CN106654020B - Bulk heterojunction perovskite thin film and preparation method thereof and solar battery - Google Patents
Bulk heterojunction perovskite thin film and preparation method thereof and solar battery Download PDFInfo
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- CN106654020B CN106654020B CN201710060215.6A CN201710060215A CN106654020B CN 106654020 B CN106654020 B CN 106654020B CN 201710060215 A CN201710060215 A CN 201710060215A CN 106654020 B CN106654020 B CN 106654020B
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Abstract
The present invention relates to bulk heterojunction perovskite thin film and preparation method thereof and solar batteries, the bulk heterojunction perovskite thin film includes: bulk heterojunction layer, and the bulk heterojunction layer includes the electron acceptor material of the perovskite polycrystal film as electron donor material and the grain boundary sites positioned at the perovskite polycrystal film；And the perovskite thin film layer positioned at the bulk heterojunction layer surface.When bulk heterojunction perovskite thin film of the invention is applied to perovskite solar battery, it can replace existing mesoporous electron transfer layer and perovskite light-absorption layer, so as to simplify the structure of battery, high-sintering process needed for independent mesoporous layer preparation process can also be avoided, suitable for preparing high-efficiency flexible perovskite solar battery in ductile basement.
Description
Technical field
The invention belongs to technical field of solar batteries more particularly to a kind of preparation method of film used for solar batteries,
More specifically, it is related to a kind of bulk heterojunction perovskite thin film and corresponding perovskite solar battery and preparation method thereof.
Background technique
It is growing day by day for the demand of the energy with the development of human society.Solar energy as it is a kind of cleaning, it is free of contamination
The energy, by extensive concern both domestic and external and further investigation.Solar battery based on hybrid inorganic-organic perovskite thin film is
A kind of novel solar battery that developed recently gets up, advantage are very prominent: 1, prepared by hybrid inorganic-organic perovskite material
Simple process, cost is relatively low；2, there is regulatable band gap；3, the electron hole mobility of balance, high quantum luminous efficiency
With biggish defect tolerant degree；4, translucent battery or flexible battery be can be made into, be easy to integrated with other devices, application scenarios are big
It widens greatly.Therefore, perovskite solar battery and associated materials have become an important research direction of photovoltaic art, obtain at present
The authentication efficiency for obtaining 22.1%, has a extensive future.
There are mainly three types of the structures that perovskite solar battery generallys use at present: plate, mesoporous type and transconfiguration.
The outstanding feature of transconfiguration is to lag smaller or do not lag, but efficiency is not relatively high.The plate calcium of formal structure
Titanium ore battery lag is larger, although using fullerene, SnO2Equal materials reduce or eliminate to lag after hole blocking layer, but electric
Pond efficiency could not also be more than Jie's pass structure.The perovskite solar battery of Jie's pass structure mesh in terms of lag is eliminated with efficiency
It is preceding that there is advantage, but one layer of independent mesoporous layer is needed in battery structure.On the one hand, the preparation process of mesoporous layer often will be
(such as 500 DEG C) sintering processes under higher temperature hinder it and prepare flexible perovskite solar battery in ductile basement.It is another
Aspect, the elimination situation of battery lag relies on filling situation of the perovskite crystal grain in mesoporous layer, if filling is insufficient, lag is very
Difficulty completely eliminates.In addition, for the battery based on the above structure, perovskite ABX3The preparation method of film to its film morphology,
Charge mobility, electron lifetime and photoelectric conversion performance are affected.For example, current step solwution method reported in the literature, two
The preparation methods such as solwution method, vapour deposition process and gas phase assisted solution method are walked, are the perovskite thin films to obtain smooth densification
For target.If prepared film pin-hole like defects are more, the compound of charge in film is easily caused, the performance of film is seriously affected.
This not only increases the preparation difficulty of perovskite thin film, and is unfavorable for prepare with scale and yield rate control.CN
104201284 A disclose a kind of integrated solar cell based on perovskite solar cell and bulk heterojunction solar cell, described
Integrated solar cell successively includes transparent electrode, hole transmission layer, perovskite light-absorption layer, organic matter blended layer, appoints from bottom to top
Selection of land hole blocking layer and metal electrode, wherein the organic matter blended layer refers to bulk heterojunction solar cell donor material
With the hybrid films of acceptor material, donor material is the conjugation for being less than 1.5eV applied to the optical band gap of bulk heterojunction solar cell
Polymer or/and small molecule, preferably any one in PDPP3T, PMDPP3T, PDPPBTT or PDTP-DFBT or at least two
The mixture of kind.The battery structure is the laminated cell of perovskite solar cell and bulk heterojunction solar cell, chief active material
Material perovskite material does not form the structure of bulk heterojunction as electron donor.
Summary of the invention
Present invention seek to address that being proposed a kind of new using the battery structure of open report and the deficiency of preparation method at present
The battery structure and its implementation based on bulk heterojunction perovskite thin film, which does not need independent mesoporous layer,
It can reach the performance of mesoporous type perovskite solar battery, and the letter of the preparation method of the type perovskite thin film and battery
Single, the reproducibility of institute's assembled battery is high.
Here, the present invention provides a kind of bulk heterojunction perovskite thin film, the bulk heterojunction perovskite thin film includes:
Bulk heterojunction layer, the bulk heterojunction layer include the perovskite polycrystal film as electron donor material and are located at
The electron acceptor material of the grain boundary sites of the perovskite polycrystal film；And
Positioned at the perovskite thin film layer of the bulk heterojunction layer surface.
Bulk heterojunction layer electronics Extracting Ability in the present invention is strong, can play the mesoporous electronics in existing perovskite battery
The effect of transport layer and perovskite light-absorption layer；Meanwhile the surface of bulk heterojunction layer also has perovskite thin film layer, such as when body is different
When being formed with hole transmission layer on matter knot perovskite thin film, which can play a protective role, and prevent body heterogeneous
Electron acceptor material in knot layer contacts with hole mobile material and leads to short circuit.By bulk heterojunction perovskite thin film of the invention
When applied to perovskite solar battery, existing mesoporous electron transfer layer and perovskite light-absorption layer can be replaced, so as to
To simplify the structure of battery, high-sintering process needed for independent mesoporous layer preparation process can also be avoided, is suitable in plasticity
High-efficiency flexible perovskite solar battery is prepared in substrate.After tested, using bulk heterojunction perovskite thin film of the invention
The photoelectric conversion efficiency of perovskite solar battery has independent mesoporous electron transfer layer and perovskite light-absorption layer with existing
Perovskite battery it is suitable or even its photoelectric conversion efficiency has been more than 17%.
Preferably, the molar ratio of electron donor material and electron acceptor material is 0.5~15:1 in bulk heterojunction layer.
Preferably, the chemical composition of the perovskite polycrystal film and/or the perovskite thin film layer is ABX3, wherein A
For monovalent cation or mixed-cation, preferably CH3NH3 +、NH2- CH=NH2 +、Cs+、Li+、C4H9NH3 +、CH6N3 +、Na+、K+
At least one of；B is Pb2+、Sn2+、Ge2+、Co2+、Fe2+、Mn2+、Cu2+、Ni2+At least one of, i.e., B can be these
One of ion, any two or more mixed structure being also possible in these ions；X is Cl-、Br-、I-、SCN-、BF4 -In
It is at least one, that is, X can be single ionic, be also possible to hybrid ionic, such as the mixing of any two or more ions.Such as
ABX3For MAPbI3、FAPbI3、FA1-xCsxPbI3、CsxMA yFA1-x-yPbI3Deng wherein MA refers to CH3NH3 +, FA refers to NH2- CH=
NH2 +。
Preferably, the electron acceptor material is nanocrystalline TiO2, nanocrystalline SnO2, Nanocrystalline ZnO Powder, fullerene, fullerene
Derivative, acid imide, naphthalimide, organic macromolecule acceptor material, graphene, carbon black, stone based on expansion thiophene condensed ring
Ink, nano-crystalline Fe2O3, nanocrystalline ZnSnO3, nanocrystalline CdS, at least one of nanocrystalline CdSe.
Preferably, the thickness of the bulk heterojunction perovskite thin film is in 100~700nm.
The present invention also provides a kind of preparation methods of above-mentioned bulk heterojunction perovskite thin film, comprising:
First perovskite precursor solution and electron acceptor material are mixed to get perovskite/electron acceptor material dispersion
Liquid；
By the perovskite/electron acceptor material dispersion in substrate, before being coated with the second perovskite thereon
Liquid solution is driven, bulk heterojunction precursor thin-film is formed；
The bulk heterojunction precursor thin-film is subjected to crystallization treatment, obtains the bulk heterojunction perovskite thin film.
In the present invention, bulk heterojunction perovskite thin film is prepared using solwution method, the bulk heterojunction perovskite thin film is with calcium titanium
Pit wood material is electron donor material, and electron acceptor material is located at the grain boundary sites of perovskite polycrystal film, and in bulk heterojunction
Surface form fine and close perovskite thin film layer.The strong electronics Extracting Ability of nanoparticulate electron acceptor material makes itself and perovskite
Crystal grain shares density of electronic states, and plays pinning effect in perovskite grain boundaries, to reduce electricity caused by the defect of grain boundaries
Lotus is compound.Independent mesoporous layer is not needed using the battery structure of bulk heterojunction perovskite thin film of the invention, that is, can reach Jie
The performance of pass perovskite solar battery, after tested, using the perovskite sun of bulk heterojunction perovskite thin film of the invention
The photoelectric conversion efficiency of energy battery has been more than 17%.Moreover, can also be avoided independent mesoporous using bulk heterojunction perovskite thin film
High-sintering process needed for layer preparation process, suitable for preparing high-efficiency flexible perovskite solar-electricity in ductile basement
Pond.And the preparation method of the type perovskite thin film and battery is simple, and the reproducibility of institute's assembled battery is high, with traditional perovskite
Film is compared, and preparation method is simpler, and film quality is more easier to control, and overcomes traditional structure complex process and to calcium titanium
The higher problem of the flatness requirement of mine film is suitable for large-scale production application.
Preferably, the preparation of the first perovskite precursor solution and/or the second perovskite precursor solution includes: by B's
Halide solution, the monovalent cation salt of X and the mixing of the first solvent, form perovskite precursor solution, wherein described the
One solvent is to possess oxygen-containing group solvent, preferably dimethylformamide (DMF), dimethyl sulfoxide (DMSO), gamma-butyrolacton (GBL),
At least one of n-methyl-2-pyrrolidone.
Preferably, in the film forming procedure of the bulk heterojunction precursor thin-film, further include in due course machine in film table
The step of the second solvent is added dropwise in face, and second solvent is in ether, n-hexane, petroleum ether, toluene, chlorobenzene, dichlorotoleune
At least one.
Preferably, the crystallization treatment uses heat treatment mode or non-heat treated mode, the heat treatment mode is heat
Plate heating, baking oven heating, sintering stove heating, microwave heating or laser irradiation processing, the temperature of the heat treatment be room temperature~
150 DEG C, the processing time is 0~120 minute, preferably greater than 0 and less than 120 minutes；The non-heat treated mode is solvent volatilization
Induce film crystallization.
In the present invention, electron acceptor material can be added with powder, can also be added with dispersion.
In the present invention, perovskite/electron acceptor material dispersion liquid coating method can be spin-coating method (Spin
Coating), slit extrusion molding (Slot-Die Coating), knife coating (Doctor-Blading Coating) etc..Coating time
Number can be one or many circulation coatings.
The present invention also provides a kind of perovskite solar battery, the perovskite solar battery successively wraps from bottom to top
It includes: electrically conducting transparent substrate, hole blocking layer, above-mentioned bulk heterojunction perovskite thin film, hole transmission layer and top electrode.
Preferably, the substrate is to cover the transparent conductive electrode of hole barrier layer material, the material of transparent conductive electrode
Can be rigidity or flexible, rigid such as FTO glass, ito glass, it is flexible such as with polyethylene naphthalate (PEN), gather
Thin polymer films such as ethylene glycol terephthalate (PET), polyimides (PI), polycarbonate (PC), polyaniline, polypyrrole etc.
For oxidation films transparent conductive films such as the metal system (sputtering type or metal gate net type) of substrate or ITO.
Detailed description of the invention
Fig. 1 shows the SEM cross-section photographs of the body heterojunction perovskite thin film of the embodiment of the present invention 1.
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that following embodiments are only used for
Illustrate the present invention, is not intended to limit the present invention.
The present invention relates to a kind of bulk heterojunction perovskite thin film and corresponding perovskite solar batteries and preparation method thereof.
By coating the perovskite precursor solution and perovskite/electron acceptor material dispersion liquid preparing and obtain in substrate, formed
Bulk heterojunction precursor thin-film, and by carrying out crystallization treatment to bulk heterojunction precursor thin-film, it is heterogeneous to obtain body of the invention
Tie perovskite thin film.Bulk heterojunction film of the invention uses perovskite material for electron donor material, electron acceptor material position
Fine and close perovskite thin film layer is formed in the grain boundary sites of perovskite polycrystal film, and on the surface of bulk heterojunction, with traditional calcium
Titanium ore film is compared, and preparation method is simpler, and film quality is more easier to control, and overcomes traditional structure complex process and right
The higher problem of the flatness requirement of perovskite thin film.It is not required to using the battery structure of bulk heterojunction perovskite thin film of the invention
Independent mesoporous layer is wanted, that is, can reach the performance of mesoporous type perovskite solar battery, can be prepared to avoid independent mesoporous layer
High-sintering process needed for journey.
Fig. 1 shows the SEM cross-section photographs of the body heterojunction perovskite thin film of an example of the present invention.In Fig. 1, from lower past
On successively are as follows: transparent conducting glass (FTO glass), hole blocking layer, bulk heterojunction perovskite thin film.Bulk heterojunction perovskite is thin
Film includes: bulk heterojunction layer, and the bulk heterojunction layer includes as the perovskite polycrystal film of electron donor material and positioned at institute
State the electron acceptor material of the grain boundary sites of perovskite polycrystal film (referring to the particle in Fig. 1)；And it is heterogeneous positioned at the body
Tie the perovskite thin film layer of layer surface.
In the present invention, using perovskite material as electron donor material, with that absorption spectrum is wide and electron mobility is high is excellent
Point.
In the present invention, the chemical composition of perovskite polycrystal film (electron donor material) and perovskite thin film layer can phase
Together, it can also be different, it is preferably identical, it can simplify preparation method in this way, and eliminate the interphase match problem between two layers.Tool
Body, the chemical composition of perovskite polycrystal film (electron donor material) and/or perovskite thin film layer can be ABX3, wherein A can
Using monovalent cation or mixed-cation, including but not limited to CH3NH3 +,NH2- CH=NH2 +,Cs+, Li+, C4H9NH3 +,CH6N3 +, Na+, K+Deng.Pb can be used in B2+,Sn2+, Ge2+, Co2+, Fe2+, Mn2+, Cu2+And Ni2+At least one of, i.e., B can be this
One of a little ions, any two or more mixed structure being also possible in these ions.In one example, ABX3For
ASn1-xPbxX3(0 < x < 1).X can use Cl-, Br-, I-,SCN-,BF4 -At least one of, that is, X can be it is single from
Son is also possible to hybrid ionic, such as the mixing of any two kinds of ions.For example, the chemical composition includes but is not limited to first
Amine lead iodine, carbonamidine lead iodine, methylamine carbonamidine lead iodine mixture, carbonamidine caesium lead iodine, methylamine carbonamidine caesium lead iodine etc..
Electron acceptor material pinning is in the grain boundaries of perovskite polycrystal film.In the present invention, electron acceptor material can be adopted
With nanocrystalline TiO2, nanocrystalline SnO2, Nanocrystalline ZnO Powder, fullerene (C60), fullerene derivate, acid imide, naphthalimide,
Based on organic macromolecule acceptor material, the graphene for expanding thiophene condensed ring, carbon black, graphite, nano-crystalline Fe2O3, nanocrystalline
ZnSnO3, nanocrystalline CdS, the materials such as nanocrystalline CdSe.If inorganic nano crystal grain, electron acceptor material can be in granular form, is short
Rodlike, linear, partial size can be 5~50nm, can uniformly be pinned at the grain boundary sites of perovskite polycrystal film in this way.
In bulk heterojunction layer, the molar ratio of electron donor material and electron acceptor material is preferably such that electron acceptor material
It can be uniformly distributed in perovskite polycrystal film grain boundary sites, assemble caused by excess without occurring with amount deficiency and cause
Hole, specifically can be different and different according to the type of selected electron acceptor material, may be, for example, 0.5~1000:1, it is excellent
It is selected as 0.5~15:1, more preferably 4~8:1.
The thickness of bulk heterojunction layer can be 90~690nm.The thickness of perovskite thin film layer can be 10~600nm.Entire body
The thickness of hetero-junctions perovskite thin film can be 100~700nm.Perovskite thin film layer primarily serves protective effect, while can be with
As light absorbent, preferably there is the film of continuous densified thin layer, can be better protected from this way electron acceptor material with
Hole mobile material contacts and leads to short circuit.
Hereinafter, illustrating the method for preparing bulk heterojunction perovskite thin film of the invention.
Firstly, preparation is used to form perovskite/electron acceptor material dispersion liquid of bulk heterojunction layer and is used to form calcium titanium
The perovskite precursor solution of mine film layer.
Perovskite/electron acceptor material dispersion liquid can by perovskite precursor solution and electron acceptor material mixing and
At.As described above, in a preferred embodiment, as electron donor material of the invention perovskite material with to be located at body heterogeneous
Therefore the perovskite thin film layer chemical composition having the same of knot layer surface is used to form the calcium positioned at bulk heterojunction layer surface
Identical perovskite forerunner can be used in the perovskite precursor solution and perovskite/electron acceptor material dispersion liquid of titanium ore film layer
Liquid solution.
As an example, preparing perovskite precursor solution for example may comprise steps of: by the halide and X of B
Monovalent cation salt (such as organic amine salt of X) shape in the first solvent is dissolved in the ratio of 1:10~10:1 (preferably 1:1)
At perovskite precursor solution.First solvent can be using oxygen-containing group solvent be possessed, which can be diformazan
The single solvent of base formamide (DMF), dimethyl sulfoxide (DMSO), gamma-butyrolacton (GBL), n-methyl-2-pyrrolidone etc. is mixed
Bonding solvent.The mass ratio of the halide of B and the first solvent can be 1:10~10:1.In one example, the halide of B, X one
Valence cationic salts, DMSO are with 1:1:(0~10) molar ratio (preferably 1:1:(0.1~10), more preferable 1:1:1) be dissolved in and possess
Perovskite precursor solution is formed in oxygen-containing group solvent.In precursor solution when containing DMSO B halide and X monovalence sun from
It is initially formed the intermediate of the presoma containing perovskite when alite is from presoma, so that the rate being precipitated relatively matches, is formed three-dimensional cross-linked
Poroid perovskite thin film.
As an example, preparing perovskite/electron acceptor material dispersion liquid for example may comprise steps of: as above
Electron acceptor material is added in the perovskite precursor solution of formation, forms perovskite/electron acceptor material dispersion liquid.Perovskite
It is different and different according to the type of selected electron acceptor material from the molar ratio of electron acceptor material, it may be, for example, 0.5~
1000:1.Electron acceptor material can be added with powder, can also be added with dispersion.
Then, body is formed on the substrate in bulk heterojunction dispersion liquid (i.e. perovskite/electron acceptor material dispersion liquid) coating
Hetero junction layer presoma.Wherein, the coating method of film can be spin-coating method (Spin Coating), slit extrusion molding
(Slot-Die Coating), knife coating (Doctor-Blading Coating) etc..Coating number can be one or many
Circulation coating.
Then, re-coating perovskite precursor solution forms one layer of perovskite protective layer on it.The coating method of film
It can be spin-coating method (Spin Coating), slit extrusion molding (Slot-Die Coating), knife coating (Doctor-
Blading Coating) etc..The bulk heterojunction precursor thin-film that surface has perovskite protective layer is obtained as a result,.
It, can be with when coating bulk heterojunction dispersion liquid film forming, and/or coating perovskite precursor solution film forming in the present invention
The second solvent can also be added dropwise in film surface in film forming procedure in one-pass film-forming, or in negative pressure (such as 5~200Pa) item
It forms a film under part, to promote solvent to volatilize, regulation nucleation and crystal growing process.
Second solvent can be the anti-solvent (abbreviation anti-solvent) of insoluble perovskite.Specifically, 1) the second solvent may is that
Insoluble solvent insoluble in bulk heterojunction dispersion liquid and/or perovskite precursor solution and insoluble perovskite is (referred to as insoluble
Anti-solvent) or be the anti-solvent for 2) being soluble in bulk heterojunction dispersion liquid and/or perovskite precursor solution but insoluble perovskite
(abbreviation ease of solubility anti-solvent) or it is 3) mixed solvent containing insoluble anti-solvent and ease of solubility anti-solvent.It is above-mentioned insoluble
Anti-solvent can be alkane, such as can be selected from n-hexane, pentane, octane, in heptane, petroleum ether etc. any one or it is two or more
Mixing.Above-mentioned ease of solubility anti-solvent can be at least one of toluene, ether, chlorobenzene, dichlorotoleune etc..In the present invention, the
Two solvents can be selected from least one of ether, n-hexane, petroleum ether, toluene, chlorobenzene, dichlorotoleune, and preferably ease of solubility is anti-
Solvent (such as toluene, ether, chlorobenzene, dichlorotoleune etc.), it is possible thereby to obtain the film layer of whole densification.
Before the dropwise addition opportunity of second solvent can start to become opaque for film, drip within 1~2 second most preferably before opaque
Add.When film becomes opaque, perovskite presoma is largely nucleated, and will lose the second solvent to the regulating and controlling effect of nucleation.
It is added dropwise within 1~2 second before opaque, perovskite precursor solution is up to hypersaturated state at this time, and the dropwise addition of the second solvent can
So that perovskite precursor solution is rapidly reached supersaturation, the regulation of nucleation mode and nucleation density is carried out.For example, the second solvent
Dropwise addition opportunity can be start film forming the 6th~30 second, be added dropwise the duration can be 2~12 seconds.The drop rate of second solvent
It can be 0.05~0.5mL/s.By selecting the drop rate, can effectively the nucleation mode to perovskite precursor solution into
Row regulation.
The coating of perovskite/electron acceptor material dispersion liquid and perovskite precursor solution can repeatedly alternately, and
In finally coating perovskite precursor solution.
Then, above-mentioned perovskite precursor thin-film is subjected to crystallization treatment.Processing can be divided into heat treatment mode and non-thermal place
Reason mode.Wherein, heat treatment temperature can be able to be hot plate in room temperature~150 DEG C (preferably room temperature~120 DEG C), heat treatment mode
Heating, baking oven heating, sintering stove heating, microwave heating, laser irradiation processing etc., processing time can be 0~120 minute.It is non-
Heat treatment mode is usually solvent volatilization induction film crystallization.Bulk heterojunction perovskite thin film of the invention is obtained as a result,.This hair
In bright, electron acceptor material can be added in perovskite precursor solution with form of nanoparticles, in solvent volatilization film forming procedure
In be uniformly embedded into precursor thin-film, in subsequent crystal growing process, with growing up for perovskite polycrystalline particle, electron acceptor
Material nanoparticle space extrusion effect effect under NATURAL DISTRIBUTION in the grain boundaries of perovskite polycrystal film.
The invention further relates to the perovskite solar batteries using above-mentioned bulk heterojunction perovskite thin film.Calcium titanium of the invention
Mine solar battery successively includes: transparent conductive substrate, hole blocking layer, perovskite bulk heterojunction active layer, sky from bottom to top
Cave transport layer and metallic top electrode.
The substrate can be used the transparent conductive electrode of covering hole barrier layer material, and the material of transparent conductive electrode can be with
It is rigid such as FTO glass for rigidity or flexible, ito glass, it is flexible such as with polyethylene naphthalate (PEN), gather to benzene
Thin polymer films such as naphthalate (PET), polyimides (PI), polycarbonate (PC), polyaniline, polypyrrole etc. are base
The oxidation films transparent conductive film such as the metal system (sputtering type or metal gate net type) of material or ITO.Its thickness can for 0.1~
10mm。
The hole blocking layer, which is one layer, can transmit electronics but the not dense film of transporting holes, such as TiO2, SnO2,
ZnO, fullerene, α-Fe2O3Deng.Its thickness can be 10~200nm.
The perovskite bulk heterojunction active layer is thin using above-mentioned bulk heterojunction perovskite, i.e., grain boundaries pinning electronics by
The perovskite polycrystal film of body material and perovskite thin film positioned at perovskite polycrystal film surface.Its thickness can for 100~
700nm。
NiO, CuI, CuSCN, MoO can be used in the hole transmission layer3、V2O5、WO3、MoS2、WS2、CoSe、CuSe、CoS、
VC Cr3C2, TiC, VN, PEDOT, poly- 3,4- ethylenedioxy thiophene: poly styrene sulfonate (PEDOT:PSS), poly- 3,4- ethylene
Dioxy thiophene: tosilate (PEDOT-TsO), 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'-
Two fluorenes of spiral shell, poly- (3- hexyl thiophene -2,5- diyl), poly- [bis- (4- phenyl) (2,4,62,4,62,4,62,4,6- trimethylbenzene)
Amine], polypyrrole (PPy), one or more of mixtures of polyaniline (PANI) etc. or its dopant and dopant mixture.Its
The partial size of middle inorganic hole transporter is 5~500 nanometers, preferably nano material.
The metallic top electrode can be gold or silver.Its thickness can be 20~200nm.
As an example, the preparation method of the perovskite solar battery for example may comprise steps of:
Prepare hole blocking layer in clean transparent conductive substrate, can using spin coating, spraying, blade coating, magnetron sputtering,
The methods of atomic layer deposition；
Perovskite body is prepared on resulting hole blocking layer using the above-mentioned method for preparing bulk heterojunction perovskite thin film
Hetero-junctions active layer can use spin-coating method, slit extrusion molding, knife coating etc.；
The spin coating hole transmission layer on resulting perovskite bulk heterojunction active layer；
The evaporation metal top electrode on resulting hole transmission layer.
It can be cleaned before using substrate, such as: it is clear with acetone, alkalis, deionized water, acetone ultrasound respectively
FTO 5~20min of glass is washed, is finally dried up with compressed air, 10~30min of processing in UV ozone machine is finally placed on, to remove
Remaining organic impurities simultaneously enhance substrate to the wetability of solution.
The preparation of perovskite bulk heterojunction active layer for example, on transparent conductive substrate/hole blocking layer matrix
Perovskite/electron acceptor material dispersion liquid is added dropwise, with 10~50s of revolving speed spin coating of 2000~7000rpm, wherein for example the 6th
Dropwise addition (dripping off in about 2~12 seconds) second solvent (such as ether) is on the matrix of rotation within~30 seconds；Then, calcium is added dropwise on it
Titanium ore precursor solution, with 10~50s of revolving speed spin coating of 2000~7000rpm, wherein be for example added dropwise (about 2 at the 6th~30 second
Being dripped off in~12 seconds) the second solvent (such as ether) is on the matrix of rotation；Above two step be repeated 1 times it is above, obtain perovskite/
Electron acceptor material precursor thin-film；Finally, coating perovskite precursor solution on it, one layer of perovskite protective layer is formed；
Then it anneals at 80~150 DEG C, obtains perovskite/electron acceptor material precursor thin-film.
In perovskite solar battery structure of the invention, perovskite bulk heterojunction active layer is one layer of 100~700nm's
Film so that the Extracting Ability of electronics greatly enhances, while in turn simplifying the structure of battery；Compared with traditional perovskite thin film,
Preparation method is simpler, and film quality is more easier to control, and overcomes traditional structure complex process and to perovskite thin film
The higher problem of flatness requirement.
Moreover, high temperature needed for independent mesoporous layer preparation process can also be avoided using bulk heterojunction perovskite thin film
Sintering process, suitable for preparing high-efficiency flexible perovskite solar battery in ductile basement.
The photoelectric conversion efficiency of the resulting porous perovskite solar battery of the present invention has been more than 17%.This explanation, this hair
Bright perovskite bulk heterojunction active layer is more suitable for large-scale production application under the premise of guaranteeing battery efficiency.
Advantages of the present invention:
Independent mesoporous layer is not needed using the battery structure of bulk heterojunction perovskite thin film of the invention, that is, can reach Jie
The performance of pass perovskite solar battery, after tested, using the perovskite sun of bulk heterojunction perovskite thin film of the invention
The photoelectric conversion efficiency of energy battery has been more than 17%.Moreover, can also be avoided independent mesoporous using bulk heterojunction perovskite thin film
High-sintering process needed for layer preparation process, suitable for preparing high-efficiency flexible perovskite solar-electricity in ductile basement
Pond.And the preparation method of the type perovskite thin film and battery is simple, and the reproducibility of institute's assembled battery is high, with traditional perovskite
Film is compared, and preparation method is simpler, and film quality is more easier to control, and overcomes traditional structure complex process and to calcium titanium
The higher problem of the flatness requirement of mine film is suitable for large-scale production application.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1:
Hydro-thermal method synthesizes TiO2It is nanocrystalline: 150mL butyl titanate being added under strong stirring and fills 0.1moL/L's
In the glass reaction kettle of dilute nitric acid solution (1000mL), white precipitate is hydrolyzed to form, reaction kettle is then heated to 120 DEG C, is held
The lower 8 hours progress dispergation of heat preservation of continuous stirring are simultaneously concentrated.Gained colloidal sol is transferred in titanium autoclave, it is small in 260 DEG C of hydro-thermal process 12
When, obtain TiO2It is nanocrystalline.Obtained TiO2Nanocrystalline partial size is about 20nm；
(1) perovskite/electron acceptor material dispersion liquid preparation.TiO is prepared first2DMF dispersion liquid: hydro-thermal method is closed
At TiO2It is nanocrystalline to be washed respectively with deionized water, ethyl alcohol and DMF, impurity is removed, is then dispersed in DMF and forms dispersion liquid
It is spare.Then, by PbI2, MAI and DMSO be dissolved in DMF and be sufficiently stirred with the ratio of 1:1:1, obtain perovskite presoma
Solution (MAPbI3), then by perovskite precursor solution and TiO2DMF dispersion liquid with certain proportion (MAPbI3With TiO2It rubs
You are than being 5:1) it is mixed to get MAPbI3/TiO2Nanocrystalline forerunner's dispersion liquid；
(2) cleaning of conductive substrates.It is cleaned by ultrasonic FTO glass with acetone, alkalis, deionized water, acetone respectively
10min is finally dried up with compressed air, is finally placed in UV ozone machine and is handled 15min, to remove remaining organic impurities
And enhance substrate to the wetability of solution；
(3) preparation of hole blocking layer.Precursor solution solvent is ethyl alcohol, including following component: four isopropyl of metatitanic acid
Ester (0.3mol/L), acetylacetone,2,4-pentanedione (0.45mol/L), hydrochloric acid (0.09mol/L), water (1.8mol/L).Precursor solution is drawn,
It is added dropwise on the FTO of step (1), making solution be paved with the entire surface FTO, spin speed 3000rpm, time 20s, then in Muffle
510 DEG C of sintering 30min in furnace；
(4) preparation of perovskite bulk heterojunction active layer.MAPbI is added dropwise on the matrix of FTO/ hole blocking layer3/TiO2
Nanocrystalline forerunner's dispersion liquid, wherein MAPbI3With TiO2Molar ratio is 5:1, with the revolving speed spin coating 20s of 5000rpm, wherein
Dropwise addition 0.5mL ether is on the matrix of rotation within 6 seconds quick (dripping off in about 2 seconds)；The spin-coating step is repeated 2 times, obtain perovskite/
Then MAPbI is added dropwise in electron acceptor material precursor thin-film on it3Forerunner's dispersion liquid, with the revolving speed spin coating of 5000rpm
20s, wherein being added dropwise at the 6th second quick (being dripped off in about 2 seconds) on matrix of the 0.5mL ether in rotation, before forming one layer of perovskite
Drive body thin film.Then anneal 20min on 100 DEG C of hot plates, obtains perovskite bulk heterojunction active layer；
(5) preparation of hole transmission layer.The spin coating hole transmission layer on the bulk heterojunction perovskite thin film that step (4) obtains
Solution, ingredient are as follows: the 2,2' of 72.3mg/mL, 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes
Chlorobenzene solution, the acetonitrile solution of bis- (fluoroform) sulfimide lithium salts of the 520mg/mL including 20 μ L/mL and the 4- of 20 μ L
Tert .-butylpyridine is as additive, revolving speed 4000rpm, time 30s；
(6) prepared by Ag top electrode.Ag layers of 120nm thickness of vapor deposition are top electrode, obtain perovskite solar battery.
Embodiment 2:
(1) perovskite/electron acceptor material dispersion liquid preparation.TiO is prepared first2DMF dispersion liquid: hydro-thermal method is closed
At TiO2It is nanocrystalline to be washed respectively with deionized water, ethyl alcohol and DMF, impurity is removed, is then dispersed in DMF and forms dispersion liquid
It is spare.Then, by PbI2, MAI and DMSO be dissolved in DMF and be sufficiently stirred with the ratio of 1:1:1, obtain perovskite presoma
Solution (MAPbI3), then by perovskite precursor solution and TiO2DMF dispersion liquid with certain proportion (MAPbI3With TiO2It rubs
You are than being 10:1) it is mixed to get MAPbI3/TiO2Nanocrystalline forerunner's dispersion liquid；
(2) cleaning of conductive substrates.With embodiment 1；
(3) preparation of hole blocking layer.With embodiment 1；
(4) preparation of perovskite bulk heterojunction active layer.MAPbI is added dropwise on the matrix of FTO/ hole blocking layer3/TiO2
Nanocrystalline forerunner's dispersion liquid, wherein MAPbI3With TiO2Molar ratio is 10:1, and other operations are the same as embodiment 1；
(5) preparation of hole transmission layer.With embodiment 1；
(6) preparation of Ag top electrode.With embodiment 1.
Embodiment 3:
(1) perovskite/electron acceptor material dispersion liquid preparation.By PbI2, MAI and DMSO dissolve with the ratio of 1:1:1
It in DMF and is sufficiently stirred, obtains perovskite precursor solution (MAPbI3), a certain amount of graphene is then added
(Aldrich, nanometer sheet, powder are hydrophobic) is simultaneously mixed to get MAPbI3/ graphene forerunner's dispersion liquid；
(2) cleaning of conductive substrates.With embodiment 1；
(3) preparation of hole blocking layer.With embodiment 1；
(4) preparation of perovskite bulk heterojunction active layer.MAPbI is added dropwise on the matrix of FTO/ hole blocking layer3/ graphite
Alkene forerunner's dispersion liquid, wherein MAPbI3It is 5:1 with graphene molar ratio, other operations are the same as embodiment 1；
(5) preparation of hole transmission layer.With embodiment 1；
(6) preparation of Ag top electrode.With embodiment 1.
Embodiment 4:
(1) perovskite/electron acceptor material dispersion liquid preparation.By PbI2, MAI and DMSO dissolve with the ratio of 1:1:1
It in DMF and is sufficiently stirred, obtains perovskite precursor solution (MAPbI3), a certain amount of fullerene is then added
(Aldrich, 99.5%) is simultaneously mixed to get MAPbI3/ fullerene forerunner's dispersion liquid；
(2) cleaning of conductive substrates.With embodiment 1；
(3) preparation of hole blocking layer.With embodiment 1；
(4) preparation of perovskite bulk heterojunction active layer.MAPbI is added dropwise on the matrix of FTO/ hole blocking layer3/ fowler
Alkene forerunner's dispersion liquid, wherein MAPbI3It is 5:1 with fullerene molar ratio, other operations are the same as embodiment 1；
(5) preparation of hole transmission layer.With embodiment 1；
(6) preparation of Ag top electrode.With embodiment 1.
Embodiment 5:
(1) perovskite/electron acceptor material dispersion liquid preparation.By PbI2, MAI and DMSO dissolve with the ratio of 1:1:1
It in DMF and is sufficiently stirred, obtains perovskite precursor solution (MAPbI3), be then added a certain amount of carbon black (Japanese Lion,
Ketjen black) and it is mixed to get MAPbI3/ carbon black forerunner's dispersion liquid；
(2) cleaning of conductive substrates.With embodiment 1；
(3) preparation of hole blocking layer.With embodiment 1；
(4) preparation of perovskite bulk heterojunction active layer.MAPbI is added dropwise on the matrix of FTO/ hole blocking layer3/ carbon black
Forerunner's dispersion liquid, wherein MAPbI3It is 5:1 with carbon black molar ratio, other operations are the same as embodiment 1；
(5) preparation of hole transmission layer.With embodiment 1；
(6) preparation of Ag top electrode.With embodiment 1.
Embodiment 6:
(1) perovskite/electron acceptor material dispersion liquid preparation.By PbI2, MAI and DMSO dissolve with the ratio of 1:1:1
It in DMF and is sufficiently stirred, obtains perovskite precursor solution (MAPbI3), be then added a certain amount of graphite (Aladdin,
8000 mesh, 99.95%) and it is mixed to get MAPbI3/ graphite forerunner's dispersion liquid；
(2) cleaning of conductive substrates.With embodiment 1；
(3) preparation of hole blocking layer.With embodiment 1；
(4) preparation of perovskite bulk heterojunction active layer.MAPbI is added dropwise on the matrix of FTO/ hole blocking layer3/ graphite
Forerunner's dispersion liquid, wherein MAPbI3It is 5:1 with graphite molar ratio, other operations are the same as embodiment 1；
(5) preparation of hole transmission layer.With embodiment 1；
(6) preparation of Ag top electrode.With embodiment 1.
Comparative example 1:
(1) cleaning of conductive substrates.With embodiment 1；
(2) preparation of hole blocking layer.With embodiment 1；
(3) preparation of mesoporous electron transfer layer.The preparation of mesoporous electron transfer layer.Above-mentioned hydro-thermal method is synthesized into TiO2Nanometer
Crystalline substance is scattered in ethyl alcohol, forms the nano-TiO of 20wt%2Slurry, using it as material, using silk-screen printing technique in hole barrier
Mesoporous TiO is coated on layer2Film forms mesoporous electron transfer layer then in 510 DEG C of sintering 30min；
(4) preparation of calcium titanium ore bed.By PbI2, MAI and DMSO be dissolved in DMF and be sufficiently stirred with the ratio of 1:1:1,
Perovskite precursor solution is formed, perovskite precursor solution is added dropwise on FTO/ hole blocking layer/mesoporous layer matrix, with
The revolving speed spin coating 20s of 5000rpm, wherein be added dropwise at the 6th second quick (being dripped off in about 2 seconds) on matrix of the 0.5mL ether in rotation,
Obtain perovskite precursor thin-film.Then anneal 10min on 100 DEG C of hot plates, obtains perovskite thin film；
(5) preparation of hole transmission layer.With embodiment 1；
(6) preparation of Ag top electrode.With embodiment 1.
Comparative example 2:
(1) cleaning of conductive substrates.With embodiment 1；
(2) preparation of hole blocking layer.With embodiment 1；
(3) preparation of mesoporous electron transfer layer.The preparation of mesoporous electron transfer layer.With the nanocrystalline TiO of 20wt%2Ethyl alcohol
Dispersion liquid (with comparative example 1) is material, coats mesoporous TiO on the hole blocking layer using spin coating proceeding2Film, then at 120 DEG C
20min is dried, mesoporous electron transfer layer is formed；
(4) preparation of calcium titanium ore bed.By PbI2, MAI and DMSO be dissolved in DMF and be sufficiently stirred with the ratio of 1:1:1,
Perovskite precursor solution is formed, perovskite precursor solution is added dropwise on FTO/ hole blocking layer/mesoporous layer matrix, with
The revolving speed spin coating 20s of 5000rpm, wherein be added dropwise at the 6th second quick (being dripped off in about 2 seconds) on matrix of the 0.5mL ether in rotation,
Obtain perovskite precursor thin-film.Then anneal 10min on 100 DEG C of hot plates, obtains perovskite thin film；
(5) preparation of hole transmission layer.With embodiment 1；
(6) preparation of Ag top electrode.With embodiment 1.
The Examples 1 to 6 manufactured as described above, the perovskite solar battery of comparative example 1 and 2 are had rated as follows.That is,
By using solar simulator (AM1.5,100mW/cm of standard type xenon lamp2), determine opening for perovskite solar battery
Road voltage Voc, short-circuit current density Jsc, fill factor FF and efficiency eta.Its result is shown in table 1.
Table 1:
As shown in Table 1, the present invention uses bulk heterojunction perovskite light absorbing layer, equally obtains high-photoelectric transformation efficiency
Perovskite solar battery, photoelectric conversion efficiency are suitable with the mesoporous type perovskite solar battery of high-sintering process is needed
It is even higher, and it is much higher than the mesoporous type perovskite solar battery without high-sintering process, overcome smooth surface
Perovskite thin film requires preparation process harsh disadvantage, enormously simplifies the preparation process of film, improves yield rate, is calcium
The scale preparation of titanium ore solar battery lays the foundation.
Fig. 1 shows the SEM cross-section photographs of the body heterojunction perovskite thin film of the embodiment of the present invention 1, can be seen by Fig. 1
TiO out2Pinning also has perovskite thin film layer in the grain boundaries of perovskite polycrystal film above perovskite polycrystal film.
More than, the embodiment of this technology is illustrated, but this technology is not limited to above-mentioned embodiment,
Various modifications can be carried out based on the technical idea of this technology.For example, the composition enumerated in above embodiment, method, step, shape
Looks, material and numerical value etc. only as an example, also can according to need using unlike this composition, method, step, pattern,
Material and numerical value etc..In addition, the composition of above embodiment, method, step, shape, pattern and numerical value etc. can not take off
From being combined with each other in the range of the purport of this technology.
Claims (11)
1. a kind of bulk heterojunction perovskite thin film, which is characterized in that the bulk heterojunction perovskite thin film includes:
Bulk heterojunction layer, the bulk heterojunction layer include the perovskite polycrystal film as electron donor material and are located at described
The electron acceptor material of the grain boundary sites of perovskite polycrystal film；And
Positioned at the perovskite thin film layer of the bulk heterojunction layer surface.
2. bulk heterojunction perovskite thin film according to claim 1, which is characterized in that the perovskite polycrystal film and/
Or the chemical composition of the perovskite thin film layer is ABX3, wherein A is monovalent cation or mixed-cation；B is Pb2+、Sn2+、
Ge2+、Co2+、Fe2+、Mn2+、Cu2+、Ni2+At least one of；X is Cl‒、Br‒、I‒、SCN-、BF4 -At least one of.
3. bulk heterojunction perovskite thin film according to claim 2, which is characterized in that A CH3NH3 +、NH2-CH=NH2 +、
Cs+、Li+、C4H9NH3 +、CH6N3 +、Na+、K+At least one of.
4. bulk heterojunction perovskite thin film according to claim 1, which is characterized in that the electron acceptor material is nanometer
Brilliant TiO2, nanocrystalline SnO2, Nanocrystalline ZnO Powder, fullerene, fullerene derivate, acid imide, naphthalimide, based on expand thiophene
Organic macromolecule acceptor material, graphene, carbon black, graphite, the nano-crystalline Fe of condensed ring2O3, nanocrystalline ZnSnO3, nanocrystalline CdS,
At least one of nanocrystalline CdSe.
5. bulk heterojunction perovskite thin film according to any one of claim 1 to 4, which is characterized in that the body is heterogeneous
The thickness of perovskite thin film is tied in 100~700nm.
6. a kind of preparation method of bulk heterojunction perovskite thin film described in claim 1 characterized by comprising
First perovskite precursor solution and electron acceptor material are mixed to get perovskite/electron acceptor material dispersion liquid；
By the perovskite/electron acceptor material dispersion in substrate, it is coated with the second perovskite presoma thereon
Solution forms bulk heterojunction precursor thin-film；
The bulk heterojunction precursor thin-film is subjected to crystallization treatment, obtains the bulk heterojunction perovskite thin film.
7. the preparation method of bulk heterojunction perovskite thin film according to claim 6, which is characterized in that the perovskite is more
The chemical composition of brilliant film and/or the perovskite thin film layer is ABX3, wherein A is monovalent cation or mixed-cation；B
For Pb2+、Sn2+、Ge2+、Co2+、Fe2+、Mn2+、Cu2+、Ni2+At least one of；X is Cl‒、Br‒、I‒、SCN-、BF4 -In extremely
Few one kind, the preparation of the first perovskite precursor solution and/or the second perovskite precursor solution includes: that the halide of B is molten
Liquid, the monovalent cation salt of X and the mixing of the first solvent；Wherein, first solvent is to possess oxygen-containing group solvent.
8. the preparation method of bulk heterojunction perovskite thin film according to claim 7, which is characterized in that first solvent
For at least one of dimethylformamide, dimethyl sulfoxide, gamma-butyrolacton, n-methyl-2-pyrrolidone.
9. the preparation method of bulk heterojunction perovskite thin film according to claim 6, which is characterized in that heterogeneous in the body
In the film forming procedure for tying precursor thin-film, further include the steps that the second solvent is added dropwise in film surface, second solvent is selected from
At least one of ether, n-hexane, petroleum ether, toluene, chlorobenzene, dichlorotoleune.
10. the preparation method of bulk heterojunction perovskite thin film according to any one of claims 6 to 9, which is characterized in that
The crystallization treatment uses heat treatment mode or non-heat treated mode, the heat treatment mode heats for hot plate, baking oven heats,
It is sintered stove heating, microwave heating or laser irradiation processing, the temperature of the heat treatment is room temperature~150 DEG C, and the processing time is 0
~120 minutes；The non-heat treated mode is solvent volatilization induction film crystallization.
11. a kind of perovskite solar battery, which is characterized in that the perovskite solar battery successively includes: from bottom to top
Electrically conducting transparent substrate, hole blocking layer, bulk heterojunction perovskite thin film, hole transport described in any one of claims 1 to 5
Layer and top electrode.
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