs transparent conducting layer is prepared in a wet coating mode, the sheet resistance is 35 omega/□, and the light transmittance is 85%. And chemically etching to form a required pattern to finish the preparation of the flexible composite substrate.
The third to seventh steps were the same as in example 5;
eighth, compounding the high barrier film
The ECTFE substrate high barrier film (WVTR of 2X 10) is prepared by adopting a lamination composite device-6g/m2And/day) is compounded with the glue layer in the seventh step to obtain the flexible perovskite thin film solar cell. The structure of the high barrier film is base material/organic barrier layer/inorganic barrier layer/organic barrier layer, and the preparation method and material of the barrier layer are the same as those in the first step.
The photoelectric conversion efficiency and aging test data of the flexible perovskite thin-film solar cell prepared by the method are shown in table 2, and the test conditions are the same as those of example 1.
Comparative example 1
Firstly, preparing a transparent electrode pattern:
the 125-micron PET/ITO is used as a base material, the sheet resistance is 30 omega/□, the light transmittance is 86%, and the electrode pattern is etched by laser.
Step two, preparing an electron transport layer:
coating SnO with the concentration of 3 wt% on the surface of the transparent electrode in a spin mode2The water solution is rotated at 1500rpm for 30 s. Drying at 150 deg.C for 30min to obtain a thickness of 25 nm.
Step three, preparing a perovskite light absorption layer:
under the protection of nitrogen, a perovskite light absorption layer is prepared on the surface of the electron transport layer through a two-step method. The spin-coating liquid in the first step is PbI2: PbBr2The molar ratio of the mixed solution to the mixed solution is 80:20, the solvent is DMF and DMSO mixed solution, the volume ratio is 90:10, and the solution concentration is 1.3M. The spin speed of the first step was 1500rpm for 30s, and then dried at 70 ℃. The spin-coating liquid in the second step is a mixed liquid of FAI, MABr and MACl with the mass ratio of 10:1:1, the solvent is IPA, and the concentration of the solution is 72 mg/ml. And the spin coating rotation speed of the second step is 1300rpm, the time is 30s, and the perovskite light absorption layer with the thickness of 600nm is obtained by annealing at 150 ℃ for 15 min.
Step four, preparing a hole transport layer:
under the protection of nitrogen, preparing a hole transport layer on the perovskite light absorption layer by adopting a spin coating method, adding 7.5 mu l of Li-TFSI/acetonitrile (170mg/1ml) and 4 mu l of tBP (tert-butyl phosphate) into a PTAA (Mn ═ 18,000g/mol) toluene solution with the concentration of 10mg/ml, dissolving to prepare a solution, and spin-coating the solution on the surface of the perovskite light absorption layer at the rotating speed of 3000rpm for 30s to obtain the hole transport layer with the thickness of 150 nm.
Step five, preparing a counter electrode:
preparing a counter electrode on the surface of the hole transport layer by thermal evaporation at 5 × 10-4Under Pa vacuum degree, gold with a thickness of 80nm was vacuum-evaporated to form a counter electrode.
Sixthly, preparing a glue layer
And coating a UV (ultraviolet) curing solvent-free adhesive on the surface of the metal electrode to form an adhesive layer. The thickness of the glue layer is 1 μm.
Seventhly, compounding the PET film
And compounding the 125 mu mPE substrate with the glue layer of the sixth step by using a laminating compounding device, and then curing. Curing conditions were 200W UV lamp for 1 min.
The device structure of the flexible perovskite thin-film solar cell prepared by the method is as follows: PET/ITO/SnO2/(FAPbI3)x(MAPbBr3)1-xPTAA/Au/adhesive layer/PET film with effective area of 0.16cm2The photoelectric conversion efficiency data are shown in Table 1, the test conditions are AM1.5G spectrum and the illumination intensity is 1000W/m2The I-V curves were tested using a model Keithly2400 digital Source Meter using an AAA-grade solar simulator (model XES-502S + ELS155, SAN-EI, Japan). The photostability tester was also a solar simulator (model XES-502S + ELS155, SAN-EI, Japan), with a spectral distribution AM1.5G, at a temperature of 25 ℃. The damp-heat aging is carried out in an aging oven with the temperature of 65 ℃ and the humidity of 85 percent.
Comparative example 2
Firstly, preparing a transparent electrode pattern:
and (3) taking 125-micron PET/ITO as a base material, and chemically etching the base material into a required electrode pattern by adopting hydrochloric acid.
Step two, preparing a hole transport layer:
adopting magnetron sputtering NiO on the surface of the transparent electrodexLayer, thickness 15 nm.
Step three, preparing a perovskite light absorption layer:
under the protection of nitrogen, a perovskite light absorption layer is prepared on the surface of the hole transport layer through a two-step method. The spin-coating liquid in the first step is PbI2: PbBr2The molar ratio of the mixed solution to the mixed solution is 80:20, the solvent is DMF and DMSO mixed solution, the volume ratio is 90:10, and the solution concentration is 1.3M. In the first step, slot-die slit coating and drying treatment are adopted. The spin-coating liquid in the second step is a mixed liquid of FAI, MABr and MACl with the mass ratio of 12:1.5:1.5, the solvent is IPA, and the concentration of the solution is 80 mg/ml. And in the second step, after slot-die slit coating, annealing at 105 ℃ for 90min to obtain a perovskite light absorption layer with the thickness of 600 nm.
Fourthly, preparing an electron transport layer:
protection by nitrogenPreparing an electron transport layer, PC, on the perovskite light absorption layer by slot-die coating61BM chlorobenzene solution with a concentration of 20mg/ml, a rotation speed of 1000rpm, a time of 30s and a thickness of 60 nm. Then at PC61BM surface vacuum evaporation of 20nm BCP and 8nm C60And finishing the preparation of the electron transport layer.
Step five, preparing a counter electrode:
preparing a counter electrode on the surface of the electron transport layer by thermal evaporation at 5 × 10-4Under Pa vacuum degree, copper with a thickness of 80nm was vacuum-evaporated to form a counter electrode.
Sixthly, preparing a glue layer
And compounding a pressure-sensitive adhesive film with the thickness of 20 mu m on the surface of the metal electrode.
Seventhly, compounding the PET film
And compounding the PET base material with the thickness of 125 microns with the glue layer in the sixth step by adopting a laminating compounding device.
The device structure of the flexible perovskite thin-film solar cell prepared by the method is as follows: PET/ITO/NiOx/(FAPbI3)x(MAPbBr3)1-x/PC61BM/BCP/C60Cu/adhesive layer/PET film with effective area of 0.16cm2The photoelectric conversion efficiency and the aging test data are shown in Table 2, and the test conditions are the same as those in example 1.
Table 1: official planar structural perovskite cell examples and comparative example data
Figure RE-GDA0002359633770000121
Figure RE-GDA0002359633770000131
Table 2: trans-planar structural perovskite cell examples and comparative example data
Figure RE-GDA0002359633770000132

Claims (6)

1. A flexible composite substrate for a perovskite thin-film solar cell is characterized in that an inorganic nano coating, a base material, a water-oxygen barrier layer and a transparent conductive film are sequentially arranged from bottom to top;
the inorganic nano coating is inorganic oxide SiO2Or Al2O3Is formed by coating nano silica sol or nano alumina sol; the solid content of the sol is 10-30 wt%, and the sol is water or glycol.
2. The flexible composite substrate for perovskite thin-film solar cells as claimed in claim 1, wherein the base material is selected from one of Polyimide (PI), tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF) or ethylene-vinylidene fluoride copolymer (ECTFE), and the light transmittance of the base material is more than 80%, preferably more than 90%; the thickness of the substrate is 10 to 150. mu.m, preferably 30 to 75 μm.
3. The flexible composite substrate for perovskite thin-film solar cells as claimed In claim 1, wherein the water-oxygen barrier layer is an inorganic barrier layer or comprises one or several organic barrier layer/inorganic barrier layer pairs, wherein the inorganic barrier layer comprises a metal oxide or nitride, the metal being selected from at least one of Al, Si, Zr, Ti, Hf, Ta, In, Sn, Zn; the thickness of the inorganic barrier layer is 10-600nm, preferably 100-300 nm; the organic barrier layer is polyacrylic resin containing silicon element, and has a thickness of 0.5-20 μm, preferably 0.8-2 μm; the water-oxygen barrier layer has a water vapor permeability WVTR < 10-4g/m2/day。
4. The flexible composite substrate for perovskite thin-film solar cells as claimed in claim 1, wherein the transparent electrode is selected from one or more of Indium Tin Oxide (ITO), Ag/ITO/Ag, Ag/AZO/Ag, silver nanowires (AgNws), silver or copper metal grids, carbon nanotubes or graphite; the square resistance of the surface is 10-40 omega/□; the light transmittance is more than 80 percent.
5. Flexible perovskite thin film solar cell according to claim 1, characterized in that the thickness of the inorganic nanocoating is 10-200nm, preferably 50-100 μ ι η; the coating hardness is 3H-6H.
6. A method for preparing a flexible composite substrate for perovskite thin film solar cells as defined in any one of claims 1 to 5, wherein the preparation is carried out by the steps of:
(1) treating the outer surface of the flexible substrate, and then coating an inorganic nano coating;
(2) treating the inner surface of the flexible substrate, and then coating an organic barrier layer;
(3) depositing an inorganic barrier layer on the surface of the organic barrier layer coated in the step (2), and finishing the preparation of the water-oxygen barrier layer after depositing one or more organic/inorganic pair layers;
(4) and (4) depositing a transparent conductive film on the surface of the water-oxygen barrier layer in the step (3) to finish the preparation of the flexible composite substrate.
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