CN109768170A

CN109768170A - A kind of preparation method of perovskite solar battery

Info

Publication number: CN109768170A
Application number: CN201910061416.7A
Authority: CN
Inventors: 原秀玲; 王立武
Original assignee: Individual
Current assignee: Individual
Priority date: 2019-01-23
Filing date: 2019-01-23
Publication date: 2019-05-17

Abstract

A kind of preparation method of perovskite solar battery, the battery uses p-i-n structure, including ito glass, hole transport layer, perovskite structure absorbed layer, electron transport layer, back electrode, the hole transmission layer uses carbazole triphenylamine analog derivative phosphonic acids, which can be with ITO substrate rigid contact and can effective transporting holes；The preparation of perovskite absorbed layer uses two-step method, passes through strict control water content and anneal gas atmosphere in preparation process, has obtained the film of large scale crystal grain and flat-satin, finally prepared the battery device of high quality and high efficiency.

Description

A kind of preparation method of perovskite solar battery

Technical field

The present invention relates to a kind of preparation methods of perovskite solar battery, belong to photovoltaic manufacturing technology field.

Background technique

Increasingly shortage and environmental pollution recently as fossil energy it is increasingly severe, human development renewable energy Step is getting faster, and solar photovoltaic technology achieves fast development.Especially from organic inorganic hybridization halogenation in 2009 Since object perovskite material is used for solar-energy photo-voltaic cell, transfer efficiency is quickly improved, at present 0.1 square centimeter of laboratory face Long-pending efficiency alreadys exceed 23%, shows the great potential for being different from conventional crystal silicon and hull cell.According to light Sequencing, conventional perovskite battery is usually n-i-p structure, successively includes TCO conductive substrates, electron transfer layer, calcium titanium Mine absorbed layer, hole transmission layer, back electrode, there are some problems for n-i-p structure device, such as its electron transfer layer generallys use Fine and close TiO2, preparation process need to be unfavorable for preparing flexible device by high-temperature heating；The voltage and current of device exists back Stagnant phenomenon；Hole transport layer material is costly and unstable, back electrode needs the noble metals such as Au or Ag.Therefore, scientific and technical personnel are again Develop the perovskite battery device of p-i-n structure, successively include TCO conductive substrates, hole transmission layer, perovskite absorbed layer, Electron transfer layer, back electrode, hole-transporting layer generally selects PEDOT:PSS or PTAA, however PEDOT:PSS has centainly Hygroscopicity and acidity, unfavorable to the stability of device, PTAA is expensive, has absorption at visible light shortwave and by subsequent handling It is affected.In order to improve the performance of p-i-n perovskite battery, on the one hand needs to select suitable hole mobile material, both need It is completely covered and is firmly combined with TCO substrate, otherwise it is low to open pressure drop for device；Thickness can not be too thick, and otherwise own absorption is big Influence transmitance；Certainly level-density parameter, hole mobility height etc. are also needed；On the other hand, perovskite absorbs the preparation of layer film Quality wants high, needs that crystal grain is big, defect is low, to improve photoelectric conversion efficiency.

Summary of the invention

It is an object of the invention to use suitable hole mobile material, well-designed preparation step, to produce The perovskite solar battery of high-performance high quality.

Technical scheme is as follows: a kind of preparation method of perovskite solar battery, which uses p-i-n junction Structure, including ito glass, hole transmission layer, perovskite structure absorbed layer, electron transport layer, back electrode, the hole transmission layer are adopted With carbazole triphenylamine analog derivative phosphonic acids, general formula of the chemical structure are as follows:

Wherein, R is benzene derivate；The perovskite structure absorbed layer is CH₃NH₃PbI₃, electron transport layer is mixed with fullerene Derivative PCBM, battery preparation step are as follows:

The first step, ito glass cleaning: using ito glass as substrate, successively using deionized water, acetone, isopropanol, ultrasound is clear respectively 3-5min is washed, with being dried with nitrogen, ozone plasma is then carried out and cleans 5-10min, it is spare；

Second step, hole transmission layer growth: the carbazole triphenyl amine that sample obtained by the first step is immersed in 0.005mol/L is spread out 50 DEG C of heat preservations stand 10-20h in biological phosphonic acids and the aqueous isopropanol of normal-butyl phosphonic acids mixing, take out 100 DEG C of annealing 1h, then It is rinsed with isopropanol；

Third step, the preparation of perovskite absorbed layer: the sample that second step is obtained is preheating to 100 DEG C, the spin coating under 2000rpm revolving speed The PbI of 85 DEG C of 1mol/L is added dropwise₂/ dimethylformamide/water precursor solution 30s stands 1min；Then turn in 2000rpm The CH of 80 DEG C of 0.5mol/L is added dropwise in the lower spin coating of speed₃NH₃I/ isopropanol/water precursor solution 20s stands 1min；Then lining is kept Bottom temperature 60 C is annealed 10min under DMF atmosphere, then heats underlayer temperature to 100 DEG C of 10min that anneal under air atmosphere, Obtain perovskite absorbed layer；

4th step, electron transport layer preparation: 2% mass fraction is added dropwise in the sample that third step is obtained spin coating under 1000rpm revolving speed Mixed with fullerene derivative PCBM chlorobenzene solution 30s, then stand 12h under chlorobenzene atmosphere；

5th step, back electrode deposition: it using aluminium film back electrode is deposited on the method perovskite absorbed layer of electron beam evaporation, obtains Perovskite solar battery.

Further, the R is benzene derivate, including 2,4,6- trimethylphenyls, and p-methoxyphenyl, to tert-butyl One of phenyl.

Further, in the second step substance of carbazole triphenylamine analog derivative phosphonic acids and normal-butyl phosphonic acids amount it Than for 1:9.

Further, PbI in the third step₂In/dimethylformamide/water precursor solution, relative to dimethyl methyl Amide, the mass fraction of water are 2%.

Further, CH in the third step₃NH₃In I/ isopropanol/water precursor solution, relative to isopropanol, the body of water Fraction is 0.5%.

Beneficial effects of the present invention: the present invention prepares sky using carbazole triphenylamine analog derivative phosphonic acids on the surface ITO Cave transport layer, prepares that growth conditions is mild, and the oxygen atom on phosphonate functional group therein and the surface ITO can form firm P-O The big conjugated system of chemical bond, carbazole triphenylamine analog derivative effectively can be extracted and be transmitted to hole, to make It is the comprehensive uniform fold that can reach to ITO that hole mobile material, which is obtained, with the smallest dosage and thickness, material utilization amount is saved, certainly Body is minimized the absorption of incident light, and combined by way of P-O covalent bond between cavitation material and ITO it is very secured, Hardly by it is subsequent prepare perovskite absorbed layer when used solvent effect.

Two-step method is used when preparing perovskite absorbed layer, uses PbI first₂Dimethyl formamide solution and control contain Water prepares PbI₂Then film uses CH again₃NH₃The aqueous isopropanol of I simultaneously controls water content to grow CH₃NH₃PbI₃Calcium Titanium ore film, due to the accurate control to water content, a small amount of water is conducive to CH₃NH₃I is to PbI₂Film penetrates, thus favorably In CH₃NH₃PbI₃Perovskite crystal grain is grown up, so that the diameter of polycrystalline particle reaches micron dimension in perovskite thin film；Lead to simultaneously The annealing under dimethylformamide atmosphere is crossed, so that the gap between polycrystalline particle becomes smaller, perovskite thin film surface becomes more Add it is flat and smooth, to greatly facilitate effect to the raising of battery device photoelectric properties.

Detailed description of the invention

Fig. 1 perovskite battery structure schematic diagram.

Fig. 2 phosphonate radical is bonded schematic diagram with ITO surface chemistry.

The SEM of Fig. 3 perovskite thin film that not prepared by aqueous solution.

The SEM of the perovskite thin film of the specific moisture content solution preparation of Fig. 4.

The SEM for the perovskite thin film annealed under Fig. 5 particular atmosphere.

The IV curve test of Fig. 6 battery.

Specific embodiment

Illustrate technical solution of the present invention with reference to the accompanying drawings and examples.

Embodiment 1:

A kind of preparation method of perovskite solar battery, which uses p-i-n structure, as shown in Figure 1, from sunlight incident side Start successively to include ito glass, hole transport layer, perovskite structure absorbed layer, electron transport layer, back electrode.Preparation step is such as Under:

The first step, ito glass cleaning:

Supplied materials ito glass is cut into 5cm*5cm, square resistance is 10 Ω, successively using deionized water, acetone, isopropanol point Not Chao Shengqingxi 5min, with being dried with nitrogen, then to ito surface carry out ozone plasma clean 10min, it is spare.

Second step, hole transmission layer growth:

(1) hole transport layer material selects: the material of hole transport layer is carbazole triphenylamine analog derivative phosphonic acids, chemistry General structure are as follows:

Wherein, R is benzene derivate, be can be to tert-butyl-phenyl, p-methoxyphenyl, 2, one in 4,6- trimethylphenyls Kind, to tert-butyl-phenyl, chemical structural formula is as follows for R selection in this example:

(2) growth of hole transport layer: the carbazole triphenyl amine that sample obtained by the first step is immersed in 0.005mol/L is derivative 50 DEG C of heat preservations stand 20h in the aqueous isopropanol of object phosphonic acids and normal-butyl phosphonic acids (the ratio between amount of substance 1:9), 100 DEG C after taking-up Anneal 1h, is then rinsed with isopropanol, i.e., grown the hole transport layer of 2-3nm thickness, chemical reaction bonding on the surface ITO Mechanism schematic diagram is as shown in Figure 2.

Third step, the preparation of perovskite absorbed layer: the sample that second step is obtained is preheating to 100 DEG C, under 2000rpm revolving speed The PbI of 85 DEG C of 1mol/L is added dropwise in spin coating₂/ dimethylformamide/water precursor solution 30s stands 1min, wherein relative to two Methylformamide, the mass fraction of water is 2% in solution；Then the 0.5mol/L of 80 DEG C of spin coating dropwise addition under 2000rpm revolving speed CH₃NH₃I/ isopropanol/water precursor solution 20s stands 1min, wherein the volume fraction of water is in solution relative to isopropanol 0.5%；Then 60 DEG C of the underlayer temperature 10min that anneal under dimethylformamide atmosphere are kept, then heat underlayer temperature to 100 DEG C anneal 10min under air atmosphere, obtains perovskite absorbed layer；In order to compare water content and dimethylformamide ambient anneal Influence to the perovskite thin film of growth, we have observed the electron scanning micrograph of different samples respectively.Fig. 3 be without The SEM of the perovskite thin film of aqueous solution preparation, Fig. 4 are the SEM of the perovskite thin film of specific moisture content solution preparation, and Fig. 5 is The SEM for the perovskite thin film annealed under dimethylformamide particular atmosphere.It can be seen from the figure that specific moisture content solution system The size of standby perovskite crystal grain reaches micron dimension than rising appreciably under not aqueous conditions；And in dimethylformamide spy Determine the gap between the crystal grain for the perovskite thin film annealed under atmosphere and obtained apparent repairing and elimination, film surface is more flat It is whole smooth.

4th step, electron transport layer preparation: 2% mass is added dropwise in the sample that third step is obtained spin coating under 1000rpm revolving speed The mixed with fullerene derivative PCBM chlorobenzene solution 30s of score, then stands 12h under chlorobenzene atmosphere.

5th step, back electrode deposition: using on the method perovskite absorbed layer of electron beam evaporation deposit aluminium film back electrode, Obtain perovskite solar battery.

The IV curve performance of forward and reverse voltage scanning of the perovskite battery of above-mentioned preparation is tested as shown in fig. 6, figure is from can See, device there's almost no hysteresis phenomenon, and open-circuit voltage reaches 1.03V, and short-circuit current density reaches 23.8mA/cm², filling because Son 81%, the transfer efficiency of battery reaches 19.8%, is a kind of very promising perovskite cell manufacturing method.

Claims

1. a kind of preparation method of perovskite solar battery, which uses p-i-n structure, including ito glass, hole transport Layer, perovskite structure absorbed layer, electron transport layer, back electrode, it is characterised in that: the hole transmission layer uses carbazole triphenyl Amine derivant phosphonic acids, general formula of the chemical structure are as follows:

Wherein, R is benzene derivate；

The perovskite structure absorbed layer is CH₃NH₃PbI₃, electron transport layer is mixed with fullerene derivative PCBM, the system of battery It is standby that steps are as follows:

Second step, hole transmission layer growth: the carbazole triphenyl amine that sample obtained by the first step is immersed in 0.005mol/L is spread out 50 DEG C of heat preservations stand 10-20h in the aqueous isopropanol of biological phosphonic acids and normal-butyl phosphonic acids mixing composition, then take out 100 DEG C and move back Fiery 1h, is then rinsed with isopropanol；

2. a kind of preparation method of perovskite solar battery according to claim 1, it is characterised in that: the R is benzene Derivative, specially to tert-butyl-phenyl, 2, one kind of 4,6- trimethylphenyls and p-methoxyphenyl.

3. a kind of preparation method of perovskite solar battery according to claim 1, it is characterised in that: the second step The ratio between amount of substance of middle carbazole triphenylamine analog derivative phosphonic acids and normal-butyl phosphonic acids is 1:9.

4. a kind of preparation method of perovskite solar battery according to claim 1, it is characterised in that: the third step Middle PbI₂In/dimethylformamide/water precursor solution, relative to dimethylformamide, the mass fraction of water is 2%.

5. a kind of preparation method of perovskite solar battery according to claim 1, it is characterised in that: the third step Middle CH₃NH₃In I/ isopropanol/water precursor solution, relative to isopropanol, the volume fraction of water is 0.5%.