CN106571427A - Novel photoelectric conversion composite material sol and preparation method thereof - Google Patents

Novel photoelectric conversion composite material sol and preparation method thereof Download PDF

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CN106571427A
CN106571427A CN201610997981.0A CN201610997981A CN106571427A CN 106571427 A CN106571427 A CN 106571427A CN 201610997981 A CN201610997981 A CN 201610997981A CN 106571427 A CN106571427 A CN 106571427A
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pbx
methylamine
photoelectric conversion
sol
colloidal sol
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李建生
刘炳光
何涛
王少杰
朱秋雨
白静伊
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Tianjin Vocational Institute
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Abstract

The invention relates to a novel photoelectric conversion composite material sol and a preparation method thereof; the method comprises the following steps: firstly using cyclophosphazene halide and methylamine to mix so as to prepare a perovskite type photoelectric conversion composite material sol; the novel photoelectric conversion composite material sol comprises lead halide, cyclophosphazene halide, methylamine halogen acids salt, a dehydration catalyst and an organic solvent; the method uses the cyclophosphazene halide to prepare the novel perovskite photoelectric conversion material, and the preparation technology condition scope is wide; the synthesis photoelectric conversion material is better in environment stability, and can expand the luminous absorption wavelength scope for sunlight and improve the photoelectric conversion efficiency by 1.8-2.2%.

Description

A kind of novel photoelectric conversion composite sol and preparation method thereof
Technical field
The present invention relates to a kind of novel photoelectric conversion composite sol and preparation method thereof, especially with ring phosphonitrile halogen Compound and methylamine are mixed with Ca-Ti ore type opto-electronic conversion composite sol, to adjust perovskite light absorbing material band gap and carry High-photoelectric transformation efficiency, belongs to new forms of energy and field of new.
Technical background
The solaode prepared based on organic metal halogenide perovskite structure light absorbing material is referred to as perovskite too Positive electricity pond, at present more than 20%, future is expected to reach 50% its photoelectric transformation efficiency.Perovskite solar cell is typically by saturating Bright electro-conductive glass, compacted zone, perovskite light absorbing zone, hole transmission layer, the part of metal back electrode five composition.Perovskite light absorbs The thickness of layer is generally 200-600nm, and Main Function is to absorb sunlight and produce electron-hole pair, and can high efficiency of transmission electricity Son-hole pair.
Perovskite light absorbing material Typical molecular formula is AMX3, wherein, A represents the ammonium ion or metal ion of monovalence, M Metal cation is represented, X represents halide anion.Research both at home and abroad to metal cation and halide anion at present is compared Thoroughly, composition but to the ammonium ion of monovalence, structurally and functionally Mechanism Study are little.
At present both at home and abroad to Ca-Ti ore type light absorbing material iodate methylamine lead（CH3NH3PbI3）Research is relatively more, by iodine first A kind of inorganic-organic double salt or coordination compound that amine and lead iodide reaction are generated, it is also a kind of Semiconductor absorption material, Its band gap is about 1.5eV, can fully absorb the visible ray of wavelength 400-800nm, with absorbing properties it is good, prepare letter The single and high characteristic of photoelectric transformation efficiency.Its main deficiency is：（1）Temperature tolerance is bad, it is desirable to the heat treatment temperature of light absorbing zone Less than 150 DEG C, the additive during at such a temperature prepared by light absorbing zone can not decompose completely；（2）Environmental stability is poor, easily Decompose for dampness, ultraviolet light or catalyst in air；（3）Absorb optical wavelength range and be confined to visible region, to ultraviolet light and red Outer light is hardly picked up；（4）Filming performance is bad, easily forms loose thick crystalline solid, it is difficult to large area even spread.
Improve Ca-Ti ore type light absorbing material performance, can start with from the composition design of Ca-Ti ore type light absorbing material.For example, The biological institute in Chinese Academy of Sciences Qingdao prepares perovskite structure light absorbing material using the primary amine of C1-C4, carbonamidine or its mixture, and acquisition is good Good photoelectric transformation efficiency；Xiamen University's patent of invention CN106058060 (2016-10-25) is open mixed using methylamine and carbonamidine Conjunction prepares perovskite structure light absorbing material thin film；Wuhan University of Technology's patent of invention CN105742502 (2016-07-06) is public Exploitation iodobenzene ethamine, Tin diiodide. and lead iodide are mixed with the adjustable perovskite structure light absorbing material of band gap；Central China section Skill university patent of invention CN103762344 (2014-04-30) is open to be mixed with calcium using aminobutyric acid amphiphatic molecule and methylamine Perovskite like structure light absorbing material；United States Patent (USP) US20150249170 (2015-09-03) disclosure long-chain organic amine prepares calcium titanium Ore deposit structure light absorbing material, but the details of long-chain organic amine is not disclosed；United States Patent (USP) US20150200377 (2015- It is 07-16) open to prepare perovskite structure light absorbing material with a series of primary, secondary, uncles, quaternary ammonium compound, but amine is not provided The embodiment of compound；Chinese patent CN103554171 (2014-02-05) is open to adopt 1- aminopyridines azomethine and chlorination Lead coordinates as potential dielectric material；The open 1- ethyl-3-methylimidazoles of Chinese patent CN102337593 (2012-02-01) Tribromide iodine perovskite structure light absorbing material preparation method.
Improve perovskite light absorping film performance, it is also possible to start with from perovskite light absorbing material structure.For example, Singapore south Foreign Polytechnics's patent of invention WO2016126211 (2016-08-11) is disclosed perovskite light absorbing material and nanoclay grain Son forms in organic solvent colloidal sol, nanoparticle as crystal seed, improve perovskite light absorbing material microstructure and into Film properties；Tianjin Professional College patent of invention CN105789339 (2016-07-20) it is open by perovskite light absorbing material with Nano-silicon dioxide particle forms in organic solvent colloidal sol, nanoparticle as light absorbing material crystal seed and framework material, one Step obtains the light absorbing zone of smooth even；Nankai University's patent of invention CN104218109 (2014-12-17) is open by polyethylene Ketopyrrolidine mixes with perovskite light absorbing material, improves microstructure and the filming performance of perovskite light absorbing material, greatly It is big to improve photoelectric transformation efficiency.
Although perovskite photoelectric conversion efficiency of the solar battery data are also constantly refreshing, what inorganic-organic hybridization was formed The unstable properties of perovskite photoelectric conversion material or light absorbing material, it is impossible to reach wet-heat resisting and ultraviolet resistance exposure experiment will Ask.Some departments study and replace methylamine to prepare the perovskite light absorbing material of full-inorganic using caesium, lithium or ammonium cation, although energy The environmental stability of Ca-Ti ore type light absorbing material is enough improved, but photoelectric transformation efficiency is greatly reduced.
Ring phosphonitrile is the compound that a class is alternately arranged the ring-type as main chain with nitrogen phosphorus double bond, and its property is between inorganization Between compound, organic compound and macromolecular compound, can be polymerized to form inorganic macromolecule compound.Most commonly ring phosphorus Nitrile halogenide, molecular formula is (NPX2)n, wherein, n=3-7, X=Cl, Br, I, F or its mixture.It can also be used as perovskite The inorganic cation of photoelectric conversion material or light absorbing material, forms novel photoelectric transition material, it is expected to while carrying with lead halide The environmental stability and photoelectric transformation efficiency of high Ca-Ti ore type photoelectric conversion material, but also do not carry out both at home and abroad correlational study and Explore.
First obtained Phosphonitrile halide compounds is exactly hexachlorocyclotriph,sphazene (NPCl2)3, by phosphorus pentachloride and ammonium chloride four Ethyl chloride（Or chlorobenzene）Heating reflux reaction certain hour is obtained in solvent.Hexachlorocyclotriph,sphazene is nitrogen and alternate six members of phosphorus Ring, it is almost a planar rings, and the chlorine on phosphorus is not in the plane that nitrogen phosphorus is constituted, and its many property is similar to benzene.
Before the document report synthesis phosphonitrile of ring two, hexachlorocyclotriph,sphazene is considered as always ring-type minimum in phosphonitrile Thing.Up to the present obtained other ring chlorophosphonitrile halogenide also have N4P4Cl8 、N5P5Cl10 、N6P6Cl12 、 N7P7Cl14And N8P8Cl16.(NPCl under normal circumstances2)nIt is solid cyclic phosphonitrile halogenation as n=3-7 in Phosphonitrile halide compounds Thing；N=8-15 is the linear Phosphonitrile halide compounds of oily.Being reacted by phosphorus pentabromide and ammonium bromide can be obtained the phosphonitrile of hexabromo ring three, and eight The synthesis of the phosphonitrile of bromine ring four also has been reported that.Phosphorus chloride eyeball has Sodium Chloride to generate with sodium iodide reaction, thus it is speculated that may have iodo ring phosphorus Nitrile is generated.The perfluor that n=3-7 is obtained at present replaces ring phosphonitrile, while being also prepared for the ring that various different halogen mixing replace Phosphonitrile.
There is a lone electron pair in ring Phosphonitrile halide compounds on nitrogen-atoms, may act on metallic atom, and the base on phosphorus atoms Group also can act on metallic compound, generate phosphonitrile metallic compound.Ring Phosphonitrile halide compounds can be with major element and some transition Metallic compound interacts, for example, [N3P3Cl5]+[ AlCl4]-It is entirely interionic effect；And [N3P3Br6][AlBr3] It is to be interacted by covalent bond between two compounds；N3P3(CH3)6SnCl4And N3P3(CH3)6TiCl4Speculate may be five, six Coordination, N participates in the structure of coordination on ring.Ring Phosphonitrile halide compounds can with H+Cation, and metallic compound are formed for correspondence Anion.
The content of the invention
It is an object of the invention to provide a kind of novel photoelectric changes composite sol, from Ca-Ti ore type photoelectric conversion material Composition and the aspect of microstructure two improve its performance, prepare needs to adapt to large area perovskite solar cell light absorption layer.
The present invention is mixed with Ca-Ti ore type opto-electronic conversion composite sol using ring Phosphonitrile halide compounds and methylamine first, Perovskite light absorbing material band gap and filming performance are adjusted, colloidal sol is by lead halide（PbX2）, ring Phosphonitrile halide compounds (NPX2)n, methylamine Halogen acid salt（CH3NH3X）, dehydration catalyst and organic solvent composition, each component mol ratio is as follows in colloidal sol：
PbX2 1
(NPX2)n 0.1-0.5
CH3NH3X 0.5-0.8
Dehydration catalyst 0.01-0.05
Nano-oxide 0.01-0.05
Organic solvent 20-60.
PbX in the present invention2It is to form Ca-Ti ore type opto-electronic conversion composite (NPX2)nPbX2And CH3NH3PbX3Original Material, is commercially available chemical reagent.
It is (NPX that medium ring Phosphonitrile halide compounds of the present invention are molecular formula2)nRing Phosphonitrile halide compounds, wherein, n=3-7, X=Cl, Br, I, F or its mixture.Lead halide can be with the calcium of a halogen atom reaction generation three dimensional structure in ring Phosphonitrile halide compounds molecule Titanium ore type photoelectric conversion material NnPnX2n-1PbX3, lead halide also can be with two halogen atom reactions in ring Phosphonitrile halide compounds molecule Generate the Ca-Ti ore type photoelectric conversion material N of two-dimensional layered structurenPnX2n-2PbX4, it is also possible in ring Phosphonitrile halide compounds molecule Multiple halogen atoms react to form labyrinth, make the sunlight wavelength that the photoelectric conversion material to be formed has wider light absorb model Enclose.Due to the stability of ring phosphonitrile, its perovskite photoelectric conversion material for being formed will be with more preferable wet-heat resisting and ultraviolet resistance The characteristics such as decomposition.
Methylamine halogen acid salt is that methylamine is generated with halogen acids reaction in colloidal sol of the present invention.
Dehydration catalyst is one of Bis(methoxy)magnesium, Diethoxymagnesium, triethyl aluminum or aluminum alkoxide in the present invention, is commercially available chemistry examination Agent.For maintaining colloidal sol in alkalescence, ring Phosphonitrile halide compounds are promoted to be formed with being compound, while producing nano oxygen with lead halide Compound particle.
Nano-oxide is the nanometer oxide particle that dehydration catalyst hydrolysis is generated in colloidal sol of the present invention, can be used as calcium Nucleus during titanium ore type photoelectric conversion material film forming, changes photoelectric conversion material microstructure and prevents from forming thick crystallization.
Organic solvent is that acetonitrile, dimethylformamide, gamma-butyrolacton or dimethyl sulfoxide and C1-C4 are fatty in the present invention The mixture of alcohol.Polar solvent is used to dissolve PbX2、(NPX2)nPbX2And CH3NH3PbX3, C1-C4 fatty alcohol as dilute it is molten Agent, is commercially available chemical reagent.
There is halogenation lead molecule, methylamine halogen acid salt molecule and ring Phosphonitrile halide compounds molecule in colloidal sol of the present invention, and it is few (NPX of the amount with inorganic nano-particle as nucleus2)nPbX2And CH3NH3PbX3Micelle or crystal seed, when solvent volatilizees, make in coordination With under, the common driving of hydrogen bond, Van der Waals force, halogenation lead molecule, methylamine halogen acid salt molecule and ring Phosphonitrile halide compounds molecule exist Ca-Ti ore type opto-electronic conversion composite material film is self-assembly of on crystal seed.
The reaction mechanism of halogenation lead molecule and ring Phosphonitrile halide compounds molecule is not clear in the present invention, first adopts in the present invention Methylamine maintains solution to be catalyzed complex reaction in the basic conditions to be carried out, and is subsequently adding in halogen acids and methylamine, in neutral conditions Catalysis complex reaction is carried out, and being eventually adding dehydrant and being further catalyzed complex reaction is carried out.Excessive methylamine halogen acid salt can be with Ring Phosphonitrile halide compounds react, so, the process condition range of the preparation process is relatively wide, and properties of product are stable and are easier to control System.
It is a further object of the present invention to provide a kind of novel photoelectric changes the preparation method of composite sol, technical scheme Comprise the following steps：
（1）Polar organic solvent, methylamine and PbX are separately added in glass reactor2, stir at 60-80 DEG C to completely molten Solution, is subsequently adding ring Phosphonitrile halide compounds, and controlling raw material molar ratio is：PbX2：Methylamine：Ring Phosphonitrile halide compounds=1:0.8- 0.9:0.1-0.5, stirring reaction 12-24 h, obtains (NPX2)n PbX2Solution；
（2）Halogen acid solution is added in above reactant liquor, controlling raw material molar ratio is：Methylamine：HX =1：1, continue Stirring reaction 12-24 h, is cooled to room temperature, obtains (NPX2)nPbX2And CH3NH3PbX3Mixed solution；
（3）Dehydration catalyst is added in above reactant liquor, controlling raw material molar ratio is：PbX2：Dehydration catalyst=1: 0.02-0.05, dehydration catalyst forms nanometer oxide particle colloidal sol with reaction of moisture 1-4h in solution, and particle diameter is 5- 10nm；
（4）C1-C4 fatty alcohol is added in above reactant liquor to PbX2Saturation is separated out, and becomes cloudy colloidal sol, then in 80-100 Flow back 12-24 h at DEG C, generates and contains (NPX2)nPbX2And CH3NH3PbX3The colloidal sol of crystal seed, the quality percentage of solid in colloidal sol Concentration is 10%-20%；
（5）With biscuit ware funnel secondary filter composite sol, with dropper by colloidal sol drop in the 200mm of compacted zone × It is uniform with the coating of stainless steel wire rod coating device in 300mm fluorine-doped tin dioxide Conducting Glass, dry solvent volatilization, most Afterwards 110-150 DEG C of hot air drying 30 minutes, forms the smooth black Ca-Ti ore type light absorbing zone in surface, assembling test perovskite Solar cell, adopts (NPX2)nPbX2And CH3NH3PbX3Composite ratio adopts merely CH3NH3PbX3Opto-electronic conversion effect during material Rate improves 1.8%-2.2%.
The absorbing properties of the photoelectric conversion material thin film type spectrophotometer test specimens of Lambda 920 in the present invention Absorbance of the product in 250-1100nm wave-length coverages determines；The assembling of test perovskite solar cell refers to Chinese invention patent Application 2019109316795（2016-10-25）The method of middle employing is carried out；Efficiency of solar cell is using the small-sized sun for customizing Battery component tester simulated solar optical tests.
Beneficial effects of the present invention are embodied in：
（1）The present invention improves its performance in terms of Ca-Ti ore type opto-electronic conversion composition and microstructure two, adapts to large area calcium titanium Prepared by ore deposit solar cell light absorption layer need；
（2）The present invention prepares new perovskite photoelectric conversion material with ring Phosphonitrile halide compounds, and preparation process condition scope is relatively wide, The photoelectric conversion material of synthesis has more preferable environmental stability, can reduce the size effect of large area perovskite solar cell Should；
（3）The present invention is mixed with Ca-Ti ore type photoelectric conversion material with ring Phosphonitrile halide compounds and methylamine, can extend to the sun The light absorption wavelength scope and raising photoelectric transformation efficiency 1.8%-2.2% of light.
Specific embodiment
Embodiment 1
Acetonitrile 246g (6mol) is separately added in the 500mL glass reactors of band stirring, the methylamine of mass percentage concentration 30% Methanol solution 8.29g (0.08mol) and lead iodide 46.1g (0.1mol), stirs 2h to being completely dissolved, then at 60-80 DEG C Hexachlorocyclotriph,sphazene 6.95g (0.02mol) is added, continues the h of stirring reaction 24, obtain N3P3Cl5PbI2Cl solution；Add The hydroiodic acid 46.1g (0.08mol) of mass percentage concentration 50%, continues the h of stirring reaction 12, is cooled to room temperature, obtains N3P3Cl5PbI2Cl and CH3NH3PbI3Mixed light absorbent solution.
Methanol magnesium solution 29.2g (0.05mol) that mass percentage concentration is 20%, Bis(methoxy)magnesium are added in above reactant liquor Bitter earth nano colloidal sol is formed with reaction of moisture 4h, particle diameter is 10nm.Dehydrated alcohol is continuously added to PbI2Saturation is separated out, Colloidal sol is set to be in slightly cloudy, then flow back 24 h at 75-80 DEG C, generation contains N3P3Cl5PbI2Cl and CH3NH3PbI3Crystal seed Colloidal sol.With G5 biscuit ware funnel secondary filter light absorbing material colloidal sols, with dropper by colloidal sol drop in the 200mm of compacted zone × It is uniform with the coating of stainless steel wire rod coating device in 300mm fluorine-doped tin dioxide Conducting Glass, dry solvent volatilization, most Afterwards 110-150 DEG C of hot air drying 30 minutes, forms the smooth black perovskite light absorbing zone in surface, as assembling test calcium titanium Ore deposit solar cell, than simple CH3NH3PbX3Material photoelectric transformation efficiency improves 1.8%.
Embodiment 2
Dimethylformamide 365.5g (5mol), mass percentage concentration are separately added in the 500mL glass reactors of band stirring The methanol solution 5.18g (0.05mol) and lead iodide 46.1g (0.1mol) of 30% methylamine, stirs 2h to complete at 60-80 DEG C CL, is subsequently adding hexachlorocyclotriph,sphazene 17.4g (0.05mol), continues the h of stirring reaction 24, obtains N3P3Cl5PbI2Cl Solution；The hydroiodic acid 28.8g (0.05mol) of mass percentage concentration 50% is added, continues the h of stirring reaction 16, be cooled to room Temperature, obtains N3P3Cl5PbI2Cl and CH3NH3PbI3Mixed light absorbent solution.
Methanol magnesium solution 29.2g (0.05mol) that mass percentage concentration is 20%, Bis(methoxy)magnesium are added in above reactant liquor Bitter earth nano colloidal sol is formed with reaction of moisture 4h, particle diameter is 10nm.Dehydrated alcohol is continuously added to PbI2Saturation is separated out, Colloidal sol is set to be in slightly cloudy, then flow back 24 h at 75-80 DEG C, generation contains N3P3Cl5PbI2Cl and CH3NH3PbI3Crystal seed Colloidal sol.With G5 biscuit ware funnel secondary filter light absorbing material colloidal sols, with dropper by colloidal sol drop in the 200mm of compacted zone × It is uniform with the coating of stainless steel wire rod coating device in 300mm fluorine-doped tin dioxide Conducting Glass, dry solvent volatilization, most Afterwards 110-150 DEG C of hot air drying 30 minutes, forms the smooth black perovskite light absorbing zone in surface, as assembling test calcium titanium Ore deposit solar cell, than simple CH3NH3PbX3Material photoelectric transformation efficiency improves 2.2%.

Claims (4)

1. a kind of novel photoelectric changes composite sol, it is characterised in that be mixed with calcium using ring Phosphonitrile halide compounds and methylamine Titanium ore type opto-electronic conversion composite sol, by lead halide, ring Phosphonitrile halide compounds, methylamine halogen acid salt, dehydration catalyst and has Machine solvent is constituted, and each component mol ratio is as follows in colloidal sol：
Lead halide 1
Ring Phosphonitrile halide compounds 0.1-0.5
Methylamine halogen acid salt 0.5-0.8
Dehydration catalyst 0.01-0.05
Nano-oxide 0.01-0.05
Organic solvent 20-60.
2. novel photoelectric as claimed in claim 1 changes composite sol, it is characterised in that ring Phosphonitrile halide compounds are molecular formula For (NPX2)nRing Phosphonitrile halide compounds, wherein, n=3-7, X=Cl, Br, I, F or its mixture.
3. novel photoelectric as claimed in claim 1 changes composite sol, it is characterised in that lead halide and ring phosphonitrile in colloidal sol Halogenide reacts the N that the Ca-Ti ore type photoelectric conversion material to be formed is three dimensional structurenPnX2n-1PbX3Or two-dimensional structure NnPnX2n-2PbX4, wherein, n=3-7.
4. novel photoelectric described in a kind of claim 1 changes the preparation method of composite sol, it is characterised in that technology of preparing Scheme is comprised the following steps：
（1）Polar organic solvent, methylamine and PbX are separately added in glass reactor2, stir at 60-80 DEG C to completely molten Solution, is subsequently adding ring Phosphonitrile halide compounds, and controlling raw material molar ratio is：PbX2：Methylamine：Ring Phosphonitrile halide compounds=1:0.5- 0.9:0.1-0.5, stirring reaction 12-24 h, obtains (NPX2)n PbX2Solution；
（2）Halogen acid solution is added in above reactant liquor, controlling raw material molar ratio is：Methylamine：HX = 1：1, continue Stirring reaction 12-24 h, is cooled to room temperature, obtains (NPX2)nPbX2And CH3NH3PbX3Mixed solution；
（3）Dehydration catalyst is added in above reactant liquor, controlling raw material molar ratio is：PbX2：Dehydration catalyst=1： 0.02-0.05, dehydration catalyst forms nanometer oxide particle colloidal sol with reaction of moisture 1-4h in solution, and particle diameter is 5- 10nm；
（4）C1-C4 fatty alcohol is added in above reactant liquor to PbX2Saturation is separated out, and becomes cloudy colloidal sol, then at 80-100 DEG C Lower backflow 12-24 h, generate and contain (NPX2)nPbX2And CH3NH3PbX3The colloidal sol of crystal seed, the quality percentage of solid is dense in colloidal sol Spend for 10%-20%；
（5）With biscuit ware funnel secondary filter composite sol, with dropper by colloidal sol drop in the 200mm of compacted zone × It is uniform with the coating of stainless steel wire rod coating device in 300mm fluorine-doped tin dioxide Conducting Glass, dry solvent volatilization, most Afterwards 110-150 DEG C of hot air drying 30 minutes, forms the smooth black Ca-Ti ore type light absorbing zone in surface, assembling test perovskite Solar cell, adopts (NPX2)nPbX2And CH3NH3PbX3Composite ratio adopts merely CH3NH3PbX3Opto-electronic conversion effect during material Rate improves 1.8%-2.2%.
CN201610997981.0A 2016-11-14 2016-11-14 Novel photoelectric conversion composite material sol and preparation method thereof Pending CN106571427A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115286939A (en) * 2022-08-01 2022-11-04 昆山协鑫光电材料有限公司 Lead-free tin-based halide perovskite thin film, composition for preparation, preparation method and application

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
梁文俊等: "磷腈类化合物的合成及应用研究进展", 《化工新型材料》 *
洪育林: "六氯环三磷腈及其衍生物的合成及性能研究", 《华中科技大学硕士学位论文》 *
胡富贞: "具有光电活性聚磷腈的合成与性能研究", 《华中科技大学硕士学位论文》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115286939A (en) * 2022-08-01 2022-11-04 昆山协鑫光电材料有限公司 Lead-free tin-based halide perovskite thin film, composition for preparation, preparation method and application
CN115286939B (en) * 2022-08-01 2024-02-23 昆山协鑫光电材料有限公司 Lead-free tin-based halide perovskite film, preparation composition, preparation method and application

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