CN106784323A - A kind of large area perovskite solar cell composite photoelectric conversion layer and preparation method thereof - Google Patents
A kind of large area perovskite solar cell composite photoelectric conversion layer and preparation method thereof Download PDFInfo
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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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Abstract
Perovskite solar cell composite photoelectric conversion layer constituted the present invention relates to a kind of three-dimensional Ca-Ti ore type photoelectric conversion material film and polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material film and preparation method thereof.Polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material film composition is NMX in the present invention4, wherein, N is cyanuric acid, melamine, trithiocyanuric acid, tripolyphosphate ammonium, the phosphonitrile of amino ring three or its mixture；M is Pb2+、Sn2+、Ge2+、Cu2+、Ni2+、Mn2+、Zn2+、Fe2+Or its mixture；X is Cl‑、Br‑、I‑Or its mixture.The present invention, simultaneously as perovskite solar cell composite photoelectric conversion layer and hole transport layer material, simplifies large area perovskite solar cell preparation technology using polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material, can stabilize and increase photoelectric transformation efficiency.
Description
Technical field
The present invention relates to a kind of perovskite solar cell composite photoelectric conversion layer containing polymerizable groups and its preparation side
Method, belongs to new energy and field of new.
Technical background
More than 28%, future is expected to reach 50% the current photoelectric transformation efficiency of perovskite solar cell, as solar cell
The new hope of industry.Perovskite solar cell is typically by transparent conducting glass, compacted zone, perovskite photoelectric conversion layer, hole
Transport layer, the part of metal back electrode five composition.The thickness of perovskite photoelectric conversion layer is generally 200-600nm, and Main Function is
Absorb sunshine and produce electron-hole pair, and can high efficiency of transmission electron-hole pair.Perovskite photoelectric conversion material typical case point
Minor is AMX3, wherein, A represents monovalent cation, usually CH3NH3 +、HNCHNH3 +Or Cs+；M represents metal cation,
Usually Pb2+、Sn2+、Ge2+、Cu2+、Ni2+、Mn2+、Sb3+、Bi3+；X represents anion, usually Cl-、Br-、I-、CNS-Or
PF6 -。
Research at present both at home and abroad to metal cation and halide anion is more thorough, and to the group of monovalent cation
Into, structurally and functionally mechanism research just it is at the early-stage.The open uses of Chinese patent CN104993058 (2015-10-12) carries
The polymer of primary amine groups builds new perovskite photoelectric conversion material as monovalent cation.Chinese patent application
2016109969221 (2016-11-14) and 2016109969522 (2016-11-14) are open to use aromatic hydroxy group ammonia and two
Acid imide improves perovskite photoelectric conversion material performance.If monovalent cation molecular proportion is larger or diamine structures molecule, three
The high symmetry for tieing up perovskite crystal structure is easy for being destroyed, and forms two-dimensional layer Ca-Ti ore type photoelectric conversion material, allusion quotation
Type molecular formula is NMX4.Although research finds the opto-electronic conversion performance of two-dimensional layer Ca-Ti ore type photoelectric conversion material not as good as conventional
Three-dimensional Ca-Ti ore type photoelectric conversion material, but with more preferable environmental stability, electric conductivity and good hole separate with
Transmission performance.Research finds should by three-dimensional Ca-Ti ore type photoelectric conversion material and two-dimentional Ca-Ti ore type photoelectric conversion material mixing
With, perovskite solar cell photoelectric conversion layer performance can be stabilized and increased, representative patents include CN104795501 (2015-
07-22) 、CN104795501(2015-07-22) 、CN105742504(2016-07-06) 、CN106098943(2016-
11-09) with CN2016109969221 (2016-11-14).
Monovalent cation kind is also fewer in current Ca-Ti ore type photoelectric conversion material, perovskite photoelectric conversion material into
Film properties are bad, are not met by the engineering coating of large area perovskite solar cell photoelectric conversion layer and require.Design new calcium
Different types of Ca-Ti ore type photoelectric conversion material combination application is to speed up calcium titanium by titanium ore photoelectric conversion material molecule or research
The important measures of ore deposit solar cell application and development.
The content of the invention
It is an object of the invention to provide a kind of large area perovskite solar cell composite photoelectric conversion layer, especially with three
Dimension Ca-Ti ore type photoelectric conversion material film and polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material film composition perovskite
Solar cell composite photoelectric conversion layer, and with polymerizable two-dimensional layer Ca-Ti ore type photoelectricity conversion thin film as hole transmission layer,
To simplify large area perovskite solar cell preparation technology.
Three-dimensional Ca-Ti ore type photoelectric conversion material film composition is AMX in the present invention3, wherein, A is CH3NH3 +、CH
(NH2)2 +、Cs+Or its mixture；M is Pb2+、Sn2+、Ge2+、Cu2+、Ni2+、Mn2+、Sb3+、Bi3+Or its mixture；X is Cl-、
Br-、I- 、CNS-、BF4 -、PF6 -Or its mixture.
Polymerizable two-dimentional Ca-Ti ore type photoelectric conversion material film composition is NMX in the present invention4, wherein, N is polymerizable
Compound, including cyanuric acid, melamine, trithiocyanuric acid, tripolyphosphate ammonium, the phosphonitrile of amino ring three or its mixture；M is
Pb2+、Sn2+、Ge2+、Cu2+、Ni2+、Mn2+、Zn2+、Fe2+Or its mixture；X is Cl-、Br-、I-Or its mixture.
Three-dimensional Ca-Ti ore type photoelectric conversion material film is AMX by constituting in the present invention3Perovskite photoelectric conversion material
It is dissolved in dimethylformamide, gamma-butyrolacton, HMPA or dimethyl sulfoxide (DMSO) polar organic solvent, then applies
Cloth is formed on photoelectric conversion layer skeleton after heating, and thickness is 100-500nm.
Polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material film is NMX by constituting in the present invention4Perovskite light
Electric transition material is dissolved in dimethylformamide, gamma-butyrolacton, HMPA or dimethyl sulfoxide (DMSO) polar organic solvent
In, then it is coated on three-dimensional Ca-Ti ore type photoelectric conversion material film, formed after heating, thickness is 50-200nm.
Polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material film and three-dimensional Ca-Ti ore type opto-electronic conversion in the present invention
The thickness ratio of material film is 1：2-10, exists between element in two layers of Ca-Ti ore type photoelectric conversion material and is exchanged with each other, spreads
And infiltration, the transition zone of complexity is formed in the contact area of two layers of perovskite photoelectric conversion material film, transition region thickness is 25-
100nm。
Three-dimensional Ca-Ti ore type photoelectric conversion material film is used as opto-electronic conversion layer main body, the tribute to opto-electronic conversion in the present invention
Rate is offered for 50%-70%, polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material film is used to make up three-dimensional Ca-Ti ore type photoelectricity
Deficiency of the transition material film in terms of uniformity, opto-electronic conversion scope and environmental stability, while as hole transmission layer, it is right
The contribution rate of opto-electronic conversion is 30%-50%.
Polymerizable compound cyanuric acid, melamine, trithiocyanuric acid, tripolyphosphate ammonium and the ammonia used in the present invention
Functional group containing three amino or active nitrogen in the molecule of the phosphonitrile of basic ring three, the presence of unshared electron pair, makes in nitrogen-atoms
It easily combines to form chemical composition for NMX with halogen acids and metal halide3Or NMX4Ca-Ti ore type photoelectric conversion material.
In polymerizable compound not with the complex bound active group of metal halide under the conditions of heating and metallic halid catalyst
Easy autohemagglutination or copolymerization form the more stable polymer molecule containing amino active group, but do not destroy nitrogen-atoms and metal halide
The coordination structure of thing.The amido polymer that reaction in-situ is produced changes the performance of Ca-Ti ore type photoelectric conversion material, makes it
Anti-oxidant, water resistant gas, ultraviolet light and the aging performance of resisting temperature are greatly improved.Contain multiple nitrogen, sulphur in polymerizable compound
Or P elements hetero atom, photosensitive polymer and conducting polymer can be formed, so as to extend the absorbing wavelength scope and work of sunshine
It is excellent hole transport layer material.
Cyanuric acid is the cyclic trimer of cyanic acid (HOCN) in the present invention, also known as " cyanuric acid ", belongs to triazines, by urinating
Element is polymerized and obtains.It has multiple dynamic isomers, triphenol form and triketone form, mainly exists in triketone form.In molecule
Three secondary amines can be with halogen acids and metal halide with mol ratio 1:1、1:2 or 1:3 combine to form ligand.Not with metal
Easily dehydration autohemagglutination is formed under the conditions of heating and metallic halid catalyst for the complex bound secondary amine of halide and active group
The more stable bicyclic or polycyclic polymers molecule containing secondary amine, but the coordination structure of nitrogen-atoms and metal halide is not destroyed,
So as to form New Two Dimensional laminated perovskite type photoelectric conversion material.
Melamine is commonly called as melamine or extract of protein in the present invention, is a kind of triazines nitrogen heterocyclic ring organic compound, by urinating
Element is produced for raw material.Three amino in molecule can be with halogen acids and metal halide with mol ratio 1:1、1:2 or 1:3 combine
Form ligand.Not with the complex bound amino of metal halide and active group under the conditions of heating and metallic halid catalyst
Easy deamination autohemagglutination forms the more stable bicyclic or polycyclic polymers molecule containing amino, but does not destroy nitrogen-atoms and metal halide
The coordination structure of thing, so as to form New Two Dimensional laminated perovskite type photoelectric conversion material.
Trithiocyanuric acid alias TTCA or tri-thiol s-triazine, have similitude with cyanuric acid in the present invention
The matter chemical reaction similar with carrying out.Three secondary amines in molecule can be with halogen acids and metal halide with mol ratio 1:1、1:
2 or 1:3 combine to form ligand.Not with the complex bound secondary amine of metal halide and active group in heating and metal halide
Easily dehydration autohemagglutination forms the more stable bicyclic or polycyclic polymers molecule containing secondary amine under thing catalytic condition, but does not destroy nitrogen
The coordination structure of atom and metal halide, so as to form New Two Dimensional laminated perovskite type photoelectric conversion material.
Tripolyphosphate ammonium is produced by phosphoric acid-urea thermal polymerization in the present invention, in molecule three amino can with halogen acids and
Metal halide is with mol ratio 1:1、1:2 or 1:3 combine to form ligand.Not with the complex bound amino of metal halide and work
Property group under the conditions of heating and metallic halid catalyst easily dehydration autohemagglutination form the more stable long-chain polymer containing amino
Molecule, but the coordination structure of nitrogen-atoms and metal halide is not destroyed, so as to form New Two Dimensional laminated perovskite type photoelectricity turn
Conversion materials.
The phosphonitrile of amino ring three is prepared by hexachlorocyclotriph,sphazene ammonification in the present invention, and the degree with ammonification is different, molecule
In contain 2-6 amino, can be with halogen acids and metal halide with mol ratio 1:1、1:2 or 1:3 combine to form ligand.Not with
The complex bound amino of metal halide and active group under the conditions of heating and metallic halid catalyst easy deamination from combinate form
Into the more stable long chain polymer molecules containing amino, but the coordination structure of nitrogen-atoms and metal halide is not destroyed, so that shape
Into New Two Dimensional laminated perovskite type photoelectric conversion material.
Polymerizable compound cyanuric acid, melamine, trithiocyanuric acid, tripolyphosphate ammonium and amino ring three in the present invention
Amino, secondary amino group, hydroxyl and sulfydryl in phosphonitrile molecule are easier copolymerization and form the more stable polymer containing amino, but do not break
The coordination structure of bad nitrogen-atoms and metal halide, so as to form various new two-dimensional layer Ca-Ti ore type photoelectric conversion material.
It is a further object of the present invention to provide a kind of preparation side of large area perovskite solar cell composite photoelectric conversion layer
Method, including the film preparation of three-dimensional Ca-Ti ore type photoelectric conversion material, polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material and
Film preparation, composite photoelectric conversion layer are prepared and evaluate three parts, and technical scheme is comprised the following steps：
（1）Three-dimensional Ca-Ti ore type photoelectric conversion material is dissolved in polar organic solvent, with biscuit ware funnel secondary filter,
The photoelectric conversion material solution of mass percentage concentration 10%-20% is formed, with bar spreader by photoelectric conversion material solution coating
On photoelectric conversion layer skeleton, it is the three-dimensional Ca-Ti ore type photoelectric conversion material knot of 100-500nm that thickness is formed after solvent volatilization
Brilliant film, the polar organic solvent be dimethylformamide, gamma-butyrolacton, dimethyl sulfoxide (DMSO), HMPA or its
Mixture；The photoelectric conversion layer skeleton is that coating thickness is 20- in the FTO Conducting Glass of 100mm × 100mm
The nano-TiO of 50nm2Compacted zone, it is 40-60nm to be then coated with particle diameter, and thickness is the TiO of 100-600nm2Film, finally exists
Sintering is formed at 450-550 DEG C；
（2）Polar organic solvent, halogen acids and metal halide are separately added into glass reactor, are stirred at 40-60 DEG C
To being completely dissolved, polymerizable compound is subsequently adding, controls the raw material molar ratio to be：Polymerizable compound：HX：MX2= 1：
2.0-2.1：0.95-1.05, continues stirring reaction 12-24 h, obtains polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material
Solution；Being concentrated in vacuo in solution has crystallization to separate out, and adds absolute ethyl alcohol to make the chemical composition dissolved in polar solvent be NMX4
Two-dimensional layer Ca-Ti ore type photoelectric conversion material be precipitated out, obtain essence after vacuum filter, absolute ethanol washing, vacuum drying
The NMX of system4Crystalline product, the polymerizable compound is cyanuric acid, melamine, trithiocyanuric acid, tripolyphosphate ammonium, ammonia
The phosphonitrile of basic ring three or its mixture；The metal halide is the halide of metallic element Pb, Sn, Ge, Cu, Ni, Mn, Zn, Fe
Or its mixture；
（3）Two-dimensional layer Ca-Ti ore type photoelectric conversion material crystallization made above is dissolved in polar organic solvent, with element
Ceramic funnel secondary filter is burnt, the perovskite photoelectric conversion material solution of mass percentage concentration 10%-20% is formed, is coated with bar
Device by perovskite photoelectric conversion material solution coating on three-dimensional Ca-Ti ore type photoelectric conversion material crystalline membrane, solvent volatilization after
It is the polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material crystalline membrane of 50-200nm to form thickness, and the polarity is organic
Solvent is dimethylformamide, gamma-butyrolacton, dimethyl sulfoxide (DMSO), HMPA or its mixture；
（4）Double Perovskite type photoelectric conversion material crystalline membrane made above is heated to 140-190 under vacuum
DEG C, and 0.5-2h is incubated, element is exchanged with each other, spreads and permeates in making two layers of Ca-Ti ore type photoelectric conversion material, in two layers of calcium
Titanium ore photoelectric conversion material thin film contact area forms two kinds of mixed transition layers of titanium ore photoelectric conversion material；Polymerizable compound
In autohemagglutination or copolymerization do not form more stable polymer in a heated condition with the complex bound active group of metal halide
Molecule；Simultaneously remove the solvent volatilization carried secretly in perovskite photoelectricity conversion thin film, so as to form surface smooth and stable performance
Black perovskite composite photoelectric conversion layer；
（5）Perovskite composite photoelectric conversion layer and substrate conduction glass made above are cut into the rectangle of 100mm × 10mm,
Without being coated with hole transmission layer, directly the applying conductive elargol film on composite photoelectric conversion layer, dries solid at 150-200 DEG C
Change, surface square resistance is 0.5-2 Ω, is 14%-15% with its perovskite photoelectric conversion efficiency of the solar battery for assembling, and interior is put
The photoelectric transformation efficiency for putting perovskite solar cell after January has no decline.
Three-dimensional Ca-Ti ore type photoelectric conversion material preparation method refers to Chinese invention patent application in the present invention
2016111009189(2016-12-05)、2016110991635(2016-12-04)、2016110837492(2016-11-30)
Middle method；Efficiency of solar cell is using the small-sized solar module tester simulated solar optical tests for customizing.
Beneficial effects of the present invention are embodied in：
（1）The present invention is changed using polymerizable two-dimentional Ca-Ti ore type photoelectric conversion material as perovskite solar cell composite photoelectric
Layer component and hole transmission layer, simplify large area perovskite solar cell preparation technology；
（2）The present invention uses perovskite solar cell composite photoelectric conversion layer, improves perovskite solar cell photoelectric conversion layer
Into film uniformity, environmental stability and sun light absorption wavelength scope, photoelectric transformation efficiency can be stabilized and increased.
Specific embodiment
Embodiment 1
Coating thickness is the nano-TiO of 20-50nm in the FTO Conducting Glass of 100mm × 100mm2Compacted zone, then
Coating particle diameter is 40-60nm, and thickness is the TiO of 100-600nm2Film, finally sintering forms opto-electronic conversion at 450-550 DEG C
Layer casing play.Weigh CH3NH3PbI3Ca-Ti ore type photoelectric conversion material 5g, is dissolved in dimethyl formyls of the 30g by dewater treatment
In amine solvent, stirring, with biscuit ware funnel secondary filter, forms mass percentage concentration 14.3% in 12 hours to whole dissolvings
Photoelectric conversion material solution, with stainless steel wire rod coating device by photoelectric conversion material solution coating on photoelectric conversion layer skeleton,
It is the iodate methylamine lead CH of 300nm that thickness is formed after solvent volatilization3NH3PbI3Photoelectric conversion material crystalline membrane.
Dimethylformamide 300g, the hydroiodic acid 63.7g of mass percentage concentration 50% are separately added into glass reactor
(0.21mol) and cupric iodide 31.7g (0.1mol), stirs at 40-60 DEG C to being completely dissolved, and is subsequently adding melamine
13.2g (0.105mol), continues the h of stirring reaction 12, obtains iodate melamine copper (NH2)3C3N3H2CuI4Solution；Vacuum
Being concentrated into solution has crystallization to separate out, and adds absolute ethyl alcohol to make the iodate melamine copper (NH dissolved in polar solvent2)3C3N3H2CuI4It is precipitated out, refined iodate melamine copper is obtained after vacuum filter, absolute ethanol washing, vacuum drying
(NH2)3C3N3H2CuI4Crystallization 67.8g, yield is 98%.By iodate melamine copper (NH made above2)3C3N3H2CuI4Knot
Brilliant 5g, in being dissolved in 30g by the solvent dimethylformamide of dewater treatment, with biscuit ware funnel secondary filter, is applied with bar
Cloth device will be coated on iodate methylamine lead CH3NH3PbI3Forming thickness on photoelectric conversion material crystalline membrane, after solvent volatilization is
The iodate melamine copper (NH of 150nm2)3C3N3H2CuI4Photoelectric conversion material crystalline membrane.
By iodate methylamine lead CH made above3NH3PbI3With iodate melamine copper (NH2)3C3N3H2CuI4Double-deck calcium
Titanium ore photoelectric conversion material crystalline membrane is heated to 180 DEG C under vacuum, and is incubated 1h, makes two layers of titanium ore opto-electronic conversion material
Material thin film contact area forms two kinds of transition zones of titanium ore photoelectric conversion material, while the methylamine carried secretly in making photoelectricity conversion thin film
With melamine raw material and the active group containing amino not being coordinated molecule aggregation, smooth and stable performance the black calcium in surface is formed
Titanium ore composite photoelectric conversion layer and hole transmission layer.
Perovskite composite photoelectric conversion layer and substrate conduction glass made above are cut into the square of 100mm × 10mm
Shape, the applying conductive elargol film on composite photoelectric conversion layer, the dry solidification at 150-200 DEG C, surface square resistance is 0.9
Ω, the test perovskite photoelectric conversion efficiency of the solar battery of assembling is 14.9%, perovskite solar cell after indoor placement January
Photoelectric transformation efficiency has no decline.
Embodiment 2
HMPA 300g, the hydroiodic acid 63.7g of mass percentage concentration 50% are separately added into glass reactor
(0.21mol) and stannous iodide 37.3g (0.1mol), stirs at 40-60 DEG C to being completely dissolved, and is subsequently adding cyanuric acid
13.6g (0.105mol), continues the h of stirring reaction 16, obtains iodate cyanuric acid stannous C3N3H2O3SnI4Solution；Vacuum is dense
Being reduced in solution has crystallization to separate out, and adds absolute ethyl alcohol to make the iodate cyanuric acid stannous dissolved in polar solvent
C3N3H2O3SnI4It is precipitated out, refined iodate cyanuric acid stannous is obtained after vacuum filter, absolute ethanol washing, vacuum drying
C3N3H2O3SnI4Crystallization 72.5g, yield is 96%.By iodate cyanuric acid stannous C made above3N3H2O3SnI4Crystallization 5g,
In being dissolved in 30g by the HMPA solvent of dewater treatment, with biscuit ware funnel secondary filter, bar spreader is used
The iodate methylamine lead CH prepared by embodiment 1 will be coated on3NH3PbI3On photoelectric conversion material crystalline membrane, shape after solvent volatilization
It is the iodate cyanuric acid stannous C of 150nm into thickness3N3H2O3SnI4Photoelectric conversion material crystalline membrane.
By iodate methylamine lead CH made above3NH3PbI3With iodate cyanuric acid stannous C3N3H2O3SnI4Double-deck calcium titanium
Ore deposit photoelectric conversion material crystalline membrane is heated to 170 DEG C under vacuum, and is incubated 1h, makes two layers of titanium ore photoelectric conversion material
Thin film contact area formed two kinds of transition zones of titanium ore photoelectric conversion material, while in making photoelectricity conversion thin film carry secretly methylamine and
Cyanuric acid raw material and be not coordinated containing secondary amine and hydroxyl reactive group molecule aggregation, form surface smooth and stable performance
Black perovskite composite photoelectric conversion layer and hole transmission layer.
Perovskite composite photoelectric conversion layer and substrate conduction glass made above are cut into the square of 100mm × 10mm
Shape, the applying conductive elargol film on composite photoelectric conversion layer, the dry solidification at 150-200 DEG C, surface square resistance is 1.1
Ω, the test perovskite photoelectric conversion efficiency of the solar battery of assembling is 14.6%, perovskite solar cell after indoor placement January
Photoelectric transformation efficiency has no decline.
Embodiment 3
Dimethyl sulfoxide (DMSO) 300g, the hydroiodic acid 63.7g of mass percentage concentration 50% are separately added into glass reactor
(0.21mol) and lead iodide 46.1g (0.1mol), stirs at 40-60 DEG C to being completely dissolved, and is subsequently adding trithiocyanuric acid
17.7g (0.10mol), continues the h of stirring reaction 24, obtains iodate trithiocyanuric acid lead C3H5N3S3PbI4Solution；Vacuum is dense
Being reduced in solution has crystallization to separate out, and adds absolute ethyl alcohol to make the iodate trithiocyanuric acid lead dissolved in polar solvent
C3H5N3S3PbI4It is precipitated out, refined iodate trithiocyanuric acid lead is obtained after vacuum filter, absolute ethanol washing, vacuum drying
C3H5N3S3PbI4Crystallization 88.5g, yield is 99%.By iodate trithiocyanuric acid lead C made above3H5N3S3PbI4Crystallization 5g,
In being dissolved in 30g by the dimethyl sulfoxide solvent of dewater treatment, with biscuit ware funnel secondary filter, will be applied with bar spreader
Cloth is in the iodate methylamine lead CH prepared by embodiment 13NH3PbI3On photoelectric conversion material crystalline membrane, form thick after solvent volatilization
Spend the iodate trithiocyanuric acid lead C for 120nm3H5N3S3PbI4Photoelectric conversion material crystalline membrane.
By iodate methylamine lead CH made above3NH3PbI3With iodate trithiocyanuric acid lead C3H5N3S3PbI4Double-deck calcium titanium
Ore deposit photoelectric conversion material crystalline membrane is heated to 170 DEG C under vacuum, and is incubated 1h, makes two layers of titanium ore photoelectric conversion material
Thin film contact area formed two kinds of transition zones of titanium ore photoelectric conversion material, while in making photoelectricity conversion thin film carry secretly methylamine and
Trithiocyanuric acid raw material and the molecule aggregation containing sulfhydryl reactive group not being coordinated, form smooth and stable performance the black calcium in surface
Titanium ore composite photoelectric conversion layer and hole transmission layer.
Perovskite composite photoelectric conversion layer and substrate conduction glass made above are cut into the square of 100mm × 10mm
Shape, the applying conductive elargol film on composite photoelectric conversion layer, the dry solidification at 150-200 DEG C, surface square resistance is 1.6
Ω, the test perovskite photoelectric conversion efficiency of the solar battery of assembling is 14.1%, perovskite solar cell after indoor placement January
Photoelectric transformation efficiency has no decline.
Claims (3)
1. a kind of large area perovskite solar cell composite photoelectric conversion layer, it is characterised in that by three-dimensional Ca-Ti ore type opto-electronic conversion
Material film and polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material film are constituted, three-dimensional Ca-Ti ore type photoelectric conversion material
On photoelectric conversion material skeleton, thickness is 100-500nm to film coated；Polymerizable two-dimensional layer Ca-Ti ore type opto-electronic conversion material
On three-dimensional Ca-Ti ore type light absorbing material film, thickness is 50-200nm to material film coated；Polymerizable two-dimensional layer perovskite
The thickness ratio of type photoelectric conversion material film and three-dimensional Ca-Ti ore type photoelectric conversion material film is 1：2-10；Two layers of Ca-Ti ore type
Exist between element in photoelectric conversion material and be exchanged with each other, spread and permeate, in two layers of perovskite photoelectric conversion material film
Contact area forms the transition zone of complexity, and transition region thickness is 25-100nm, polymerizable two-dimensional layer Ca-Ti ore type opto-electronic conversion
Film is simultaneously as hole transmission layer.
2. large area perovskite solar cell composite photoelectric conversion layer as claimed in claim 1, it is characterised in that polymerizable two dimension
Laminated perovskite type photoelectric conversion material film composition is NMX4, wherein, N is polymerizable compound, including cyanuric acid, three
Poly cyanamid, trithiocyanuric acid, tripolyphosphate ammonium, the phosphonitrile of amino ring three or its mixture；M is Pb2+、Sn2+、Ge2+、Cu2+、Ni2+、
Mn2+、Zn2+、Fe2+Or its mixture；X is Cl-、Br-、I-Or its mixture.
3. a kind of preparation method of large area perovskite solar cell composite photoelectric conversion layer, it is characterised in that including three-dimensional calcium titanium
The film preparation of ore deposit type photoelectric conversion material, polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material and film preparation, complex light
Electric conversion layer is prepared and evaluates three parts, and technical scheme is comprised the following steps：
（1）Three-dimensional Ca-Ti ore type photoelectric conversion material is dissolved in polar organic solvent, with biscuit ware funnel secondary filter,
The photoelectric conversion material solution of mass percentage concentration 10%-20% is formed, with bar spreader by photoelectric conversion material solution coating
On photoelectric conversion layer skeleton, it is the three-dimensional Ca-Ti ore type photoelectric conversion material knot of 100-500nm that thickness is formed after solvent volatilization
Brilliant film, the polar organic solvent be dimethylformamide, gamma-butyrolacton, dimethyl sulfoxide (DMSO), HMPA or its
Mixture；The photoelectric conversion layer skeleton is that coating thickness is 20- in the FTO Conducting Glass of 100mm × 100mm
The nano-TiO of 50nm2Compacted zone, it is 40-60nm to be then coated with particle diameter, and thickness is the TiO of 100-600nm2Film, finally exists
Sintering is formed at 450-550 DEG C；
（2）Polar organic solvent, halogen acids and metal halide are separately added into glass reactor, are stirred at 40-60 DEG C
To being completely dissolved, polymerizable compound is subsequently adding, controls the raw material molar ratio to be：Polymerizable compound：HX：MX2= 1：
2.0-2.1：0.95-1.05, continues stirring reaction 12-24 h, obtains polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material
Solution；Being concentrated in vacuo in solution has crystallization to separate out, and adds absolute ethyl alcohol to make the chemical composition dissolved in polar solvent be NMX4
Two-dimensional layer Ca-Ti ore type photoelectric conversion material be precipitated out, obtain essence after vacuum filter, absolute ethanol washing, vacuum drying
The NMX of system4Crystalline product, the polymerizable compound is cyanuric acid, melamine, trithiocyanuric acid, tripolyphosphate ammonium, ammonia
The phosphonitrile of basic ring three or its mixture；The metal halide is the halide of metallic element Pb, Sn, Ge, Cu, Ni, Mn, Zn, Fe
Or its mixture；
（3）Two-dimensional layer Ca-Ti ore type photoelectric conversion material crystallization made above is dissolved in polar organic solvent, with element
Ceramic funnel secondary filter is burnt, the perovskite photoelectric conversion material solution of mass percentage concentration 10%-20% is formed, is coated with bar
Device by perovskite photoelectric conversion material solution coating on three-dimensional Ca-Ti ore type photoelectric conversion material crystalline membrane, solvent volatilization after
It is the polymerizable two-dimensional layer Ca-Ti ore type photoelectric conversion material crystalline membrane of 50-200nm to form thickness, and the polarity is organic
Solvent is dimethylformamide, gamma-butyrolacton, dimethyl sulfoxide (DMSO), HMPA or its mixture；
（4）Double Perovskite type photoelectric conversion material crystalline membrane made above is heated to 140-190 under vacuum
DEG C, and 0.5-2h is incubated, element is exchanged with each other, spreads and permeates in making two layers of Ca-Ti ore type photoelectric conversion material, in two layers of calcium
Titanium ore photoelectric conversion material thin film contact area forms two kinds of mixed transition layers of titanium ore photoelectric conversion material；Polymerizable compound
In autohemagglutination or copolymerization do not form more stable polymer in a heated condition with the complex bound active group of metal halide
Molecule；Simultaneously remove the solvent volatilization carried secretly in perovskite photoelectricity conversion thin film, so as to form surface smooth and stable performance
Black perovskite composite photoelectric conversion layer；
（5）Perovskite composite photoelectric conversion layer and substrate conduction glass made above are cut into the rectangle of 100mm × 10mm,
Without being coated with hole transmission layer, directly the applying conductive elargol film on composite photoelectric conversion layer, dries solid at 150-200 DEG C
Change, surface square resistance is 0.5-2 Ω, is 14%-15% with its perovskite photoelectric conversion efficiency of the solar battery for assembling, and interior is put
The photoelectric transformation efficiency for putting perovskite solar cell after January has no decline.
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