CN106449994B - A kind of large area perovskite solar cell light absorption multilayer film and preparation method thereof - Google Patents
A kind of large area perovskite solar cell light absorption multilayer film and preparation method thereof Download PDFInfo
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- CN106449994B CN106449994B CN201611173307.7A CN201611173307A CN106449994B CN 106449994 B CN106449994 B CN 106449994B CN 201611173307 A CN201611173307 A CN 201611173307A CN 106449994 B CN106449994 B CN 106449994B
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Abstract
The present invention relates to a kind of perovskite solar cell light absorption multilayer films and preparation method thereof being made of three-dimensional perovskite light absorping film/two dimension perovskite light absorping film/polyurethane complex compound film.Two-dimentional perovskite light absorping film group becomes NMX in the present invention4, wherein N is imidazoles or triazole compounds；M is Pb2+、Sn2+、Ge2+、Cu2+、Ni2+、Mn2+、Zn2+、Fe2+Or mixtures thereof；X is Cl‑、Br‑、I‑Or mixtures thereof.Polyurethane complex compound film is the organic covalent compound film of hydrophobic inorganic-that isocyanate compound solution coating is formed in situ on two-dimentional perovskite light absorping film in the present invention, can be used as perovskite solar cell hole transmission layer.Retained material is removed using the polymerization reaction of isocyanates in the present invention and forms hole transmission layer, simplifies large area perovskite solar cell preparation process.
Description
Technical field
The present invention relates to one kind by three-dimensional perovskite light absorping film/two dimension perovskite light absorping film/polyurethane complex compound film
Perovskite solar cell light absorption multilayer film of composition and preparation method thereof, belongs to new energy and field of new materials.
Technical background
More than 28%, future is expected to reach 50% the current photoelectric conversion efficiency of perovskite solar cell, becomes solar cell
The new hope of industry.Perovskite solar cell is usually to be passed by transparent conducting glass, compacted zone, perovskite light absorbing layer, hole
Defeated layer, five part of metal back electrode composition.The thickness of perovskite light absorbing layer is generally 200-600nm, and main function is to absorb
Sunlight simultaneously generates electron-hole pair, and can high efficiency of transmission electron-hole pair.
For perovskite light absorbing material the most commonly used is three-dimensional structure halide, Typical molecular formula is AMX3, wherein A is represented
Monovalent cation, usually CH3NH3 +、CH(NH2)2 +Or Cs+；M represents metal cation, usually Pb2+、Sn2+、Ge2+、Cu2 +、Ni2+、Mn2+、Sb3+、Bi3+；X represents anion, usually Cl-、Br-、I-、CNS-、BF4 -Or PF6 -.If monovalent cation
Molecule is bigger, and the high symmetry of three-dimensional perovskite crystal structure is easy for being destroyed, and is changed into two-dimensional layer Ca-Ti ore type
Photoelectric conversion material, Typical molecular formula are NMX4, wherein N represents monovalent cation, usually contains two amino or imido grpup
Compound, amino-containing macromolecular compound；M represents metal cation, usually Pb2+、Sn2+、Ge2+、Cu2+、Ni2+、Mn2 +、Sb3+、Bi3+；X represents anion, usually Cl-、Br-、I-、CNS-、BF4 -Or PF6 -。
Although research finds that the photoelectric conversion performance of two-dimensional layer Ca-Ti ore type photoelectric conversion material is three-dimensional not as good as common
Ca-Ti ore type photoelectric conversion material but has better environmental stability, electric conductivity and the separation of good hole and transporting
Energy.Three-dimensional perovskite light absorbing material and two-dimentional perovskite light absorbing material are mixed or are prepared into duplicature and answered by patent disclosure
With to stabilize and increase perovskite solar cell light absorbing layer performance.Monovalent cation in perovskite light absorbing material at present
Kind is also fewer, and perovskite light absorbing material filming performance and ambient stable performance are also undesirable, is not met by large area
The preparation of perovskite solar cell light absorbing layer requires.
Summary of the invention
The object of the present invention is to provide a kind of large area perovskite solar cell light absorption multilayer films, especially by three-dimensional calcium
Titanium ore light absorping film/two dimension perovskite light absorping film/polyurethane complex compound film composition perovskite solar cell light absorption multilayer
Film, and use polyurethane complex compound film as perovskite solar cell hole transmission layer, to simplify large area perovskite solar cell
Preparation process.
Three-dimensional perovskite light absorping film group becomes AMX in the present invention3, wherein A CH3NH3 +、CH(NH2)2 +、Cs+Or its
Mixture；M is Pb2+、Sn2+、Ge2+、Cu2+、Ni2+、Mn2+、Sb3+、Bi3+Or mixtures thereof；X is Cl-、Br-、I- 、CNS-、
BF4 -、PF6 -Or mixtures thereof；Dimethylformamide, gamma-butyrolacton, hexamethyl are dissolved in by three-dimensional perovskite light absorbing material
In phosphoric triamide or dimethyl sulfoxide isopolarity organic solvent, it is coated on light absorbing layer skeleton, is formed after heat treatment, thickness
For 100-500nm.
Two-dimentional perovskite light absorping film group becomes NMX in the present invention4, wherein N is imidazoles or triazole compounds；M is Pb2 +、Sn2+、Ge2+、Cu2+、Ni2+、Mn2+、Zn2+、Fe2+Or mixtures thereof；X is Cl-、Br-、I- -Or mixtures thereof；The imidazoles or
Triazole compounds are imidazoles, alkyl imidazole, nitroimidazole, aminooimidazole, imidazolone, benzimidazole, diphenyl-imidazole, three
Azoles, aminotriazole(ATA), benzotriazole, methylbenzotrazole, phenyl hydroxyl triazole etc.；It is dissolved in by two-dimentional perovskite light absorbing material
In dimethylformamide, gamma-butyrolacton, hexamethylphosphoramide or dimethyl sulfoxide isopolarity organic solvent, it is coated on three-dimensional
It on perovskite light absorping film, is formed after heat treatment, with a thickness of 50-200nm.
Polyurethane complex compound film is that isocyanate compound is dissolved in non-polar organic solvent in the present invention, by isocyanide
The organic covalent compound of hydrophobic inorganic-that ester compound solution coating is formed in situ on two-dimentional perovskite light absorping film
Film, with a thickness of 25-100nm, the isocyanate compound is hexamethylene diisocyanate（HDI）, toluene di-isocyanate(TDI)
（TDI）, methyl diphenylene diisocyanate（MDI）, trifluoromethyl diisocyanate（TMPI）, naphthalene diisocyanate, triphenyl
Methane triisocyanate, the addition product of hexamethylene diisocyanate and polyalcohol, toluene di-isocyanate(TDI) and polyalcohol plus
At object；The non-polar organic solvent is ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether fourth
Or mixtures thereof ether, tetrahydrofuran, gamma-butyrolacton.
Three-dimensional perovskite light absorping film is the main body of light absorption multilayer film in the present invention, and the contribution rate to photoelectric conversion is
50%-70%, two-dimentional perovskite light absorping film make up three-dimensional perovskite light absorping film in terms of uniformity and light absorption wavelength range
Deficiency, be 20%-30% to the contribution rate of photoelectric conversion；Polyurethane complex compound film can be improved the ambient stable of light absorbing layer
Property, while as hole transmission layer, the contribution rate to photoelectric conversion is 10%-20%.
Contain two or three active functional groups of nitrogen in the imidazoles or triazole compounds molecule used in the present invention, nitrogen is former
The presence of unshared electron pair in son makes it be readily adsorbed in metal surface or form stable comple, so being widely used as
The corrosion inhibiter of non-ferrous metal.Imidazoles or triazole compounds can also form stable comple with some metal halides, be used as organic conjunction
At catalyst and epoxy resin or the curing agent of ureaformaldehyde.
It is NMX that imidazoles or triazole compounds, which can form chemical composition with halogen acids and metal halide complex,4Perovskite
Light absorbing material not only absorbs visible light in sunlight, but also can absorb the near infrared light in sunlight and generate electronics and sky
Cave carrier, to extend the absorbing wavelength range of sunlight.
The isocyanate compound solution coating used in the present invention forms polyurethane on two-dimentional perovskite light absorping film
Complex compound film, two tunics contact area there are the diffusion of bioactive molecule and infiltration, seep a part of isocyanate compound
It penetrates into two-dimentional perovskite light absorption film layer, is NMX with chemical composition4Perovskite light absorbing material chemically reacted,
Polyurethane complex compound film is formed on surface, and the Nomenclature Composition and Structure of Complexes inside two-dimentional perovskite light absorping film and is had not been changed.
Polyurethane complex compound film formation basic theory is that isocyanate compound has two or more active groups in the present invention, can
It is more stable with not formed with the complex bound nitrogen active group combined polymerization of metal halide in imidazoles or triazole compounds molecule
Polyurethane complex compound film, but the coordination structure of nitrogen-atoms and metal halide in imidazoles and triazole compounds molecule is not destroyed, gold
Belong to the promotor that halide itself is used as copolyreaction, so that copolyreaction is done under room temperature and carry out.It does not penetrate into inside film layer
Isocyanate compound absorb Environmental Water and autohemagglutination can occur generate more stable amino-containing urethanes, into
One step forms polyurethane complex compound film with the metal halide diffused out.Polyurethane complex compound film improves perovskite light absorption
The performance of layer, greatly improves its anti-oxidant, water resistant gas, ultraviolet light and the performance of resisting temperature aging.Polyurethane complex compound point
Contain a large amount of nitrogen active groups and unshared electron pair in son, there is the condition for forming photosensitive polymer and conducting polymer, institute
Using can be as the hole transport layer material of perovskite solar cell.
It is a further object of the present invention to provide a kind of preparation method of large area perovskite solar cell light absorption multilayer film,
Including the preparation of three-dimensional perovskite light absorping film, two-dimentional perovskite light absorbing material and film preparation, the preparation of polyurethane complex compound film
Three parts, the technical scheme comprises the following steps：
（1）Three-dimensional Ca-Ti ore type photoelectric conversion material is dissolved in polar organic solvent, it is accurate with biscuit ware funnel
Filtering forms the light absorbing material solution of mass percentage concentration 10%-20%, is coated on light absorbing layer skeleton with bar spreader
On, the three-dimensional perovskite light absorbing material crystalline membrane with a thickness of 100-500nm is formed after solvent volatilization, the polarity is organic molten
Agent is or mixtures thereof dimethylformamide, gamma-butyrolacton, dimethyl sulfoxide, hexamethylphosphoramide；The light absorbing layer bone
Frame is the nano-TiO that coating thickness is 20-50nm in the FTO Conducting Glass of 100mm × 100mm2Compacted zone, then
Coating partial size is 40-60nm, with a thickness of the TiO of 100-600nm2Film is finally sintered at 450-550 DEG C；
（2）Polar organic solvent, halogen acids and metal halide are separately added into glass reactor, at 40-60 DEG C
Then imidazoles or triazole compounds are added to being completely dissolved in stirring, control raw material molar ratio is：Imidazoles or triazole chemical combination
Object：HX：MX2= 1：2.0-2.1：0.95-1.05 continues to be stirred to react 12-24 h, obtains two-dimentional perovskite light absorbing material
Solution；Being concentrated in vacuo in solution has crystallization to be precipitated, and dehydrated alcohol, which is added, makes the chemical composition NMX dissolved in polar solvent4
Two-dimentional perovskite light absorbing material be precipitated out, the NMX that is refined after vacuum filter, dehydrated alcohol washing, vacuum drying4
Crystalline product, the imidazoles or triazole compounds are imidazoles, alkyl imidazole, nitroimidazole, aminooimidazole, imidazolone, benzo
One of imidazoles, diphenyl-imidazole, triazole, aminotriazole(ATA), benzotriazole, methylbenzotrazole, phenyl hydroxyl triazole；The metal
Halide is or mixtures thereof the halide of metallic element Pb, Sn, Ge, Cu, Ni, Mn, Zn, Fe；
（3）Two-dimentional perovskite light absorbing material crystallization made above is dissolved in polar organic solvent, is made pottery with biscuiting
Buchner funnel secondary filter forms the perovskite light absorbing material solution of mass percentage concentration 10%-20%, is coated with bar spreader
On three-dimensional perovskite light absorbing material crystalline membrane, the two-dimentional perovskite light with a thickness of 50-200nm is formed after solvent volatilization
Absorbing material crystalline membrane, the polar organic solvent are dimethylformamide, gamma-butyrolacton, dimethyl sulfoxide, hempa
Or mixtures thereof acyl triamine；
（4）It is separately added into non-polar organic solvent and isocyanate compound in glass reactor, forms quality percentage
The isocyanate solution of concentration 10%-20% is coated on two-dimentional perovskite light absorbing material crystalline membrane with bar spreader
On, control isocyanates and imidazoles or triazole compounds molar ratio are 0.05-0.2：1, it is formed after solvent volatilization with a thickness of 25-
The polyurethane complex compound film of 100nm, the non-polar organic solvent are ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, second two
Or mixtures thereof alcohol ether, butyl glycol ether butyl ether, tetrahydrofuran, gamma-butyrolacton, the isocyanate compound are six methylenes
Group diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, trifluoromethyl diisocyanate, two isocyanide of naphthalene
Acid esters, triphenylmethane triisocyanate, the addition product of hexamethylene diisocyanate and polyalcohol, toluene di-isocyanate(TDI) with
The addition product of polyalcohol；
（5）By three-dimensional perovskite light absorping film made above/two dimension perovskite light absorping film/polyurethane complex compound film three
Tunic is heated to 80-100 DEG C under vacuum conditions, carries out aging process 1-2h, makes the phase of element and group in trilamellar membrane material
Mutually migration, diffusion and infiltration reach balance, make the quick autohemagglutination of remaining isocyanates or are combined with not being coordinated with metal halide
Active group be copolymerized to form more stable polyurethane complex molecules, while the solvent of entrainment being made to volatilize completely removing, thus
Form smooth surface and the stable black perovskite light absorption multilayer film of performance；
（6）Perovskite light absorption multilayer film and substrate conduction glass made above are cut into the square of 100mm × 10mm
Shape, does not have to coating hole transmission layer, and the applying conductive elargol film directly on light absorption multilayer film is dry at 150-200 DEG C
Solidification, surface square resistance are 0.5-2 Ω, are 14%-15% with its perovskite solar cell photoelectric conversion efficiency assembled, indoor
The photoelectric conversion efficiency of perovskite solar cell does not decline after placing January.
The beneficial effects of the present invention are embodied in：
（1）The present invention chemically reacts using isocyanates and imidazoles or triazole compounds and to form polyurethane complex compound film, clearly
Except remaining raw material and hole transmission layer is formed, simplifies large area perovskite solar cell preparation process；
（2）The present invention uses perovskite solar cell light absorption multilayer film, improves perovskite solar cell light absorbing layer
Uniformity, extend light absorption wavelength range, polyurethane complex compound film substantially increases the environmental stability of light absorbing layer.
Specific embodiment
Embodiment 1
Coating thickness is the nano-TiO of 20-50nm in the FTO Conducting Glass of 100mm × 100mm2Compacted zone,
Then coating partial size is 40-60nm, with a thickness of the TiO of 100-600nm2Film, finally sintering forms light suction at 450-550 DEG C
Receive multilayer film casing play.Weigh CH3NH3PbI3Ca-Ti ore type photoelectric conversion material 5g is dissolved in diformazan of the 30g Jing Guo dehydration
In base formamide solvent, mass percentage concentration is formed with biscuit ware funnel secondary filter to whole dissolutions within stirring 12 hours
14.3% light absorbing material solution, with bar spreader by solution coating on light absorbing layer skeleton, formed after solvent volatilization thick
Degree is the iodate methylamine lead CH of 400nm3NH3PbI3Light absorbing 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 to being completely dissolved at 40-60 DEG C, 2-methylimidazole is then added
8.6g (0.105mol) continues to be stirred to react 12 h, obtains iodide copper imidazolate C6N2H8CuI4Solution；It is concentrated in vacuo to
There is crystallization to be precipitated in solution, dehydrated alcohol, which is added, makes the iodide copper imidazolate C dissolved in polar solvent6N2H8CuI4It is settled out
Come, the iodide copper imidazolate C refined after vacuum filter, dehydrated alcohol washing, vacuum drying6N2H8CuI4Crystallization.It will be with
The iodide copper imidazolate C of upper preparation6N2H8CuI45g is crystallized, solvent dimethylformamide of the 30g Jing Guo dehydration is dissolved in
In, with biscuit ware funnel secondary filter, iodate methylamine lead CH will be coated on bar spreader3NH3PbI3Light absorbing material knot
On brilliant film, the iodide copper imidazolate C with a thickness of 200nm is formed after solvent volatilization6N2H8CuI4Light absorbing material crystallization is thin
Film.
Hexamethylene diisocyanate 5g is dissolved in 20g ethyl acetate, is coated on iodate first with bar spreader
Base copper imidazolate C6N2H8CuI4On light absorbing material crystalline membrane, control hexamethylene diisocyanate and methylimidazole molar ratio
For 0.05-0.1：1, the polyurethane complex compound film with a thickness of 100nm is formed after solvent volatilization.By the CH of preparation3NH3PbI3/
C6N2H8CuI4/ polyurethane complex compound film three-layer thin-film is heated to 80 DEG C under vacuum conditions, carries out aging process 1h, makes to carry secretly
Solvent volatilize completely removing, to form smooth surface and the stable black perovskite light absorption multilayer film and hole of performance passes
Defeated layer.
Perovskite light absorption multilayer film and substrate conduction glass made above are cut into the rectangle of 100mm × 10mm,
The applying conductive elargol film on light absorption multilayer film, the dry solidification at 150-200 DEG C, the test perovskite sun electricity of assembling
Pond photoelectric conversion efficiency is 14.3%, and the photoelectric conversion efficiency of perovskite solar cell does not decline after indoor placement January.
Embodiment 2
Dimethylformamide 300g, the hydroiodic acid 63.7g of mass percentage concentration 50% are separately added into glass reactor
(0.21mol) and zinc iodide 31.9g (0.1mol), stirs to being completely dissolved at 40-60 DEG C, benzotriazole is then added
12.5g (0.105mol) continues to be stirred to react 16 h, obtains iodate benzotriazole zinc C6N3H7ZnI4Solution；Vacuum concentration
There is crystallization to be precipitated into solution, dehydrated alcohol, which is added, makes the iodate benzotriazole zinc C dissolved in polar solvent6N3H7ZnI4Precipitating
Out, the iodate benzotriazole zinc C refined after vacuum filter, dehydrated alcohol washing, vacuum drying6N3H7ZnI4Crystallization.
By iodate benzotriazole zinc C made above6N3H7ZnI45g is crystallized, diformazan of the 30g Jing Guo dehydration is dissolved in
In base formamide solvent, with biscuit ware funnel secondary filter, it will be coated on by the preparation of 1 method of embodiment with bar spreader
Iodate methylamine lead CH3NH3PbI3On light absorbing material crystalline membrane, the iodate benzo with a thickness of 150nm is formed after solvent volatilization
Triazole zinc C6N3H7ZnI4Light absorbing material crystalline membrane.
Toluene di-isocyanate(TDI) 5g is dissolved in 20g glycol dinitrate ether solvents, is coated on iodine with bar spreader
Change benzotriazole zinc C6N3H7ZnI4On light absorbing material crystalline membrane, control toluene di-isocyanate(TDI) and benzotriazole molar ratio
For 0.1-0.2：1, the polyurethane complex compound film with a thickness of 50-100nm is formed after solvent volatilization.By the CH of preparation3NH3PbI3/
C6N3H7ZnI4/ polyurethane complex compound film three-layer thin-film is heated to 100 DEG C under vacuum conditions, carries out aging process 1h, makes to carry secretly
Solvent volatilize completely removing, to form smooth surface and the stable black perovskite light absorption multilayer film and hole of performance passes
Defeated layer.
Perovskite light absorption multilayer film and substrate conduction glass made above are cut into the rectangle of 100mm × 10mm,
The applying conductive elargol film on light absorption multilayer film, the dry solidification at 150-200 DEG C, the test perovskite sun electricity of assembling
Pond photoelectric conversion efficiency is 14.7%, and the photoelectric conversion efficiency of perovskite solar cell does not decline after indoor placement January.
Claims (5)
1. a kind of large area perovskite solar cell light absorption multilayer film, it is characterised in that by three-dimensional perovskite light absorping film/bis-
Perovskite light absorping film/polyurethane complex compound film composition is tieed up, three-dimensional Ca-Ti ore type photoelectric conversion material film coated is in light absorption
On layer skeleton, with a thickness of 100-500nm；Two-dimentional perovskite light absorping film is coated on three-dimensional perovskite light absorping film, with a thickness of
50-200nm；Polyurethane complex compound film be by isocyanate compound solution coating on two-dimentional perovskite light absorping film shape in situ
At the organic covalent compound film of hydrophobic inorganic-can be passed simultaneously as perovskite solar cell hole with a thickness of 25-100nm
Defeated layer.
2. large area perovskite solar cell light absorption multilayer film as described in claim 1, it is characterised in that three-dimensional Ca-Ti ore type
Light absorping film group becomes AMX3, wherein A CH3NH3 +、CH(NH2)2 +、Cs+Or mixtures thereof；M is Pb2+、Sn2+、Ge2+、Cu2 +、Ni2+、Mn2+、Sb3+、Bi3+Or mixtures thereof；X is Cl-、Br-、I- 、CNS-、BF4 -、PF6 -Or mixtures thereof.
3. large area perovskite solar cell light absorption multilayer film as described in claim 1, it is characterised in that two-dimentional perovskite light
Absorbing film group becomes NMX4, wherein N is imidazoles or triazole compounds；M is Pb2+、Sn2+、Ge2+、Cu2+、Ni2+、Mn2+、Zn2+、
Fe2+Or mixtures thereof；X is Cl-、Br-、I--Or mixtures thereof, the imidazoles or triazole compounds are imidazoles, alkyl imidazole, nitre
Base imidazoles, aminooimidazole, imidazolone, benzimidazole, diphenyl-imidazole, triazole, aminotriazole(ATA), benzotriazole, methyl benzo
Triazole, phenyl hydroxyl triazole.
4. large area perovskite solar cell light absorption multilayer film as described in claim 1, it is characterised in that isocyanates chemical combination
Object is hexamethylene diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, trifluoromethyl diisocyanate
Ester, naphthalene diisocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate and polyalcohol addition product, toluene
The addition product of diisocyanate and polyalcohol.
5. a kind of preparation method of large area perovskite solar cell light absorption multilayer film, it is characterised in that preparation method includes three
It ties up the preparation of perovskite light absorping film, two-dimentional perovskite light absorbing material and film preparation, polyurethane complex compound film and prepares three parts,
The technical scheme comprises 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 light absorbing material solution for forming mass percentage concentration 10%-20%, is coated on light absorbing layer skeleton, solvent with bar spreader
The three-dimensional perovskite light absorbing material crystalline membrane with a thickness of 100-500nm is formed after volatilization, the polar organic solvent is two
Or mixtures thereof methylformamide, gamma-butyrolacton, dimethyl sulfoxide, hexamethylphosphoramide；The light absorbing layer skeleton be
Coating thickness is the nano-TiO of 20-50nm in the FTO Conducting Glass of 100mm × 100mm2Then compacted zone is coated with grain
Diameter is 40-60nm, with a thickness of the TiO of 100-600nm2Film is finally sintered at 450-550 DEG C；
（2）It is separately added into polar organic solvent, halogen acids and metal halide in glass reactor, is stirred at 40-60 DEG C
To being completely dissolved, imidazoles or triazole compounds are then added, control raw material molar ratio is：Imidazoles or triazole compounds：HX：
MX2= 1：2.0-2.1：0.95-1.05 continues to be stirred to react 12-24 h, obtains two-dimentional perovskite light absorbing material solution；
Being concentrated in vacuo in solution has crystallization to be precipitated, and dehydrated alcohol, which is added, makes the chemical composition NMX dissolved in polar solvent4Two dimension
Perovskite light absorbing material is precipitated out, the NMX refined after vacuum filter, dehydrated alcohol washing, vacuum drying4Crystallization produces
Product, the imidazoles or triazole compounds are imidazoles, alkyl imidazole, nitroimidazole, aminooimidazole, imidazolone, benzimidazole, two
One of phenylimidazole, triazole, aminotriazole(ATA), benzotriazole, methylbenzotrazole, phenyl hydroxyl triazole；The metal halide
For or mixtures thereof the halide of metallic element Pb, Sn, Ge, Cu, Ni, Mn, Zn, Fe；
（3）Two-dimentional perovskite light absorbing material crystallization made above is dissolved in polar organic solvent, is leaked with biscuit ware
Struggle against secondary filter, forms the perovskite light absorbing material solution of mass percentage concentration 10%-20%, is coated on three with bar spreader
It ties up on perovskite light absorbing material crystalline membrane, forms the two-dimentional perovskite light absorption with a thickness of 50-200nm after solvent volatilization
Material crystalline film, the polar organic solvent are dimethylformamide, gamma-butyrolacton, dimethyl sulfoxide, hexamethyl phosphinylidyne three
Or mixtures thereof amine；
（4）It is separately added into non-polar organic solvent and isocyanate compound in glass reactor, forms mass percentage concentration
The isocyanate solution of 10%-20% is coated on two-dimentional perovskite light absorbing material crystalline membrane with bar spreader, control
Isocyanates processed and imidazoles or triazole compounds molar ratio are 0.05-0.2：1, it is formed after solvent volatilization with a thickness of 25-100nm
Polyurethane complex compound film, the non-polar organic solvent be ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether,
Or mixtures thereof butyl glycol ether butyl ether, tetrahydrofuran, gamma-butyrolacton, the isocyanate compound are that hexa-methylene two is different
Cyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, trifluoromethyl diisocyanate, naphthalene diisocyanate, three
Phenylmethane triisocyanate, the addition product of hexamethylene diisocyanate and polyalcohol, toluene di-isocyanate(TDI) and polyalcohol
Addition product；
（5）By three-dimensional perovskite light absorping film made above/two dimension perovskite light absorping film/polyurethane complex compound film trilamellar membrane
It is heated to 80-100 DEG C under vacuum conditions, carries out aging process 1-2h, make mutually moving for element and group in trilamellar membrane material
Move, diffusion and infiltration reach balance, make the quick autohemagglutination of remaining isocyanates or with not with the complex bound work of metal halide
Property group be copolymerized to form more stable polyurethane complex molecules, while the solvent of entrainment being made to volatilize completely removing, to be formed
Smooth surface and the stable black perovskite light absorption multilayer film of performance.
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| CN106711338B (en) * | 2017-02-24 | 2019-06-28 | 哈尔滨工业大学深圳研究生院 | A kind of tin based perovskites film, preparation method and its solar cell device |
| CN107611190A (en) * | 2017-09-18 | 2018-01-19 | 南昌大学 | A kind of perovskite solar cell resistant to bending and preparation method |
| CN107768524B (en) * | 2017-12-04 | 2024-02-09 | 湖南师范大学 | Efficient and stable perovskite solar cell and preparation method thereof |
| CN110660911B (en) * | 2018-06-28 | 2022-09-13 | 华中科技大学鄂州工业技术研究院 | Perovskite thin film and preparation method and application thereof |
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