CN111668375A - Perovskite photovoltaic cell, preparation method thereof and preparation method of photoelectric component - Google Patents

Perovskite photovoltaic cell, preparation method thereof and preparation method of photoelectric component Download PDF

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CN111668375A
CN111668375A CN202010558361.3A CN202010558361A CN111668375A CN 111668375 A CN111668375 A CN 111668375A CN 202010558361 A CN202010558361 A CN 202010558361A CN 111668375 A CN111668375 A CN 111668375A
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layer
cutting line
line groove
electrode layer
perovskite
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不公告发明人
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Hangzhou Microquanta Semiconductor Corp ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a perovskite photovoltaic cell which comprises a substrate, a front electrode layer, a first current carrier transmission layer, a perovskite layer, a second current carrier transmission layer and a top electrode layer, wherein a cutting line groove P1 is formed in the front electrode layer, the cutting line groove P1 cuts the front electrode layer, a preparation material which is the same as that of the first current carrier transmission layer is filled in the cutting line groove P1, a cutting line groove P3 is formed in the top electrode layer, the bottom of the cutting line groove P3 is exposed out of the front electrode layer, isolation layers are respectively arranged on the side faces of the perovskite layer on two sides of the cutting line groove P3 to shield the perovskite layer, and a preparation material which is the same as that of the top electrode layer is filled in one side of the cutting line groove P3 and is in. The invention also discloses a preparation method of the perovskite photovoltaic cell. The invention prepares the isolating layer in advance to protect the subsequently prepared perovskite layer, and effectively avoids the problems of degradation of perovskite materials and reduction of electrode conductivity caused by the exposure of the side surface of the perovskite film.

Description

Perovskite photovoltaic cell, preparation method thereof and preparation method of photoelectric component
Technical Field
The invention belongs to the technical field of perovskite photovoltaic cell preparation, and particularly relates to a perovskite photovoltaic cell and a preparation method thereof, and a preparation method of a photoelectric component.
Background
Perovskites are a class with ABX3The general term crystalline material of structure. Researches find that some halogenated perovskite materials have excellent semiconductor characteristics and can realize the interconversion of high-quality light energy and electric energy, so that the halogenated perovskite materials can be applied to a plurality of fields such as photovoltaic cells, light-emitting diodes, detectors and the like.
The perovskite tandem component is used as a main structure of a large-area perovskite photoelectric conversion device. At present, perovskite thin films are usually isolated into a plurality of small parts after being prepared and then connected in series, so that the performance of the whole active region is improved. The side surface of the perovskite exposed in the cutting process has higher reactivity and is easy to react with water and oxygen to degrade; on the other hand, direct contact between the side perovskite and the metal electrode causes generation of metal halide, which lowers the conductivity of the electrode.
In patent publication No. CN110534651A, a perovskite solar cell and module and a method for preparing the same are disclosed, and a method for protecting the active layer after cutting and then coating an isolation layer on the side surface is disclosed. The method has more defects in practical application, for example, the dispensing operation is exposed in the air for a long time, so that the perovskite is seriously corroded by water and oxygen; high-energy ultraviolet rays used for glue curing can cause perovskite degradation; the glue has volume expansion or contraction after being cured, and the protective effect of the side face of the perovskite is influenced. The isolation layer is prepared by adopting an evaporation method, so that the mask precision requirement is very high, and the method is not suitable for practical production. Therefore, the conventional method of cutting and segmenting after preparing the active layer is not suitable for the perovskite thin film component.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel large-area perovskite photovoltaic cell, a preparation method thereof and a preparation method of a photoelectric component. The preparation method of the isolation layer is more diversified, and the problem that the perovskite material is degraded due to side exposure when the perovskite layer is cut in the prior art is solved.
The invention is realized in such a way, a perovskite photovoltaic cell is provided, the internal structure of the perovskite photovoltaic cell sequentially comprises a substrate, a front electrode layer, a first carrier transmission layer, a perovskite layer, a second carrier transmission layer and a top electrode layer from bottom to top, n-1 cutting wire slots P1 are arranged on the front electrode layer, the cutting wire slots P1 are used for cutting off the front electrode layer, the cutting wire slots P1 are filled with a preparation material which is the same as that of the first carrier transmission layer and are in conductive connection with the first carrier transmission layer, n-1 cutting wire slots P3 are arranged on the top electrode layer, each cutting wire slot P3 is positioned at one side of the corresponding cutting wire slot P1, the bottom of the cutting wire slot P3 is exposed out of the front electrode layer, isolation layers are respectively arranged on the side surfaces of the perovskite layer at two sides of the cutting wire slot P3 for shielding the perovskite layer, one side of each cutting wire slot P3 is filled with a preparation material which is the same as that of, the perovskite photovoltaic cell is divided into n perovskite photovoltaic sub-cells under the combined action of n-1 cutting line grooves P1 and cutting line grooves P3.
The invention is realized in such a way, the perovskite photovoltaic cell comprises a substrate, a front electrode layer, a first carrier transmission layer, a perovskite layer, a second carrier transmission layer and a top electrode layer from bottom to top in sequence, wherein n-1 cutting wire slots P1 are arranged on the first carrier transmission layer, the cutting wire slots P1 simultaneously cut off the front electrode layer and the first carrier transmission layer, the cutting wire slots P1 are filled with a prepared material the same as that of the perovskite layer and are in conductive connection with the perovskite layer, the top electrode layer is provided with n-1 cutting wire slots P3, each cutting wire slot P3 is positioned at one side of the corresponding cutting wire slot P1, the bottom of the cutting wire slot P3 is exposed out of the front electrode layer, the side surfaces of the perovskite layer at the two sides of the cutting wire slot P3 are respectively provided with an isolating layer for shielding the perovskite layer, one side of the cutting wire slot P3 is filled with a prepared material the same as that of the top electrode layer and is in conductive connection with the top electrode layer, the perovskite photovoltaic cell is divided into n perovskite photovoltaic sub-cells under the combined action of n-1 cutting line grooves P1 and cutting line grooves P3.
The invention is thus achieved by providing a method of manufacturing a perovskite photovoltaic cell as hereinbefore described, comprising the steps of:
step one, scribing a front electrode layer prepared on a substrate to obtain a cutting line groove P1;
secondly, preparing an isolation region with the thickness not less than the sum of the thicknesses of the first carrier transmission layer and the perovskite layer at one side of the cutting line groove P1 and the position of the cutting line groove P3 by using a mask plate, wherein the width of the hollow region of the mask plate is greater than the width of the cutting line groove P3;
step three, sequentially preparing a first current carrier transmission layer, a perovskite layer and a second current carrier transmission layer by using a mask plate opposite to the hollow area in the step two;
scribing the middle area of the cutting isolation area to obtain a cutting line groove P2, wherein isolation layers are reserved on the left side and the right side of the cutting line groove P2 respectively, and the bottom of the isolation layer is exposed out of the front electrode layer;
step five, preparing a top electrode layer on the substrate film processed in the step four;
step six, scribing the area where the cutting line groove P2 is located to obtain a cutting line groove P3, wherein the bottom of the cutting line groove P3 is exposed out of the front electrode layer, the width of the cutting line groove P3 is smaller than that of the cutting line groove P2, a preparation material of a top electrode layer is reserved on one side, close to the cutting line groove P1, of the cutting line groove P3, and the other side of the cutting line groove P3 is close to the isolation layer.
The invention is thus achieved by providing a method of manufacturing a perovskite photovoltaic cell as hereinbefore described, comprising the steps of:
step I, scribing the front electrode layer prepared on the substrate to obtain a cutting line groove P1;
step II, preparing a first carrier transmission layer on the substrate film processed in the step I;
step III, preparing an isolation region with the thickness not smaller than that of the perovskite layer at one side of the cutting line groove P1 and at the position of the cutting line groove P3 by using a mask plate, wherein the width of the hollow region of the mask plate is larger than that of the cutting line groove P3;
step IV, sequentially preparing a perovskite layer and a second carrier transmission layer by using a mask plate opposite to the hollow area in the step III;
step V, etching the middle area of the cutting isolation area to obtain a cutting line groove P2, wherein isolation layers are reserved on the left side and the right side of the cutting line groove P2 respectively, and the bottom of the isolation layer is exposed out of the front electrode layer;
step VI, preparing a top electrode layer on the substrate film treated in the step V;
and step VII, scribing the region where the cutting line groove P2 is located to obtain a cutting line groove P3, wherein the bottom of the cutting line groove P3 is exposed out of the front electrode layer, the width of the cutting line groove P3 is smaller than that of the cutting line groove P2, a preparation material of a top electrode layer is reserved on one side, close to the cutting line groove P1, of the cutting line groove P3, and the other side of the cutting line groove P3 is close to the isolation layer.
The invention is thus achieved by providing a method of manufacturing a perovskite photovoltaic cell as hereinbefore described, comprising the steps of:
step 1, preparing an isolation region with the thickness not less than the sum of the thicknesses of a first carrier transmission layer and a perovskite layer at the position of a cutting line groove P3 by using a mask plate or a silk screen on a front electrode layer prepared on a substrate, wherein the width of a hollow region of the mask plate is greater than the width of the cutting line groove P3;
step 2, preparing a first carrier transmission layer on the film processed in the step 1, simultaneously scribing the first carrier transmission layer and the front electrode layer to obtain a cutting line groove P1, wherein the bottom of the cutting line groove P1 is exposed out of the substrate;
step 3, sequentially preparing a perovskite layer and a second carrier transmission layer on the first carrier transmission layer processed in the step 2;
step 4, etching the middle area of the cutting isolation area to obtain a cutting line groove P2, wherein isolation layers are respectively reserved on the left side and the right side of the cutting line groove P2, and the bottom of the isolation layer is exposed out of the front electrode layer;
step 5, preparing a top electrode layer on the substrate film treated in the step 4;
step 6, scribing the region where the cutting line groove P2 is located to obtain a cutting line groove P3, wherein the bottom of the cutting line groove P3 is exposed out of the front electrode layer, the width of the cutting line groove P3 is smaller than that of the cutting line groove P2, a preparation material of a top electrode layer is reserved on one side, close to the cutting line groove P1, of the cutting line groove P3, and the other side of the cutting line groove P3 is close to the isolation layer.
The invention is realized in such a way, and provides a preparation method of a photoelectric component, wherein the internal structure of the photoelectric component comprises a substrate, and a front electrode layer, a first current carrier transmission layer, a perovskite layer, a second current carrier transmission layer and a top electrode layer are sequentially arranged on the substrate from bottom to top, and the preparation method comprises the following steps:
step S1, etching the front electrode layer to obtain a first wire groove, and then preparing a first carrier transmission layer; preparing an isolation region with the thickness not less than the thickness of the perovskite layer at one side of the first wire groove and at the position of the third wire groove by using a mask plate, wherein the width of the hollow region of the mask plate is greater than that of the third wire groove;
step S2, sequentially preparing a perovskite layer and a second carrier transmission layer by using a mask plate opposite to the hollowed-out region of the step S1;
step S3, etching the middle area of the isolation area to obtain a second wire groove, wherein isolation layers are reserved on the left side and the right side of the second wire groove respectively;
and S4, preparing a top electrode layer on the film processed in the step S3, scribing the area where the second wire groove is located to obtain a third wire groove, wherein the width of the third wire groove is smaller than that of the second wire groove, the preparation material of the top electrode layer is reserved on one side of the third wire groove, and the other side of the third wire groove is close to the isolation layer.
The invention is realized in such a way, and provides a preparation method of a photoelectric component, wherein the internal structure of the photoelectric component comprises a substrate, and a front electrode layer, a first current carrier transmission layer, a perovskite layer, a second current carrier transmission layer and a top electrode layer are sequentially arranged on the substrate from bottom to top, and the preparation method comprises the following steps:
step S5, preparing an isolation region on the front electrode layer, wherein the thickness of the isolation region is larger than the sum of the thicknesses of the first carrier transmission layer and the perovskite layer, and the width of the isolation region is larger than the width of the second wire slot; preparing a first carrier transport layer in a region outside the isolation region; simultaneously etching the first carrier transmission layer and the front electrode layer to obtain a first wire groove;
step S6, sequentially preparing a perovskite layer and a second carrier transmission layer on the first carrier transmission layer;
step S7, etching the middle area of the isolation area to obtain a second wire groove, and reserving isolation layers on the left side and the right side of the second wire groove respectively;
and S8, preparing a top electrode layer on the film processed in the step S7, scribing the area where the second wire groove is located to obtain a third wire groove, wherein the width of the third wire groove is smaller than that of the second wire groove, the preparation material of the top electrode layer is reserved on one side of the third wire groove, and the other side of the third wire groove is close to the isolation layer.
Compared with the prior art, the perovskite photovoltaic cell, the preparation method thereof and the preparation method of the photoelectric component have the following characteristics: the isolation layer is prepared in advance, the subsequently prepared perovskite layer is protected, and the problems that perovskite materials are degraded and the electrode conductivity is reduced due to the fact that the side face of a perovskite film is exposed in a cutting process used for preparing the series perovskite photovoltaic module in the prior art are effectively solved.
Drawings
Fig. 1 is a schematic plan view of the internal structure of perovskite photovoltaic cells of examples 1 and 3 of the present invention;
fig. 2 is a schematic plan view of the internal structure of perovskite photovoltaic cells of examples 2 and 5 of the present invention;
fig. 3 is a schematic plan view of the internal structure of a perovskite photovoltaic cell according to example 4 of the present invention;
fig. 4 is a schematic plan view of the internal structure of the optoelectronic device in embodiment 6 of the present invention;
fig. 5 is a schematic plan view of the internal structure of the photovoltaic device according to embodiment 7 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Referring to fig. 1, an internal structure of a first preferred embodiment of the perovskite photovoltaic cell of the present invention sequentially includes, from bottom to top, a substrate 1, a front electrode layer 2, a first carrier transport layer 3, a perovskite layer 4, a second carrier transport layer 5, a barrier layer 6, and a top electrode layer 7.
N-1 cutting line grooves P1 are formed in the front electrode layer 2, the cutting line grooves P1 cut the front electrode layer 2, and the cutting line grooves P1 are filled with a preparation material which is the same as that of the first carrier transport layer 3 and are in conductive connection with the first carrier transport layer 3. N-1 cutting line grooves P3 are arranged on the top electrode layer 7, each cutting line groove P3 is located at the position 75-350 microns on the right side of the corresponding cutting line groove P1, and the bottom of each cutting line groove P3 is exposed out of the front electrode layer 2.
The isolation layers 8 are arranged on the side surfaces of the perovskite layer 4 on the two sides of the cutting line groove P3 respectively to shield the perovskite layer, and one side of the cutting line groove P3 is filled with the same preparation material as the top electrode layer 7 and is in conductive connection with the top electrode layer 7. The perovskite photovoltaic cell is divided into n perovskite photovoltaic sub-cells 9 under the combined action of n-1 cutting line grooves P1 and cutting line grooves P3. An isolating layer 8 is arranged on one side of each cutting line groove P3, which is far away from the corresponding cutting line groove P1, so as to shield one side surface of the perovskite layer 4, and another isolating layer 8 is arranged on the other side surface of the perovskite layer 4 so as to shield the perovskite layer. The other side of the cutting line groove P3 is filled with the same preparation material as the top electrode layer 7 and is in conductive connection with the top electrode layer 7, and the other isolating layer 8 is positioned between the perovskite layer 4 and the preparation material of the top electrode layer 7 filled in the cutting line groove P3.
The preparation material of the isolation layer 8 comprises any one of organic polymethyl methacrylate, polyvinyl butyral resin, ethylene methacrylic acid copolymer, polyethylene naphthalate, polyethylene terephthalate, tetrafluoroethylene copolymer, polyvinylidene chloride, polyvinylidene fluoride and polyamide, or comprises inorganic magnesium oxide, aluminum oxide, silicon oxide, zinc sulfide, zirconium acetylacetonate and C3N4Any one of boron nitride, a carbon material and a derivative thereof. The thickness of the isolation layer 8 exceeds the thickness of the perovskite layer 4, the thickness of the isolation layer is 400nm to 1000nm, and the width of the isolation layer is 50 μm to 200 μm. The isolation layer 8 is prepared by evaporation, spraying, screen printing, magnetron sputtering and dispensingAnd any one of coating and atomic layer deposition processing modes.
The perovskite layer 4 is prepared from an ABX3A halide crystal of the structure wherein A is a compound comprising methylamino (CH)3NH3 +) Formamidino (CH (NH)2)2 +) Cesium (Cs)+) At least one of monovalent cations, B is a cation including lead ion (Pb)2 +) Stannous ion (Sn)2+) At least one of divalent cations, X is Cl-、Br-、I-At least one halide anion.
Adding ion dopant comprising organic amine cation guanidino cation (C (NH) into the preparation material of perovskite layer 42)3 +) Butylamine radical Cation (CH)3(CH2)3NH3 +) Phenylethylamine cation (C)6H5(CH2)2NH3 +) Or comprises at least one of the cations of inorganic elements lithium, sodium, potassium, rubidium, boron, silicon, germanium, arsenic, antimony, beryllium, magnesium, calcium, strontium, barium, aluminum, indium, gallium, tin, thallium, lead, bismuth, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, or further comprises thiocyanate (SCN)-) Acetate ion (CH)3COO-) At least one kind of anion.
The width of the cutting line groove P1 is 25-200 μm, the width of the cutting line groove P3 is 15-300 μm, and the distance between the cutting line groove P1 and the nearest isolation layer 8 is 25-100 μm.
Example 2
Referring to fig. 2, an internal structure of a second preferred embodiment of the perovskite photovoltaic cell of the present invention sequentially includes, from bottom to top, a substrate 1, a front electrode layer 2, a first carrier transport layer 3, a perovskite layer 4, a second carrier transport layer 5, a barrier layer 6, and a top electrode layer 7.
N-1 cutting line grooves P1 are provided on the first carrier transport layer 3, and the cutting line grooves P1 simultaneously scribe the first carrier transport layer 3 and the front electrode layer 2. The cutting line groove P1 is filled with the same preparation material as the perovskite layer 4 and is electrically connected to the perovskite layer 4. N-1 cutting line grooves P3 are arranged on the top electrode layer 7, each cutting line groove P3 is located at the position 75-350 microns on the left side of the corresponding cutting line groove P1, and the bottom of each cutting line groove P3 is exposed out of the front electrode layer 2.
The isolation layers 8 are arranged on the side surfaces of the perovskite layer 4 on the two sides of the cutting line groove P3 respectively to shield the perovskite layer, and one side of the cutting line groove P3 is filled with the same preparation material as the top electrode layer 7 and is in conductive connection with the top electrode layer 7. The perovskite photovoltaic cell is divided into n perovskite photovoltaic sub-cells 9 under the combined action of n-1 cutting line grooves P1 and cutting line grooves P3. An isolating layer 8 is arranged on one side of each cutting line groove P3, which is far away from the corresponding cutting line groove P1, so as to shield one side surface of the perovskite layer 4, and another isolating layer 8 is arranged on the other side surface of the perovskite layer 4 so as to shield the perovskite layer. The other side of the cutting line groove P3 is filled with the same preparation material as the top electrode layer 7 and is in conductive connection with the top electrode layer 7, and the isolation layer 8 is located between the perovskite layer 4 and the preparation material of the top electrode layer 7 filled in the cutting line groove P3.
Other structures and features are the same as those of embodiment 1 and are not described again.
Example 3
Referring again to fig. 1, a first embodiment of a method for preparing a perovskite photovoltaic cell according to embodiment 1 of the present invention includes the steps of:
and step 11, scribing (laser cutting) the conductive glass substrate 1 deposited with the ITO front electrode layer 2, and etching to remove the ITO with the width of 100 microns to obtain a cutting line groove P1. And cleaning the conductive glass substrate 1, drying by using nitrogen, and carrying out ultraviolet ozone treatment.
The scribing method includes laser cutting, physical scribing and other processing methods, and the laser cutting method is adopted in the step. The same is as follows.
And step 12, covering a mask plate on the conductive substrate 1 processed in the step 11, wherein the hollow area of the mask plate corresponds to the position of the cutting line groove P3, the width of the hollow area of the mask plate is 150 micrometers, the width of the hollow area of the mask plate is greater than the width of the cutting line groove P3, and the hollow area of the mask plate is located at the position of 50 micrometers on the right side of the cutting line groove P1. Magnetron sputtering was used to deposit 500nm thick silicon oxide as the isolation regions. The thickness of the isolation region is not less than the sum of the thicknesses of the first carrier transport layer 3, the perovskite layer 4, the second carrier transport layer 5 and the barrier layer 6.
And step 13, preparing a first current carrier transmission layer 3, a perovskite layer 4, a second current carrier transmission layer 5 and a barrier layer 6 on the ITO front electrode layer 2 in sequence by using a mask plate opposite to the hollowed area in the step 12.
A 20nm hole-transporting material NiOx was sprayed as the first carrier-transporting layer 3 (hole-transporting layer) on the ITO front electrode layer 2. After drying, keeping the temperature of the substrate 1 at 70 ℃, spraying 0.7mol/L lead iodide solution, using N, N-dimethylformamide and dimethyl sulfoxide with the volume ratio of 9:1 as a mixed solvent, and annealing at 70 ℃ for 10min to prepare a 200nm thick lead iodide layer. A mixed isopropanol solution of formamidine hydroiodide and methylamine hydrochloride in a molar ratio of 10:1 was spin coated thereon. Wherein, the concentration of the formamidine hydroiodide is 60 mg/mL. Then annealed at 150 ℃ for 60 min. After cooling, tert-butyl alcohol is used for quickly dissolving and removing formamidine hydroiodide and methylamine hydrochloride which are remained on the surface, and annealing is carried out for 10min at 100 ℃ to prepare the perovskite layer 4. Then respectively spraying PC with the thickness of 30nm71BM, 5nm thick zirconium acetylacetonate as the second carrier transport layer 5 (electron transport layer) and the barrier layer 6.
And step 14, cutting the middle area of the isolation area by adopting a laser etching mode to obtain a cutting line groove P2 with the width of 100 microns. The left and right sides of the scribe line groove P2 are respectively retained with an isolation layer 8 having a width of 25 μm, and the bottom thereof is exposed from the front electrode layer 2.
And step 15, performing vacuum evaporation on the silver with the thickness of 150nm on the substrate 1 film processed in the step 14 to form a top electrode layer 7.
And step 16, cutting the area where the cutting line groove P2 is located by adopting a laser etching mode to obtain a cutting line groove P3, wherein the width of the cutting line groove P3 is 40 microns, and the bottom of the cutting line groove P3 is also exposed out of the front electrode layer 2. The width of the cutting line groove P3 is smaller than that of the cutting line groove P2, the top electrode layer 7 in the cutting line groove P3 is etched by laser, the preparation material of the top electrode layer 7 is reserved on one side (left side) of the cutting line groove P3 close to the cutting line groove P1, and the other side (right side) of the cutting line groove P3 is close to the isolation layer 8.
Example 4
Referring to fig. 3, a second embodiment of the method for manufacturing a perovskite photovoltaic cell according to embodiment 1 of the present invention includes the following steps:
and step 21, carrying out laser etching on the conductive glass substrate 1 deposited with the FTO front electrode layer 2, and etching to remove the FTO with the width of 150 microns to obtain a cutting line groove P1. And cleaning the conductive glass substrate 1, drying by using nitrogen, and carrying out ultraviolet ozone treatment.
22, depositing 30nm SnO on the substrate 1 film treated in the step 212As the first carrier transport layer 3 (electron transport layer).
And step 23, covering a mask plate on the conductive substrate 1 processed in the step 22, wherein the hollow area of the mask plate corresponds to the position of the cutting line groove P3, the width of the hollow area of the mask plate is 400 microns, the width of the hollow area of the mask plate is greater than the width of the cutting line groove P3, and the hollow area of the mask plate is located at the position of 10 microns on the right side of the cutting line groove P1. Magnetron sputtering was used to deposit 750nm thick silicon nitride as the isolation region. The thickness of the isolation region is not less than the sum of the thicknesses of the perovskite layer 4, the second carrier transport layer 5 and the barrier layer 6. And then evaporating hydrophobic material polystyrene with the thickness of 20nm on the surface of the isolation layer 8.
And 24, sequentially preparing the perovskite layer 4, the second carrier transmission layer 5 and the barrier layer 6 on the first carrier transmission layer 3.
Keeping the temperature of the substrate 1 at 100 ℃, and continuously coating the perovskite precursor solution Cs in a slit way0.15FA0.85PbI3Onto the first carrier transport layer 3, wherein the concentration of the solution is 1mol/L, and the solvent is 1, 4-butyrolactone and a small amount of N-methylpyrrolidone. Annealing at 100 deg.C for 30min to obtain 600nm thick perovskite layer 4. And dissolving chlorobenzene to remove polystyrene, so that the perovskite material on the surface of the polystyrene falls off, and then blowing the surface of the film clean by nitrogen.
Spraying Spiro-MeOTAD (doped bis (trifluoromethane sulfonyl)) with the thickness of 100nmLithium imide, t-butylpyridine) as the second carrier transport layer 5 (hole transport layer), and MoO was evaporated to a thickness of 20nm3As a barrier layer 6.
And 25, cutting the middle area of the isolation area by adopting a laser etching mode to obtain a cutting line groove P2 with the width of 200 mu m. The isolation layers 8 with a width of 100 μm are left on the left and right sides of the scribe line groove P2, respectively, and the front electrode layer 2 is exposed at the bottom thereof.
Step 26, depositing copper with a thickness of 150nm as the top electrode layer 7 on the thin film of the substrate 1 processed in step 25 by vacuum evaporation.
And 27, cutting the area where the cutting line groove P2 is located by adopting a laser etching mode to obtain a cutting line groove P3, wherein the width of the cutting line groove P3 is 100 microns, and the bottom of the cutting line groove P3 is also exposed out of the front electrode layer 2. The width of the cutting line groove P3 is smaller than that of the cutting line groove P2, the top electrode layer 7 in the cutting line groove P3 is etched by laser, the preparation material of the top electrode layer 7 is reserved on one side of the cutting line groove P3 close to the cutting line groove P1, and the other side of the cutting line groove P3 is close to the isolation layer 8.
Example 5
Referring again to fig. 2, a first embodiment of a method for manufacturing a perovskite photovoltaic cell according to embodiment 2 of the present invention includes the following steps:
and 31, cleaning the conductive flexible PEN substrate 1 deposited with the AZO front electrode layer 2, drying by blowing nitrogen, and carrying out ultraviolet ozone treatment. Polyvinylidene fluoride with the thickness of 550nm and the width of 300 mu m is deposited on the AZO conductive glass substrate 1 as an isolation region by a screen printing method, and the width of the adjacent isolation region is 10 mm. And the thickness of the isolation region is not less than the sum of the thicknesses of the first carrier transmission layer 3, the perovskite layer 4 and the second carrier transmission layer 5, and the width of the adjacent isolation region is greater than the width of the cutting line groove P3.
And step 32, coating 20 nm-thick PEDOT (PSS) on the film processed in the step 31 to serve as a first carrier transport layer 3 (hole transport layer), and carrying out laser etching on the first carrier transport layer 3 to obtain a cutting line groove P1, wherein the bottom of the cutting line groove P1 is exposed out of the substrate 1. The dicing line groove P1 is 20 μm on the right side of the isolation region and has a width of 50 μm.
And step 33, preparing the perovskite layer 4, the second carrier transport layer 5 and the barrier layer 6 on the first carrier transport layer 3 processed in the step 32 in sequence.
Adding 1.2mol/L MAPbI3And (3) coating a methylamine acetic acid solution on the surface of the first carrier transmission layer 3, and annealing at 100 ℃ for 10 minutes to obtain a 500nm perovskite layer. Then evaporating 30nm of C6020nm of chromium as the second carrier transport layer 5 (electron transport layer) and the barrier layer 6.
And step 34, cutting the middle area of the isolation area by adopting a laser etching mode to obtain a cutting line groove P2 with the width of 200 mu m. The left and right sides of the scribe line groove P2 are respectively retained with a 50 μm-wide isolation layer 8, the bottom of which is exposed from the front electrode layer 2.
And step 35, performing magnetron sputtering of ITO with the thickness of 100nm on the substrate film treated in the step 4 to serve as a top electrode layer 7.
And step 36, cutting the area where the cutting line groove P2 is located by adopting a laser etching mode to obtain a cutting line groove P3, wherein the width of the cutting line groove P3 is 100 microns, and the bottom of the cutting line groove P3 is also exposed out of the front electrode layer 2. The width of the cutting line groove P3 is smaller than that of the cutting line groove P2, the top electrode layer 7 in the cutting line groove P3 is etched by laser, the preparation material of the top electrode layer 7 is reserved on one side of the cutting line groove P3 close to the cutting line groove P1, and the other side of the cutting line groove P3 is close to the isolation layer 8.
Example 6
Referring to fig. 4, in a first embodiment of the method for manufacturing an optoelectronic device according to the present invention, an internal structure of the optoelectronic device includes a substrate 1, and a front electrode layer 2, a first carrier transport layer 3, a perovskite layer 4, a second carrier transport layer 5, and a top electrode layer 7 are sequentially included on the substrate 1 from bottom to top, including the following steps:
step S1, the front electrode layer 2 is scribed to obtain a first wire groove 10, and then the first carrier transmission layer 3 is prepared; an isolation region with the thickness not less than that of the perovskite layer 4 is prepared on one side of the first wire grooves 10 and at the position of the third wire grooves 12 by using a mask plate, and the width of the hollow region of the mask plate is greater than that of the third wire grooves 12.
Step S2, sequentially preparing a perovskite layer 4 and a second carrier transport layer 5 using a mask opposite to the hollowed-out region of step S1.
Step S3, performing laser cutting on the middle region of the isolation region to obtain a second wire groove 11, and reserving the isolation layer 8 on the left and right sides of the second wire groove 11 respectively.
Step S4, preparing the top electrode layer 7 on the film processed in step S3, performing laser cutting on the region where the second wire groove 11 is located to obtain a third wire groove 12, where the width of the third wire groove 12 is smaller than that of the second wire groove 11, and the top electrode layer 7 in the third wire groove 12 is etched away by the laser, so that the preparation material of the top electrode layer 7 is remained on one side of the third wire groove 12, and the other side is adjacent to the isolation layer 8.
The internal structure of the photoelectric component shown in the embodiment can be suitable for devices of light-emitting diodes, detectors, field-effect tubes and the like which relate to perovskite materials.
Example 7
Referring to fig. 5, in a second embodiment of the method for manufacturing an optoelectronic device according to the present invention, an internal structure of the optoelectronic device includes a substrate 1, and a front electrode layer 2, a first carrier transport layer 3, a perovskite layer 4, a second carrier transport layer 5, and a top electrode layer 7 are sequentially included on the substrate from bottom to top, and the method includes the following steps:
step S5, an isolation region is first prepared on the front electrode layer 2, the thickness of the isolation region is not less than the sum of the thicknesses of the first carrier transport layer 3, the perovskite layer 4 and the second carrier transport layer 5, and the width of the isolation region is greater than the width of the second wire slot 11. The first carrier transport layer 3 is prepared in a region other than the isolation region. And simultaneously carrying out laser etching on the first carrier transmission layer 3 and the front electrode layer 2 to obtain a first wire groove 10.
Step S6 is to sequentially prepare the perovskite layer 4 and the second carrier transport layer 5 on the first carrier transport layer 3.
Step S7, performing laser cutting on the middle region of the isolation region to obtain a second wire groove 11, and reserving the isolation layer 8 on the left and right sides of the second wire groove 11 respectively.
Step S8, preparing the top electrode layer 7 on the film processed in step S7, performing laser cutting on the region where the second wire groove 11 is located to obtain a third wire groove 12, where the width of the third wire groove 12 is smaller than that of the second wire groove 11, and the top electrode layer 7 in the third wire groove 12 is etched away by the laser, so that the preparation material of the top electrode layer 7 is remained on one side of the third wire groove 12, and the other side is adjacent to the isolation layer 8.
Other structures and features are the same as those of embodiment 6 and are not described again.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A perovskite photovoltaic cell is characterized in that n-1 cutting wire grooves P1 are formed in the front electrode layer, the cutting wire grooves P1 cut the front electrode layer, the cutting wire grooves P1 are filled with a preparation material which is the same as that of the first carrier transmission layer and are in conductive connection with the first carrier transmission layer, n-1 cutting wire grooves P3 are formed in the top electrode layer, each cutting wire groove P3 is located on one side of the corresponding cutting wire groove P1, the front electrode layer is exposed at the bottom of each cutting wire groove P3, isolation layers are arranged on the side faces of the perovskite layers on the two sides of each cutting wire groove P3 to shield the perovskite layer, a preparation material which is the same as that of the top electrode layer is filled on one side of each cutting wire groove P3 and is in conductive connection with the top electrode layer, the perovskite photovoltaic cell is divided into n perovskite photovoltaic sub-cells under the combined action of n-1 cutting line grooves P1 and cutting line grooves P3.
2. A perovskite photovoltaic cell is characterized in that n-1 cutting wire grooves P1 are formed in the first carrier transmission layer, the cutting wire grooves P1 are used for simultaneously cutting off the front electrode layer and the first carrier transmission layer, the cutting wire grooves P1 are filled with a preparation material the same as that of the perovskite layer and are in conductive connection with the perovskite layer, n-1 cutting wire grooves P3 are formed in the top electrode layer, each cutting wire groove P3 is located on one side of the corresponding cutting wire groove P1, the bottom of each cutting wire groove P3 is exposed out of the front electrode layer, isolation layers are respectively arranged on the side faces of the perovskite layer on the two sides of each cutting wire groove P3 to shield the perovskite layer, one side of each cutting wire groove P3 is filled with a preparation material the same as that of the top electrode layer and is in conductive connection with the top electrode layer, the perovskite photovoltaic cell is divided into n perovskite photovoltaic sub-cells under the combined action of n-1 cutting line grooves P1 and cutting line grooves P3.
3. The perovskite photovoltaic cell of claim 1 or 2, wherein the separator layer preparation material comprises any one of polymethylmethacrylate, polyvinylbutyral resin, ethylene methacrylic acid copolymer, polyethylene naphthalate, polyethylene terephthalate, tetrafluoroethylene copolymer, polyvinylidene chloride, polyvinylidene fluoride, polyamide organyl, or comprises magnesium oxide, aluminum oxide, silicon oxide, zinc sulfide, zirconium acetylacetonate, C3N4Boron nitride, a carbon material, or a derivative inorganic substance thereof, wherein the thickness of the isolation layer exceeds the thickness of the perovskite layer.
4. The perovskite photovoltaic cell of claim 1 or 2, wherein the perovskite layer is prepared from a material having an ABX3Halide crystal of type structure, wherein A is at least one of methylamino, amidino and cesium monocations, B is at least one of divalent cations including lead ion and stannous ion, and X is Cl-、Br-、I-At least one halide anion.
5. The perovskite photovoltaic cell of claim 4, wherein an ionic dopant is added to the perovskite layer preparation material, the ionic dopant being at least one of organic amine cations including guanidinium cations, butylamine cations, phenethylamine cations, or lithium, sodium, potassium, rubidium, boron, silicon, germanium, arsenic, antimony, beryllium, magnesium, calcium, strontium, barium, aluminum, indium, gallium, tin, thallium, lead, bismuth, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold inorganic elements, or further including at least one of thiocyanate, acetate ion anions.
6. A method of making the perovskite photovoltaic cell of claim 1, comprising the steps of:
step one, scribing a front electrode layer prepared on a substrate to obtain a cutting line groove P1;
secondly, preparing an isolation region with the thickness not less than the sum of the thicknesses of the first carrier transmission layer and the perovskite layer at one side of the cutting line groove P1 and the position of the cutting line groove P3 by using a mask plate, wherein the width of the hollow region of the mask plate is greater than the width of the cutting line groove P3;
step three, sequentially preparing a first current carrier transmission layer, a perovskite layer and a second current carrier transmission layer by using a mask plate opposite to the hollow area in the step two;
scribing the middle area of the isolation area to obtain a cutting line groove P2, wherein isolation layers are reserved on the left side and the right side of the cutting line groove P2 respectively, and the bottom of the isolation layer is exposed out of the front electrode layer;
step five, preparing a top electrode layer on the substrate film processed in the step four;
step six, scribing the area where the cutting line groove P2 is located to obtain a cutting line groove P3, wherein the bottom of the cutting line groove P3 is exposed out of the front electrode layer, the width of the cutting line groove P3 is smaller than that of the cutting line groove P2, a preparation material of a top electrode layer is reserved on one side, close to the cutting line groove P1, of the cutting line groove P3, and the other side of the cutting line groove P3 is close to the isolation layer.
7. A method of making the perovskite photovoltaic cell of claim 1, comprising the steps of:
step I, scribing the front electrode layer prepared on the substrate to obtain a cutting line groove P1;
step II, preparing a first carrier transmission layer on the substrate film processed in the step I;
step III, preparing an isolation region with the thickness not smaller than that of the perovskite layer at one side of the cutting line groove P1 and at the position of the cutting line groove P3 by using a mask plate, wherein the width of the hollow region of the mask plate is larger than that of the cutting line groove P3;
step IV, sequentially preparing a perovskite layer and a second carrier transmission layer by using a mask plate opposite to the hollow area in the step III;
step V, etching the middle area of the cutting isolation area to obtain a cutting line groove P2, wherein isolation layers are reserved on the left side and the right side of the cutting line groove P2 respectively, and the bottom of the isolation layer is exposed out of the front electrode layer;
step VI, preparing a top electrode layer on the substrate film treated in the step V;
and step VII, scribing the region where the cutting line groove P2 is located to obtain a cutting line groove P3, wherein the bottom of the cutting line groove P3 is exposed out of the front electrode layer, the width of the cutting line groove P3 is smaller than that of the cutting line groove P2, a preparation material of a top electrode layer is reserved on one side, close to the cutting line groove P1, of the cutting line groove P3, and the other side of the cutting line groove P3 is close to the isolation layer.
8. A method of producing the perovskite photovoltaic cell as defined in claim 2, comprising the steps of:
step 1, preparing an isolation region with the thickness not less than the sum of the thicknesses of a first carrier transmission layer and a perovskite layer at the position of a cutting line groove P3 by using a mask plate or a silk screen on a front electrode layer prepared on a substrate, wherein the width of a hollow region of the mask plate is greater than the width of the cutting line groove P3;
step 2, preparing a first carrier transmission layer on the film processed in the step 1, simultaneously scribing the first carrier transmission layer and the front electrode layer to obtain a cutting line groove P1, wherein the bottom of the cutting line groove P1 is exposed out of the substrate;
step 3, sequentially preparing a perovskite layer and a second carrier transmission layer on the first carrier transmission layer processed in the step 2;
step 4, etching the middle area of the cutting isolation area to obtain a cutting line groove P2, wherein isolation layers are respectively reserved on the left side and the right side of the cutting line groove P2, and the bottom of the isolation layer is exposed out of the front electrode layer;
step 5, preparing a top electrode layer on the substrate film treated in the step 4;
step 6, scribing the region where the cutting line groove P2 is located to obtain a cutting line groove P3, wherein the bottom of the cutting line groove P3 is exposed out of the front electrode layer, the width of the cutting line groove P3 is smaller than that of the cutting line groove P2, a preparation material of a top electrode layer is reserved on one side, close to the cutting line groove P1, of the cutting line groove P3, and the other side of the cutting line groove P3 is close to the isolation layer.
9. The preparation method of the photoelectric component is characterized by comprising the following steps of: step S1, etching the front electrode layer to obtain a first wire groove, and then preparing a first carrier transmission layer; preparing an isolation region with the thickness not less than the thickness of the perovskite layer at one side of the first wire groove and at the position of the third wire groove by using a mask plate, wherein the width of the hollow region of the mask plate is greater than that of the third wire groove;
step S2, sequentially preparing a perovskite layer and a second carrier transmission layer by using a mask plate opposite to the hollowed-out region of the step S1;
step S3, etching the middle area of the isolation area to obtain a second wire groove, and reserving isolation layers on the left side and the right side of the second wire groove respectively;
and S4, preparing a top electrode layer on the film processed in the step S3, scribing the area where the second wire groove is located to obtain a third wire groove, wherein the width of the third wire groove is smaller than that of the second wire groove, the preparation material of the top electrode layer is reserved on one side of the third wire groove, and the other side of the third wire groove is close to the isolation layer.
10. The preparation method of the photoelectric component is characterized by comprising the following steps of:
step S5, firstly, preparing an isolation region on the front electrode layer, wherein the thickness of the isolation region is not less than the sum of the thicknesses of the first carrier transmission layer and the perovskite layer, and the width of the isolation region is greater than the width of the second wire slot; preparing a first carrier transport layer in a region outside the isolation region; simultaneously etching the first carrier transmission layer and the front electrode layer to obtain a first wire groove;
step S6, sequentially preparing a perovskite layer and a second carrier transmission layer on the first carrier transmission layer;
step S7, etching the middle area of the isolation area to obtain a second wire groove, and reserving isolation layers on the left side and the right side of the second wire groove respectively;
and S8, preparing a top electrode layer on the film processed in the step S7, scribing the area where the second wire groove is located to obtain a third wire groove, wherein the width of the third wire groove is smaller than that of the second wire groove, the preparation material of the top electrode layer is reserved on one side of the third wire groove, and the other side of the third wire groove is close to the isolation layer.
CN202010558361.3A 2020-05-13 2020-06-18 Perovskite photovoltaic cell, preparation method thereof and preparation method of photoelectric component Pending CN111668375A (en)

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