CN106654020A - Bulk-heterojunction perovskite thin film, production method thereof and solar cell - Google Patents
Bulk-heterojunction perovskite thin film, production method thereof and solar cell Download PDFInfo
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- CN106654020A CN106654020A CN201710060215.6A CN201710060215A CN106654020A CN 106654020 A CN106654020 A CN 106654020A CN 201710060215 A CN201710060215 A CN 201710060215A CN 106654020 A CN106654020 A CN 106654020A
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- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
- H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
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- H10K30/353—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising blocking layers, e.g. exciton blocking layers
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Abstract
The invention relates to a bulk-heterojunction perovskite thin film, a production method thereof and a solar cell. The bulk-heterojunction perovskite thin film comprises a bulk-heterojunction layer and a perovskite thin film layer located on the surface of the bulk-heterojunction layer, wherein the bulk-heterojunction layer comprises a perovskite polycrystalline thin film serving as an electron donor material and an electron acceptor material located at the crystal boundary position of the perovskite polycrystalline thin film. The bulk-heterojunction perovskite thin film has the advantages that when the bulk-heterojunction perovskite thin film is applied to the perovskite solar cell, the bulk-heterojunction perovskite thin film can replace an existing mesoporous electron transfer layer and an existing perovskite light absorption layer, and accordingly the structure of the cell can be simplified; the high-temperature sintering process needed by the production of the independent mesoporous layer can be omitted, and the bulk-heterojunction perovskite thin film is suitable for producing the efficient and flexible perovskite solar cell on a plastic substrate.
Description
Technical field
The invention belongs to technical field of solar batteries, more particularly to a kind of preparation method of thin film used for solar batteries,
More specifically, it is related to a kind of bulk heterojunction perovskite thin film and corresponding perovskite solaode and preparation method thereof.
Background technology
With the development of human society, for the demand of the energy grows with each passing day.Solar energy is used as a kind of cleaning, free of contamination
The energy, by extensive concern both domestic and external and further investigation.It is based on the solaode of hybrid inorganic-organic perovskite thin film
The class novel solar battery that developed recently gets up, its advantage is very prominent：1st, prepared by hybrid inorganic-organic perovskite material
Process is simple, cost are relatively low；2nd, with regulatable band gap；3rd, electron hole mobility, the high quantum luminous efficiency of balance
With larger defect tolerant degree；4th, translucent battery or flexible battery be can be made into, it is easy to integrated with other devices, application scenarios are big
Widen greatly.Therefore, perovskite solaode and associated materials have become an important research direction of photovoltaic art, obtain at present
22.1% authentication efficiency was obtained, was had a extensive future.
The structure that at present perovskite solaode is generally adopted mainly has three kinds：Plate, mesoporous type and transconfiguration.
The outstanding feature of transconfiguration is delayed less or no delayed, but efficiency is not relatively high.The plate calcium of formal structure
Titanium ore battery is delayed larger, although using fullerene, SnO2It is reduced or eliminated for delayed after hole blocking layer Deng material, but it is electric
Pond efficiency could not also exceed Jie's pass structure.The perovskite solaode of Jie's pass structure mesh in terms of delayed elimination and efficiency
It is front with advantage, but one layer of independent mesoporous layer is needed in battery structure.On the one hand, the preparation technology of mesoporous layer often will be
Under higher temperature (such as 500 DEG C) sintering processes, hinder it and flexible perovskite solaode prepared in ductile basement.It is another
Aspect, the delayed elimination situation of battery relies on filling situation of the perovskite crystal grain in mesoporous layer, if filling is insufficient, it is delayed very
Difficulty is completely eliminated.Additionally, for the battery based on above structure, perovskite ABX3The preparation method of thin film to its film morphology,
Charge mobility, electron lifetime and opto-electronic conversion performance affect larger.For example, in current document report a step solwution method, two
The preparation methoies such as step solwution method, vapour deposition process and gas phase assisted solution method, are to obtain the perovskite thin film of smooth densification
For target.If prepared thin film pin-hole like defects are more, the compound of electric charge in thin film is easily caused, have a strong impact on the performance of thin film.
This not only increased the preparation difficulty of perovskite thin film, and be unfavorable for prepare with scale and yield rate control.CN
104201284 A disclose a kind of based on perovskite solar cell and the integrated solar cell of bulk heterojunction solar cell, described
Integrated solar cell from bottom to top successively include transparency electrode, hole transmission layer, perovskite light-absorption layer, Organic substance blended layer, appoint
Selection of land hole blocking layer and metal electrode, wherein, the Organic substance blended layer refers to bulk heterojunction solar cell donor material
With the hybrid films of acceptor material, donor material is conjugation of the optical band gap less than 1.5eV for being applied to bulk heterojunction solar cell
Polymer or/and small molecule, any one in preferred PDPP3T, PMDPP3T, PDPPBTT or PDTP-DFBT or at least two
The mixture planted.The battery structure is perovskite solar cell and the laminated cell of bulk heterojunction solar cell, chief active material
Material perovskite material does not form the structure of bulk heterojunction as electron donor.
The content of the invention
Present invention seek to address that at present using the battery structure and the deficiency of preparation method of open report, it is proposed that Yi Zhongxin
The battery structure based on bulk heterojunction perovskite thin film and its implementation, the battery structure do not need independent mesoporous layer,
Can reach the performance of mesoporous type perovskite solaode, and the preparation method letter of the type perovskite thin film and battery
Single, the repeatability 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 is included as the perovskite polycrystal film of electron donor material and positioned 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.
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, the perovskite thin film layer can play a protective role, and prevent body heterogeneous
Electron acceptor material in knot layer is contacted with hole mobile material and causes short circuit.By the bulk heterojunction perovskite thin film of the present invention
When being applied to perovskite solaode, it can replace existing mesoporous electron transfer layer and perovskite light-absorption layer, so as to can
To simplify the structure of battery, the high-sintering process needed for independent mesoporous layer preparation process can also be avoided, be suitable in plasticity
High-efficiency flexible perovskite solaode is prepared in substrate.Jing is tested, using bulk heterojunction perovskite thin film of the invention
The photoelectric transformation efficiency of perovskite solaode is with existing with independent mesoporous electron transfer layer and perovskite light-absorption layer
Perovskite battery quite, or even its photoelectric transformation efficiency has exceeded 17%.
It is preferred that in bulk heterojunction layer, electron donor material is 0.5～15 with the mol ratio of electron acceptor material：1.
It is preferred that 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+
In at least one；B is Pb2+、Sn2+、Ge2+、Co2+、Fe2+、Mn2+、Cu2+、Ni2+In at least one, i.e. B can be these
Any two or more mixed structure in one of ion, or these ions；X is Cl-、Br-、I-、SCN-、BF4 -In
It is at least one, i.e. X can be single ionic, or hybrid ionic, such as arbitrarily mixing of two or more ions.For example
ABX3For MAPbI3、FAPbI3、FA1-xCsxPbI3、CsxMA yFA1-x-yPbI3Deng wherein MA refers to CH3NH3 +, FA refers to NH2- CH=
NH2 +。
It is preferred that the electron acceptor material is nanocrystalline TiO2, nanocrystalline SnO2, Nanocrystalline ZnO Powder, fullerene, fullerene
Derivant, perylene diimide, naphthalimide, organic macromolecule acceptor material, Graphene, white carbon black, stone based on expansion thiophene condensed ring
Ink, nano-crystalline Fe2O3, nanocrystalline ZnSnO3, nanocrystalline CdS, at least one in nanocrystalline CdSe.
It is preferred that the thickness of the bulk heterojunction perovskite thin film is in 100～700nm.
The present invention also provides a kind of preparation method of above-mentioned bulk heterojunction perovskite thin film, including：
First perovskite precursor solution and electron acceptor material are mixed to get into perovskite/electron acceptor material dispersion liquid；
The perovskite/electron acceptor material dispersion is coated with into the second perovskite presoma in substrate, thereon
Solution, forms bulk heterojunction precursor thin-film；
The bulk heterojunction precursor thin-film is carried out into crystallization treatment, the bulk heterojunction perovskite thin film is obtained.
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 causes itself and perovskite
Crystal grain shares density of electronic states, and plays pinning effect in perovskite grain boundaries, so as to the electricity that the defect for reducing grain boundaries causes
Lotus is combined.Independent mesoporous layer is not needed using the battery structure of the bulk heterojunction perovskite thin film of the present invention, you can reach Jie
The performance of pass perovskite solaode, Jing tests, using the perovskite sun of the bulk heterojunction perovskite thin film of the present invention
The photoelectric transformation efficiency of energy battery has exceeded 17%.And, using bulk heterojunction perovskite thin film, can also avoid independent mesoporous
High-sintering process needed for layer preparation process, is suitable to prepare high-efficiency flexible perovskite solar-electricity in ductile basement
Pond.And the preparation method of the type perovskite thin film and battery is simple, the repeatability of institute's assembled battery is high, with traditional perovskite
Thin film is compared, and preparation method is simpler, and film quality is more prone to control, overcomes traditional structure complex process and to calcium titanium
The higher problem of the flatness requirement of ore deposit thin film, it is adaptable to large-scale production application.
It is preferred that the preparation of the first perovskite precursor solution and/or the second perovskite precursor solution includes：By B's
The mixing of halide solution, the monovalent cation salt of X and the first solvent, forms perovskite precursor solution, wherein, described the
One solvent to possess oxy radical solvent, preferred dimethylformamide (DMF), dimethyl sulfoxide (DMSO), gamma-butyrolacton (GBL),
At least one in METHYLPYRROLIDONE.
It is preferred that in the film forming procedure of the bulk heterojunction precursor thin-film, being additionally included in opportune moment in thin film table
The step of face the second solvent of Deca, second solvent is in ether, normal hexane, petroleum ether, toluene, chlorobenzene, dichlorotoleune
At least one.
It is preferred that the crystallization treatment is using heat treatment mode or non-heat treated mode, the heat treatment mode is heat
Plate heating, baking oven for heating, sintering stove heat, microwave heating or laser treatment with irradiation, the temperature of the heat treatment be room temperature～
150 DEG C, process time is 0～120 minute, preferably greater than 0 and less than 120 minutes；The non-heat treated mode is solvent volatilization
Induction thin film crystallization.
In the present invention, electron acceptor material can be added with powder, it is also possible to dispersion addition.
In the present invention, the coating method of perovskite/electron acceptor material dispersion liquid 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 coating.
The present invention also provides a kind of perovskite solaode, and the perovskite solaode is wrapped successively from bottom to top
Include：Electrically conducting transparent substrate, hole blocking layer, above-mentioned bulk heterojunction perovskite thin film, hole transmission layer and top electrode.
It is preferred that the substrate is the transparency conductive electrode for covering hole barrier layer material, the material of transparency conductive electrode
Can be rigidity or flexible, rigid such as FTO glass, ito glass is flexible such as with PEN (PEN), poly-
Thin polymer films such as ethylene glycol terephthalate (PET), polyimides (PI), Merlon (PC), polyaniline, polypyrrole etc.
The oxidation film transparent conductive films such as the metal system (sputtering type or metal gate net type) or ITO for base material.
Description of the drawings
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 accompanying drawing and following embodiments, it should be appreciated that following embodiments are only used for
Illustrate the present invention, and the unrestricted present invention.
The present invention relates to a kind of bulk heterojunction perovskite thin film and corresponding perovskite solaode and preparation method thereof.
The perovskite precursor solution and perovskite/electron acceptor material dispersion liquid that obtain are prepared by the coating in substrate, is formed
Bulk heterojunction precursor thin-film, and by carrying out crystallization treatment to bulk heterojunction precursor thin-film, the body for obtaining the present invention is heterogeneous
Knot perovskite thin film.The bulk heterojunction thin film of the present invention adopts perovskite material for electron donor material, electron acceptor material position
In the grain boundary sites of perovskite polycrystal film, and fine and close perovskite thin film layer is formed on the surface of bulk heterojunction, with traditional calcium
Titanium ore thin film is compared, and preparation method is simpler, and film quality is more prone to control, 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 the bulk heterojunction perovskite thin film of the present invention
Want independent mesoporous layer, you can reach the performance of mesoporous type perovskite solaode, independent mesoporous layer can be avoided to prepare
High-sintering process needed for journey.
Fig. 1 illustrates the SEM cross-section photographs of the body heterojunction perovskite thin film of an example of the invention.In Fig. 1, from lower past
On be followed successively by：Transparent conducting glass (FTO glass), hole blocking layer, bulk heterojunction perovskite thin film.Bulk heterojunction perovskite is thin
Film includes：Bulk heterojunction layer, the bulk heterojunction layer is included as the perovskite polycrystal film of electron donor material and positioned at institute
State the electron acceptor material (referring to the granule in Fig. 1) of the grain boundary sites of perovskite polycrystal film；And it is heterogeneous positioned at the body
The perovskite thin film layer of knot layer surface.
In the present invention, with perovskite material as electron donor material, with high excellent of absorbing light spectrum width and electron mobility
Point.
In the present invention, the chemical composition of perovskite polycrystal film (electron donor material) and perovskite thin film layer can phase
Together, it is also possible to different, it is preferably identical, can so simplify preparation method, and eliminate the interphase match problem between two-layer.Tool
The chemical composition of body ground, 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.B can adopt Pb2+,Sn2+, Ge2+, Co2+, Fe2+, Mn2+, Cu2+, and Ni2+In at least one, i.e. B can be this
Any two or more mixed structure in one of a little ions, or these ions.In one example, ABX3For
ASn1-xPbxX3(0 ＜ x ＜ 1).X can adopt Cl-, Br-, I-,SCN-,BF4 -In at least one, i.e. X can be it is single from
Son, or hybrid ionic, such as 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
Use nanocrystalline TiO2, nanocrystalline SnO2, Nanocrystalline ZnO Powder, fullerene (C60), fullerene derivate, perylene diimides, naphthalimide,
Based on organic macromolecule acceptor material, the Graphene of expanding thiophene condensed ring, carbon black, graphite, nano-crystalline Fe2O3, it is nanocrystalline
ZnSnO3, the material such as nanocrystalline CdS, nanocrystalline CdSe.If inorganic nano crystal grain, electron acceptor material can be in granular form, short
Bar-shaped, wire, its particle diameter can be 5～50nm, so can uniformly be pinned at the grain boundary sites of perovskite polycrystal film.
In bulk heterojunction layer, electron donor material is preferably such that electron acceptor material with the mol ratio of electron acceptor material
Can be uniformly distributed in perovskite polycrystal film grain boundary sites, and occur without causes because excessive and caused aggregation and amount are not enough
Hole, specifically can be different according to the species of selected electron acceptor material and different, for example can be 0.5～1000：1, it is excellent
Elect 0.5～15 as：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.Whole 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, its preferably thin film with continuous densified thin layer, so can be better protected from electron acceptor material with
Hole mobile material is contacted and causes short circuit.
Hereinafter, the method for illustrating the bulk heterojunction perovskite thin film for preparing the present invention.
First, perovskite/electron acceptor material dispersion liquid for forming bulk heterojunction layer is prepared and for forming calcium titanium
The perovskite precursor solution of ore deposit thin layer.
Perovskite/electron acceptor material dispersion liquid can be by perovskite precursor solution and electron acceptor material mixing
Into.As described above, in a preferred version, it is heterogeneous with positioned at body as the perovskite material of the electron donor material of the present invention
The perovskite thin film layer of knot layer surface has identical chemical composition, therefore, for forming the calcium positioned at bulk heterojunction layer surface
The perovskite precursor solution of titanium ore thin layer can adopt identical perovskite forerunner with perovskite/electron acceptor material dispersion liquid
Liquid solution.
As an example, prepare perovskite precursor solution and for example may comprise steps of：By the halogenide and X of B
Monovalent cation salt (organic amine salt of such as X) with 1：10～10：1 (preferably 1：1) ratio is dissolved in shape in the first solvent
Into perovskite precursor solution.First solvent can be using oxy radical solvent be possessed, and the oxy radical solvent can be diformazan
The single solvent of base Methanamide (DMF), dimethyl sulfoxide (DMSO), gamma-butyrolacton (GBL), METHYLPYRROLIDONE etc. is mixed
Bonding solvent.The mass ratio of the halogenide of B and the first solvent can be 1：10～10：1.In one example, the halogenide of B, the one of X
Valency cationic salts, DMSO are with 1：1：The mol ratio (preferably 1 of (0～10)：1：(0.1～10), more preferably 1：1：1) it is dissolved in and possesses
Perovskite precursor solution is formed in oxy radical solvent.In precursor solution when containing DMSO B halogenide and X monovalence sun from
Alite from presoma when be initially formed the intermediate containing perovskite presoma so that the speed of precipitation is relatively matched, and is formed three-dimensional cross-linked
Poroid perovskite thin film.
As an example, prepare perovskite/electron acceptor material dispersion liquid and for example may comprise steps of：As above
Electron acceptor material is added in the perovskite precursor solution of formation, perovskite/electron acceptor material dispersion liquid is formed.Perovskite
It is different and different according to the species of selected electron acceptor material from the mol ratio of electron acceptor material, for example can for 0.5～
1000：1.Electron acceptor material can be added with powder, it is also possible to dispersion addition.
Then, bulk heterojunction dispersion liquid (i.e. perovskite/electron acceptor material dispersion liquid) is coated in substrate and forms body
Hetero junction layer presoma.Wherein, the coating method of thin film can be spin-coating method (Spin Coating), slit extrusion molding
(Slot-Die Coating), knife coating (Doctor-Blading Coating) etc..Coating number of times can be one or many
Circulation coating.
Then, perovskite precursor solution is coated with thereon forms one layer of perovskite protective layer.The coating method of thin film
Can be spin-coating method (Spin Coating), slit extrusion molding (Slot-Die Coating), knife coating (Doctor-
Blading Coating) etc..Thus, the bulk heterojunction precursor thin-film that surface has perovskite protective layer is obtained.
In the present invention, when coating bulk heterojunction dispersion liquid film forming, and/or coating perovskite precursor solution film forming, can be with
One-pass film-forming, it is also possible in the solvent of film surface Deca second in film forming procedure, or in negative pressure (such as 5～200Pa) bar
Film forming under part, to promote solvent to volatilize, regulates and controls nucleation and crystal growing process.
Second solvent can be the anti-solvent (abbreviation anti-solvent) of insoluble perovskite.Specifically, the second solvent can be：1)
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, for example may be selected from normal hexane, pentane, octane, 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 in toluene, ether, chlorobenzene, dichlorotoleune etc..In the present invention, the
Two solvents may be selected from least one in ether, normal 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 overall densification.
Before the Deca opportunity of the second solvent can start to become opaque for thin film, drip within 1～2 second most preferably before opaque
Plus.When thin film becomes opaque, perovskite presoma a large amount of nucleation, will lose regulating and controlling effect of second solvent to nucleation.
1～2 second Deca before opaque, now perovskite precursor solution be up to hypersaturated state, the Deca of the second solvent can
So that perovskite precursor solution is rapidly reached supersaturation, the regulation and control of nucleation mode and nucleation density are carried out.For example, the second solvent
Deca opportunity can be to start the 6th～30 second of film forming, the Deca persistent period can be 2～12 seconds.The drop rate of the second solvent
Can be 0.05～0.5mL/s.By selecting the drop rate, effectively the nucleation mode of perovskite precursor solution can be entered
Row regulation and control.
The coating of perovskite/electron acceptor material dispersion liquid and perovskite precursor solution can repeatedly alternately, and
In last coating perovskite precursor solution.
Then, above-mentioned perovskite precursor thin-film is carried out into crystallization treatment.Process can be divided into heat treatment mode with non-thermal place
Reason mode.Wherein, heat treatment temperature can be in room temperature～150 DEG C (preferred room temperature～120 DEG C), and heat treatment mode can be hot plate
Heating, baking oven for heating, sintering stove heat, microwave heating, laser treatment with irradiation etc., process time can be 0～120 minute.It is non-
Heat treatment mode is usually solvent volatilization induction thin film crystallization.Thus, the bulk heterojunction perovskite thin film of the present invention is obtained.This
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 using the perovskite solaode of above-mentioned bulk heterojunction perovskite thin film.The calcium titanium of the present invention
Ore deposit solaode includes successively from bottom to top：Transparent conductive substrate, hole blocking layer, perovskite bulk heterojunction active layer, sky
Cave transport layer and metallic top electrode.
The substrate can adopt the transparency conductive electrode for covering hole barrier layer material, and the material of transparency conductive electrode can be with
Rigid such as FTO glass for rigidity or flexible, ito glass is flexible such as with PEN (PEN), poly- to benzene
Thin polymer films such as naphthalate (PET), polyimides (PI), Merlon (PC), polyaniline, polypyrrole etc. are base
The oxidation film 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。
Described hole blocking layer 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 is received
The perovskite polycrystal film and the perovskite thin film positioned at perovskite polycrystal film surface of body material.Its thickness can for 100～
700nm。
The hole transmission layer can adopt NiO, CuI, CuSCN, MoO3、V2O5、WO3、MoS2、WS2、CoSe、CuSe、CoS、
VC Cr3C2, TiC, VN, PEDOT, poly- 3,4- ethylenedioxy thiophenes:Poly styrene sulfonate (PEDOT:PSS), poly- 3,4- ethylenes
Dioxy thiophene:Tosilate (PEDOT-TsO), 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'-
The fluorenes of spiral shell two, poly- (3- hexyl thiophene -2,5- diyls), poly- [double (4- phenyl) (2,4,62,4,62,4,62,4,6- trimethylbenzenes)
Amine], polypyrrole (PPy), the mixture of one or more mixture of polyaniline (PANI) etc. or its alloy and alloy.Its
The particle diameter of middle inorganic hole transporter is 5～500 nanometers, preferred nano material.
Described metallic top electrode can be gold or silver.Its thickness can be 20～200nm.
Used as an example, the preparation method of the perovskite solaode for example may comprise steps of：
Hole blocking layer is prepared in clean transparent conductive substrate, spin coating, spraying, blade coating, magnetron sputtering, atom can be adopted
The methods such as layer deposition；
Perovskite body is prepared on the hole blocking layer of gained using the above-mentioned method for preparing bulk heterojunction perovskite thin film heterogeneous
Knot active layer, can adopt spin-coating method, slit extrusion molding, knife coating etc.；
The spin coating hole transmission layer on the perovskite bulk heterojunction active layer of gained；
The evaporation metal top electrode on the hole transmission layer of gained.
Can be cleaned before using substrate, for example：It is clear with acetone, alkalis, deionized water, acetone ultrasound respectively
FTO 5～20min of glass are washed, is finally dried up with compressed air, be finally placed on 10～30min of process in UV ozone machine, to remove
The organic impurities of residual simultaneously strengthen wettability of the substrate to solution.
The preparation of perovskite bulk heterojunction active layer for example includes：On the matrix of transparent conductive substrate/hole blocking layer
Deca perovskite/electron acceptor material dispersion liquid, with the rotating speed 10～50s of spin coating of 2000～7000rpm, wherein, such as the 6th
～30 seconds Deca (dripping off in about 2～12 seconds) the second solvent (such as ether) in rotation matrix on；Then, Deca calcium thereon
Titanium ore precursor solution, with the rotating speed 10～50s of spin coating of 2000～7000rpm, wherein, such as in the 6th～30 second Deca (about 2
Drip off in～12 seconds) the second solvent (such as ether) in rotation matrix on；The step of the above two is repeated 1 times the above, obtain perovskite/
Electron acceptor material precursor thin-film；Finally, perovskite precursor solution is coated thereon, form one layer of perovskite protective layer；
Then in 80～150 DEG C of annealing, perovskite/electron acceptor material precursor thin-film is obtained.
In the perovskite solar battery structure of the present invention, perovskite bulk heterojunction active layer is one layer of 100～700nm
Thin film so that the Extracting Ability of electronics is greatly enhanced, while in turn simplify the structure of battery；Compared with traditional perovskite thin film,
Preparation method is simpler, and film quality is more prone to control, overcomes traditional structure complex process and to perovskite thin film
The higher problem of flatness requirement.
And, using bulk heterojunction perovskite thin film, the high temperature needed for independent mesoporous layer preparation process can also be avoided
Sintering process, is suitable to prepare high-efficiency flexible perovskite solaode in ductile basement.
The photoelectric transformation efficiency of the porous perovskite solaode obtained by the present invention has exceeded 17%.This explanation, this
Bright perovskite bulk heterojunction active layer, on the premise of battery efficiency is ensured, is more suitable for large-scale production application.
Advantages of the present invention：
Independent mesoporous layer is not needed using the battery structure of the bulk heterojunction perovskite thin film of the present invention, you can reach mesoporous type
The performance of perovskite solaode, Jing tests, using the perovskite solar-electricity of the bulk heterojunction perovskite thin film of the present invention
The photoelectric transformation efficiency in pond has exceeded 17%.And, using bulk heterojunction perovskite thin film, independent mesoporous layer system can also be avoided
Required high-sintering process, is suitable to prepare high-efficiency flexible perovskite solaode in ductile basement during standby.And
And the preparation method of the type perovskite thin film and battery is simple, the repeatability of institute's assembled battery is high, with traditional perovskite thin film
Compare, preparation method is simpler, film quality is more prone to control, overcome traditional structure complex process and thin to perovskite
The higher problem of the flatness requirement of film, it is adaptable to large-scale production application.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that 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 the concrete numerical value of hereafter example.
Embodiment 1：
Hydro-thermal method synthesizes TiO2It is nanocrystalline：150mL butyl titanates are added under strong stirring the dilute nitre for filling 0.1moL/L
In the glass reaction kettle of acid solution (1000mL), white precipitate is hydrolyzed to form, then reactor is heated to into 120 DEG C, persistently stirred
Mixing lower insulation carries out dispergation for 8 hours and concentrates.Gained colloidal sol is proceeded in titanium autoclave, in 260 DEG C of hydrothermal treatment consists 12 hours, is obtained
To TiO2It is nanocrystalline.The TiO for obtaining2Nanocrystalline particle diameter is for about 20nm；
(1) preparation of perovskite/electron acceptor material dispersion liquid.TiO is prepared first2DMF dispersion liquids：Hydro-thermal method is synthesized
TiO2Nanocrystalline deionized water, ethanol and DMF washing respectively, goes the removal of impurity, is then dispersed in formation dispersion liquid in DMF standby
With.Then, by PbI2, MAI and DMSO is with 1:1:1 ratio is dissolved in DMF and is sufficiently stirred for, and obtains perovskite presoma molten
Liquid (MAPbI3), then by perovskite precursor solution and TiO2DMF dispersion liquids with certain proportion (MAPbI3With TiO2Mole
Than for 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 10min with acetone, alkalis, deionized water, acetone respectively,
Finally dried up with compressed air, be finally placed in UV ozone machine and process 15min, to remove the organic impurities of residual and strengthen
Wettability of the substrate to solution；
(3) preparation of hole blocking layer.Precursor solution solvent is ethanol, including following component：Tetraisopropyl titanate
(0.3mol/L), acetylacetone,2,4-pentanedione (0.45mol/L), hydrochloric acid (0.09mol/L), water (1.8mol/L).Draw precursor solution, drop
It is added on the FTO of step (1), makes solution be paved with whole FTO surfaces, spin speed 3000rpm, time 20s, then in Muffle furnace
In 510 DEG C sintering 30min；
(4) preparation of perovskite bulk heterojunction active layer.Deca MAPbI on the matrix of FTO/ hole blocking layers3/TiO2Nanometer
Brilliant forerunner's dispersion liquid, wherein MAPbI3With TiO2Mol ratio is 5:1, with the rotating speed spin coating 20s of 5000rpm, wherein at the 6th second
Quickly (drip off in about 2 seconds) Deca 0.5mL ether in rotation matrix on；The spin-coating step is repeated 2 times, and obtains perovskite/electricity
Sub- acceptor material precursor thin-film, then, Deca MAPbI thereon3Forerunner's dispersion liquid, with the rotating speed spin coating of 5000rpm
20s, wherein in the 6th second quick (dripping off in about 2 seconds) Deca 0.5mL ether on the matrix of 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.Spin coating hole transmission layer is molten on the bulk heterojunction perovskite thin film that step (4) is obtained
Liquid, its composition is：The chlorine of the 2,2' of 72.3mg/mL, 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] fluorenes of -9,9'- spiral shells two
Benzole soln, including the acetonitrile solution and uncle 4- of 20 μ L of double (fluoroform) sulfimide lithium salts of the 520mg/mL of 20 μ L/mL
Butyl-pyridinium is used as additive, rotating speed 4000rpm, time 30s；
(6) prepared by Ag top electrodes.Evaporation 120nm thickness Ag layers are top electrode, obtain perovskite solaode.
Embodiment 2：
(1) preparation of perovskite/electron acceptor material dispersion liquid.TiO is prepared first2DMF dispersion liquids：Hydro-thermal method is synthesized
TiO2Nanocrystalline deionized water, ethanol and DMF washing respectively, goes the removal of impurity, is then dispersed in formation dispersion liquid in DMF standby
With.Then, by PbI2, MAI and DMSO is with 1:1:1 ratio is dissolved in DMF and is sufficiently stirred for, and obtains perovskite presoma molten
Liquid (MAPbI3), then by perovskite precursor solution and TiO2DMF dispersion liquids with certain proportion (MAPbI3With TiO2Mole
Than for 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.Deca MAPbI on the matrix of FTO/ hole blocking layers3/TiO2Nanometer
Brilliant forerunner's dispersion liquid, wherein MAPbI3With TiO2Mol ratio is 10:1, other operations are with embodiment 1；
(5) preparation of hole transmission layer.With embodiment 1；
(6) preparation of Ag top electrodes.With embodiment 1.
Embodiment 3：
(1) preparation of perovskite/electron acceptor material dispersion liquid.By PbI2, MAI and DMSO is with 1:1:1 ratio is dissolved in DMF
In and be sufficiently stirred for, obtain perovskite precursor solution (MAPbI3), it is subsequently adding a certain amount of Graphene (Aldrich, nanometer
Piece, powder body is hydrophobic) and it is 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.Deca MAPbI on the matrix of FTO/ hole blocking layers3Before/Graphene
Drive dispersion liquid, wherein MAPbI3It is 5 with Graphene mol ratio:1, other operations are with embodiment 1；
(5) preparation of hole transmission layer.With embodiment 1；
(6) preparation of Ag top electrodes.With embodiment 1.
Embodiment 4：
(1) preparation of perovskite/electron acceptor material dispersion liquid.By PbI2, MAI and DMSO is with 1:1:1 ratio is dissolved in DMF
In and be sufficiently stirred for, obtain perovskite precursor solution (MAPbI3), be subsequently adding a certain amount of fullerene (Aldrich,
99.5%) and it is 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.Deca MAPbI on the matrix of FTO/ hole blocking layers3Before/fullerene
Drive dispersion liquid, wherein MAPbI3It is 5 with fullerene mol ratio:1, other operations are with embodiment 1；
(5) preparation of hole transmission layer.With embodiment 1；
(6) preparation of Ag top electrodes.With embodiment 1.
Embodiment 5：
(1) preparation of perovskite/electron acceptor material dispersion liquid.By PbI2, MAI and DMSO is with 1:1:1 ratio is dissolved in DMF
In and be sufficiently stirred for, obtain perovskite precursor solution (MAPbI3), it is subsequently adding a certain amount of carbon black (Japanese Lion, section's qin
It is 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.Deca MAPbI on the matrix of FTO/ hole blocking layers3/ carbon black forerunner
Dispersion liquid, wherein MAPbI3It is 5 with carbon black mol ratio:1, other operations are with embodiment 1；
(5) preparation of hole transmission layer.With embodiment 1；
(6) preparation of Ag top electrodes.With embodiment 1.
Embodiment 6：
(1) preparation of perovskite/electron acceptor material dispersion liquid.By PbI2, MAI and DMSO is with 1:1:1 ratio is dissolved in DMF
In and be sufficiently stirred for, obtain perovskite precursor solution (MAPbI3), be subsequently adding 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.Deca MAPbI on the matrix of FTO/ hole blocking layers3/ graphite forerunner
Dispersion liquid, wherein MAPbI3It is 5 with graphite mol ratio:1, other operations are with embodiment 1；
(5) preparation of hole transmission layer.With embodiment 1；
(6) preparation of Ag top electrodes.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 TiO2Nanocrystalline point
Dissipate the nano-TiO that 20wt% is formed in ethanol2Slurry, with it as material, using silk-screen printing technique on hole blocking layer
Coat mesoporous TiO2Film, subsequently sinters 30min at 510 DEG C, forms mesoporous electron transfer layer；
(4) preparation of calcium titanium ore bed.By PbI2, MAI and DMSO is with 1:1:1 ratio is dissolved in DMF and is sufficiently stirred for, and is formed
Perovskite precursor solution, the Deca perovskite precursor solution on the matrix of FTO/ hole blocking layers/mesoporous layer, with
The rotating speed spin coating 20s of 5000rpm, wherein in the 6th second quick (dripping off in about 2 seconds) Deca 0.5mL ether on the matrix of 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 electrodes.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%2Ethanol disperses
Liquid (with comparative example 1) is material, and mesoporous TiO is coated on hole blocking layer using spin coating proceeding2Film, subsequently in 120 DEG C of drying
20min, forms mesoporous electron transfer layer；
(4) preparation of calcium titanium ore bed.By PbI2, MAI and DMSO is with 1:1:1 ratio is dissolved in DMF and is sufficiently stirred for, and is formed
Perovskite precursor solution, the Deca perovskite precursor solution on the matrix of FTO/ hole blocking layers/mesoporous layer, with
The rotating speed spin coating 20s of 5000rpm, wherein in the 6th second quick (dripping off in about 2 seconds) Deca 0.5mL ether on the matrix of 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 electrodes.With embodiment 1.
Embodiment 1～6, the perovskite solaode of comparative example 1 and 2 for manufacturing as described above is have rated as follows.That is,
By using solar simulator (AM1.5,100mW/cm of standard type xenon lamp2), determine opening for perovskite solaode
Road voltage Voc, short-circuit current density Jsc, fill factor, curve factor FF and efficiency eta.Its result is illustrated in table 1.
Table 1：
As shown in Table 1, the present invention adopts bulk heterojunction perovskite light absorbing zone, equally obtains high-photoelectric transformation efficiency
Perovskite solaode, its photoelectric transformation efficiency is suitable with the mesoporous type perovskite solaode for needing high-sintering process
Even more high, and far above the mesoporous type perovskite solaode without high-sintering process, overcome surfacing smooth
Perovskite thin film requires harsh shortcoming to preparation technology, enormously simplify the preparation technology of thin film, improves yield rate, is calcium
The scale of titanium ore solaode is prepared and laid 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
Go out TiO2Pinning 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,
The technological thought of this technology can be based on carries out various modifications.For example, composition, method, step, the shape enumerated in above-mentioned embodiment
Looks, material and numerical value etc. are only as an example, it is also possible to as needed using composition unlike this, method, step, pattern,
Material and numerical value etc..In addition, the composition of above-mentioned embodiment, method, step, shape, pattern and numerical value etc. can not take off
It is mutually combined in the range of the purport of this technology.
Claims (9)
1. a kind of bulk heterojunction perovskite thin film, it is characterised in that the bulk heterojunction perovskite thin film includes：
Bulk heterojunction layer, the bulk heterojunction layer is included as the perovskite polycrystal film of electron donor material and positioned 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, it is characterised 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, preferably CH3NH3 +、NH2-CH=NH2 +、Cs+、Li+、C4H9NH3 +、CH6N3 +、Na+、K+In at least one；B is Pb2+、Sn2+、Ge2+、Co2+、Fe2+、
Mn2+、Cu2+、Ni2+In at least one；X is Cl‒、Br‒、I‒、SCN-、BF4 -In at least one.
3. bulk heterojunction perovskite thin film according to claim 1 and 2, it is characterised in that the electron acceptor material is
Nanocrystalline TiO2, nanocrystalline SnO2, Nanocrystalline ZnO Powder, fullerene, fullerene derivate, perylene diimides, naphthalimide, based on expansion
The organic macromolecule acceptor material of thiophene condensed ring, Graphene, white carbon black, graphite, nano-crystalline Fe2O3, nanocrystalline ZnSnO3, it is nanocrystalline
At least one in CdS, nanocrystalline CdSe.
4. bulk heterojunction perovskite thin film according to any one of claim 1 to 3, it is characterised in that the body is heterogeneous
The thickness of knot perovskite thin film is in 100～700nm.
5. the preparation method of the bulk heterojunction perovskite thin film any one of a kind of Claims 1-4, it is characterised in that
Including：
First perovskite precursor solution and electron acceptor material are mixed to get into perovskite/electron acceptor material dispersion liquid；
The perovskite/electron acceptor material dispersion is coated with into the second perovskite presoma in substrate, thereon
Solution, forms bulk heterojunction precursor thin-film；
The bulk heterojunction precursor thin-film is carried out into crystallization treatment, the bulk heterojunction perovskite thin film is obtained.
6. the preparation method of bulk heterojunction perovskite thin film according to claim 5, it is characterised in that before the first perovskite
Driving the preparation of liquid solution and/or the second perovskite precursor solution includes：By the halide solution of B, the monovalent cation salt of X,
And first solvent mixing；Wherein, first solvent is to possess oxy radical solvent, and preferred dimethylformamide, diformazan are sub-
At least one in sulfone, gamma-butyrolacton, METHYLPYRROLIDONE.
7. the preparation method of the bulk heterojunction perovskite thin film according to claim 5 or 6, it is characterised in that in the body
In the film forming procedure of hetero-junctions precursor thin-film, the step of be additionally included in film surface the second solvent of Deca, second solvent
At least one in ether, normal hexane, petroleum ether, toluene, chlorobenzene, dichlorotoleune.
8. the preparation method of the bulk heterojunction perovskite thin film according to any one of claim 5 to 7, it is characterised in that
The crystallization treatment using heat treatment mode or non-heat treated mode, the heat treatment mode be hot plate heating, baking oven for heating,
Sintering stove heat, microwave heating or laser treatment with irradiation, the temperature of the heat treatment is room temperature～150 DEG C, and process time is 0
～120 minutes；The non-heat treated mode is solvent volatilization induction thin film crystallization.
9. a kind of perovskite solaode, it is characterised in that the perovskite solaode includes successively from bottom to top：Thoroughly
Bulk heterojunction perovskite thin film any one of bright conductive substrates, hole blocking layer, Claims 1-4, hole transmission layer
And top electrode.
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