CN212695178U

CN212695178U - Perovskite photovoltaic cell

Info

Publication number: CN212695178U
Application number: CN202020787883.6U
Authority: CN
Inventors: 不公告发明人
Original assignee: Hangzhou Microquanta Semiconductor Corp ltd
Current assignee: Hangzhou Microquanta Semiconductor Corp ltd
Priority date: 2020-05-13
Filing date: 2020-05-13
Publication date: 2021-03-12
Anticipated expiration: 2030-05-13

Abstract

The utility model relates to a perovskite photovoltaic cell, which comprises a substrate, the front electrode layer, first carrier transmission layer, the perovskite layer, second carrier transmission layer, the top electrode layer, be provided with cutting wire casing P1 on the front electrode layer, cutting wire casing P1 is drawn absolutely with the front electrode layer, it is full of the preparation material the same with first carrier transmission layer to fill in cutting wire casing P1, be provided with cutting wire casing P3 on the top electrode layer, its bottom exposes the front electrode layer, the side on the perovskite layer of cutting wire casing P3 both sides is equipped with the isolation layer respectively and shields it, it has the preparation material the same with the top electrode layer and is connected with top electrode layer electrically conductive to fill in one side of cutting wire casing P3. The utility model discloses prepare the isolation layer in advance, protect the perovskite layer of follow-up preparation, effectively avoided because of the perovskite film side exposes the problem that leads to the perovskite material degradation, electrode conductivity descends.

Description

Perovskite photovoltaic cell

Technical Field

The utility model belongs to the technical field of the perovskite photovoltaic cell preparation, in particular to perovskite photovoltaic cell.

Background

Perovskites are a class with ABX₃The general term crystalline material of structure. The research finds thatThe halogenated perovskite materials have excellent semiconductor characteristics, can realize the interconversion of high-quality light energy and electric energy, and 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.

SUMMERY OF THE UTILITY MODEL

The utility model aims to solve the technical problem that a new large tracts of land perovskite photovoltaic cell is provided, prepares isolation layer refabrication perovskite layer earlier, combines to do many times in isolation layer region and keep apart the processing to preparation perovskite series module. 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 utility model is realized like this, a perovskite photovoltaic cell is provided, its inner structure includes the basement from bottom to top in proper order, the front electrode layer, first carrier transmission layer, the perovskite layer, the second carrier transmission layer, the top electrode layer, be provided with n-1 cutting wire casing P1 on the front electrode layer, cutting wire casing P1 cuts off the front electrode layer, fill in cutting wire casing P1 with the same preparation material as first carrier transmission layer and be connected with first carrier transmission layer electrically conductive, be provided with n-1 cutting wire casing P3 on the top electrode layer, every cutting wire casing P3 is located corresponding cutting wire casing P1 one side, the bottom of cutting wire casing P3 exposes the front electrode layer, the side of the perovskite layer of cutting wire casing P3 both sides is equipped with the isolation layer respectively and shields it, it is filled with the same preparation material as top electrode layer and is connected with top electrode layer electrically conductive in one side of cutting wire casing P3, 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 utility model is realized like this, a perovskite photovoltaic cell is provided, its inner structure includes the basement from bottom to top in proper order, the front electrode layer, first carrier transmission layer, the perovskite layer, the second carrier transmission layer, the top electrode layer, be provided with n-1 cutting wire casing P1 on first carrier transmission layer, cutting wire casing P1 cuts off front electrode layer and first carrier transmission layer simultaneously, fill in the same preparation material of perovskite layer and be connected with the perovskite layer electrically conductive in cutting wire casing P1, be provided with n-1 cutting wire casing P3 on the top electrode layer, every cutting wire casing P3 is located corresponding cutting wire casing P1 one side, the bottom of cutting wire casing P3 exposes the front electrode layer, the side of the perovskite layer in cutting wire casing P3 both sides is equipped with the isolation layer respectively and shields it, it is filled with the same preparation material and is connected with the top electrode layer electrically conductive in one side of cutting wire casing P3, 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.

Further, the perovskite layer is prepared from a material having 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 packageIncluding Cl^-、Br^-、I^-At least one halide anion.

Further, an ionic dopant is added into the preparation material of the perovskite layer, wherein the ionic dopant is at least one of organic amine cations including guanidinium cations, butylamine cations and phenethylamine cations, or at least one of cations including 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 and gold inorganic elements, or at least one of thiocyanate and acetate ion anions is included.

Compared with the prior art, the utility model discloses a perovskite photovoltaic cell has 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 the perovskite photovoltaic cell according to embodiments 1 and 3 of the present invention;

fig. 2 is a schematic plan view of the internal structure of the perovskite photovoltaic cell according to embodiments 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 embodiment 4 of the present invention.

Detailed Description

In order to make the technical problem, technical solution and advantageous effects to be solved by the present invention more clearly understood, the following description is given in conjunction with the accompanying drawings and embodiments to illustrate the present invention in further detail. 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, the perovskite photovoltaic cell according to the first preferred embodiment of the present invention includes 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 from bottom to top in sequence.

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 that of the perovskite layer 4, the thickness of the film is 400 nm-1000 nm, and the width of the film is wideThe degree is 50 μm to 200 μm. The preparation method of the isolation layer 8 adopts any one of the processing modes of evaporation plating, spraying, screen printing, magnetron sputtering, dispensing coating and atomic layer deposition.

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, the perovskite photovoltaic cell according to the second preferred embodiment of the present invention includes 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 from bottom to top in sequence.

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 the method for manufacturing a perovskite photovoltaic cell according to embodiment 1 of the present invention includes the following steps:

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 way_0.15FA_0.85PbI₃Onto 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. Dissolving in chlorobenzene to remove polystyrene, stripping off perovskite material on its surface, and adding nitrogenAnd (5) blowing the surface of the film clean.

Spraying 100nm thick Spiro-MeOTAD (doped lithium bistrifluoromethanesulfonimide, tert-butylpyridine) as a second carrier transport layer 5 (hole transport layer), and evaporating to form 20nm thick MoO₃As 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.

The above description is only exemplary of the present invention and should not be taken as limiting the scope of the present invention, as any modifications, equivalents, improvements and the like made within the spirit and principles of the present invention are intended to be included within the scope of the present invention.

Claims

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 perovskite layer is prepared from a material having an ABX₃A halide crystal of type structure.