CN109103337A - A kind of technique and its application using bustamentite carbonamidine as solar battery light-absorption layer - Google Patents

A kind of technique and its application using bustamentite carbonamidine as solar battery light-absorption layer Download PDF

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CN109103337A
CN109103337A CN201810771232.5A CN201810771232A CN109103337A CN 109103337 A CN109103337 A CN 109103337A CN 201810771232 A CN201810771232 A CN 201810771232A CN 109103337 A CN109103337 A CN 109103337A
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carbonamidine
bustamentite
precursor liquid
dmso
fapbi
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韩宏伟
侯晓萌
梅安意
胡玥
荣耀光
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/12Deposition of organic active material using liquid deposition, e.g. spin coating
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30Coordination compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

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  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The technique and its application that the invention discloses a kind of using bustamentite carbonamidine as solar battery light-absorption layer, the solar battery light-absorption layer are specially the perovskite of the component of carbonamidine containing bustamentite, and preparation method is specifically that (1) prepares meso-hole structure;(2) contain FAPbI3The preparation of the precursor liquid of bustamentite carbonamidine perovskite: will include PbI2, the raw material including FAI, CsI etc. matched by chemical dosage ratio, be then dissolved in solvent, stir evenly, obtain the precursor liquid of clear;(3) precursor liquid is filled in meso-hole structure, is stood, then the internal structure containing bustamentite carbonamidine can be obtained in annealing under solvent atmosphere.The present invention can slow down crystallization while inhibiting the volatilization of iodine carbonamidine (FAI) etc., enable to FAPbI by the annealing in the case where solvent vapour assists, the steam auxiliary of solvent3Black phase is stabilized in mesoporous membrane structure.

Description

A kind of technique and its application using bustamentite carbonamidine as solar battery light-absorption layer
Technical field
The invention belongs to area of solar cell, more particularly, to one kind with bustamentite carbonamidine (FAPbI3) it is used as the sun The technique and its application of energy battery light-absorption layer.
Background technique
Solar energy is developed and utilized as a kind of reproducible clean energy resource.The perovskite of organic inorganic hybridization Material is direct band-gap semicondictor, have light absorpting ability is strong, carrier mobility is high, band gap is adjustable, bipolar carrier conduction, The features such as solution processable is the ideal material for preparing solar battery.Between a few years, the performance of perovskite solar battery Rapid development, started the research boom of countries in the world researcher, laboratory notarization efficiency has broken through 22.7%, be more than Take the lead in race in photovoltaic art many years polysilicon solar cell highest photoelectric conversion efficiency.
MAPbI3(Eg=1.5eV, absorbing cut-off side is 800nm) is to be studied most commonly used perovskite material.For More concerns have been invested bustamentite carbonamidine (FAPbI by further promotion device performance, researcher3).Compared to MAPbI3, FAPbI3The band gap for possessing 1.48eV, closer to the ideal value (1.4eV) of single-unit solar photovoltaic device, correspondingly, it It absorbs cut-off side and has widened 840~850nm (also having document report to 870nm), there are stronger absorbing properties, provide more High photoelectric current.On the other hand, MAPbI3Under device operating temperature (55 DEG C) there are reversible by cubic opposite cubic phase Transformation, the transformation of this structure may illumination to device, temperature stability all adversely affect, and FAPbI3Show ratio MAPbI3Excellent thermal stability.Bustamentite carbonamidine (FAPbI3) there is the phase transition of black phase and yellow phase for perovskite.Black phase It is but not easy to be obtained for ideal photoelectric material.And (about 13 microns of the thickness of whole meso-hole structure is even more in meso-hole structure High: the thickness of mesoporous carbon electrode is generally 10-15 microns, and the thickness of titanium dioxide and zirconium dioxide is generally 2.5-3 microns, Therefore thickness of detector is at least at 13 microns), it is mutually particularly difficult to generate black.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide one kind with bustamentite carbonamidine work For the technique and its application of solar battery light-absorption layer, wherein passing through its preparation side of structure to mesoporous inside containing bustamentite carbonamidine Ambiance locating for the integral process flow design of method, especially crucial annealing process is controlled, with prior art phase Than can effectively solve the problem that bustamentite carbonamidine effectively cannot be stable at meso-hole structure (especially thicker Jie with the Perovskite Phase of black Pore structure, such as with a thickness of 13 microns or more of meso-hole structure) the problem of, the present invention passes through the annealing in the case where solvent vapour assists The steam auxiliary of processing, solvent can slow down crystallization while inhibiting the volatilization of iodine carbonamidine (FAI) etc., enable to FAPbI3? Black phase is stabilized in mesoporous membrane structure;Also, Cs in precursor liquid+Introducing can also further decrease FAPbI3Inversion of phases Activation energy, improve FAPbI3The stability of black phase and service life.Present invention process is simple, it is low in cost, can effectively by FAPbI3Stablize in black Perovskite Phase, promotes the performance of such as solar battery.
To achieve the above object, according to one aspect of the present invention, a kind of structure of the inside containing bustamentite carbonamidine is provided Preparation method, which comprises the following steps:
(1) meso-hole structure is prepared;
(2) contain FAPbI3The preparation of the precursor liquid of bustamentite carbonamidine perovskite: will include PbI2, raw material including FAI is by chemistry Dose ratio proportion, is then dissolved in solvent, stirs evenly, obtain the precursor liquid of clear;
The solvent is the mixture of DMF, DMSO or both, perhaps for DMSO and chlorobenzene mixture or be DMSO With the mixture of alcohol;
(3) precursor liquid that the step (2) obtains is filled in the meso-hole structure that the step (1) obtains In, it stands, then annealing can be obtained inside and contain iodine under the solvent atmosphere containing DMSO or simultaneously containing DMSO and DMF The structure of lead carbonamidine.
As present invention further optimization, for the precursor liquid that the step (2) obtains, the precursor liquid is corresponding Presoma solute be include FAPbI3The mixture of a variety of perovskite materials including perovskite contains Cs in the mixture+It is corresponding Perovskite material, the mixture is preferably CsxFA1-xPbI3Or (CsPbI3)x((FAPbI3)0.85(MAPbBr3)0.15)1-x, Wherein x meets x=0~0.15;
When the presoma solute is CsxFA1-xPbI3Or (CsPbI3)x((FAPbI3)0.85(MAPbBr3)0.15)1-xWhen, institute Stating raw material accordingly further includes CsI, PbBr2, at least one of MAI and MABr.
As present invention further optimization, in the precursor liquid that the step (2) obtains, the presoma solute Concentration is 1M, Cs+Content in 0~0.15M;
In the step (3), precursor liquid described in 2.5~3.1 μ L is filled specifically into the meso-hole structure, is preferably filled out Fill precursor liquid described in 3.0 μ L.
As present invention further optimization, in the step (2), the solvent is DMF, or presses for DMF and DMSO Volume ratio is 6/1~4/1 mixture being mixed to get.
As present invention further optimization, in the step (3), the annealing is carried out under DMSO atmosphere 's;
Preferably, annealing temperature used in the annealing is not less than 75 DEG C, and annealing temperature is more preferably 100 DEG C, annealing Time is 30~60min, more preferably 30min.
It is another aspect of this invention to provide that the present invention provides the inside being prepared using above-mentioned preparation method to contain iodine The structure of lead carbonamidine.
Another aspect according to the invention, the structure the present invention provides above-mentioned inside containing bustamentite carbonamidine is in solar-electricity Application in pond or photodetector.
It is another aspect of this invention to provide that the present invention provides a kind of using bustamentite carbonamidine as solar battery light-absorption layer The preparation method of solar battery, which comprises the following steps:
(1) it is sequentially prepared transparency conducting layer, charge transport layer, insulating layer and carbon electrode layer on substrate, the charge passes Defeated layer, the insulating layer and the carbon electrode layer all have meso-hole structure, thus obtain the blank with three layers of mesoporous membrane structure Device;
(2) contain FAPbI3The preparation of the precursor liquid of bustamentite carbonamidine perovskite: will include PbI2, raw material including FAI is by chemistry Dose ratio proportion, is then dissolved in solvent, stirs evenly, obtain the precursor liquid of clear;
The solvent is the mixture of DMF, DMSO or both, perhaps for DMSO and chlorobenzene mixture or be DMSO With the mixture of alcohol;
(3) precursor liquid that the step (2) obtains is filled in the blank device that the step (1) obtains In, it stands, then annealing can be obtained inside and contain iodine under the solvent atmosphere containing DMSO or simultaneously containing DMSO and DMF The solar battery of lead carbonamidine, the solar battery is i.e. using bustamentite carbonamidine as the solar battery of solar battery light-absorption layer.
As present invention further optimization, for the precursor liquid that the step (2) obtains, the precursor liquid is corresponding Presoma solute be include FAPbI3The mixture of a variety of perovskite materials including perovskite contains Cs in the mixture+It is corresponding Perovskite material, the mixture is preferably CsxFA1-xPbI3Or (CsPbI3)x((FAPbI3)0.85(MAPbBr3)0.15)1-x, Wherein x meets x=0~0.15;
When the presoma solute is CsxFA1-xPbI3Or (CsPbI3)x((FAPbI3)0.85(MAPbBr3)0.15)1-xWhen, institute Stating raw material accordingly further includes CsI, PbBr2, at least one of MAI and MABr.
As present invention further optimization, in the step (1), the substrate is glass, and the charge transport layer is TiO2Nanometer crystal film, ZnO nano epitaxial, BaSnO3Nanometer crystal film or SnO2Nanometer crystal film, the insulating layer are ZrO2Insulating layer, SrTiO3Insulating layer, Al2O3Insulating layer or BaTiO3Insulating layer.
Contemplated above technical scheme through the invention contains bustamentite first by the way that preparation is internal compared with prior art The structure of amidine can effectively improve mesoporous interior bustamentite carbonamidine perovskite material (such as CsxFA1-xPbI3、(CsPbI3)x((FAPbI3)0.85 (MAPbBr3)0.15)1-xDeng) stability/service life, and can further apply in solar battery or photodetector, improve Stability/service life of these devices.Present invention process is simple, it is low in cost, can be effectively by FAPbI3Stablize in black calcium titanium Mine phase promotes the performance of such as solar battery.The present invention can by using DMF, DMSO or the mixture of both (when The mixture of DMSO and chlorobenzene, or the mixture for DMSO and alcohol can also so be used) contain FAPbI as preparation3Bustamentite The precursor liquid of carbonamidine perovskite material, after precursor liquid is packed into meso-hole structure, by auxiliary in the solvent vapour containing DMSO The steam auxiliary of annealing under helping, solvent can slow down crystallization while inhibiting the volatilization of iodine carbonamidine (FAI) etc., can make Obtain FAPbI3Black phase is stabilized in mesoporous membrane structure;Also, Cs in precursor liquid+Introducing can also further decrease FAPbI3The activation energy of inversion of phases improves FAPbI3The stability of black phase and service life.
For structure of the mesoporous inside containing bustamentite carbonamidine is applied to solar battery, light absorbent is organic-inorganic The perovskite material of hydridization, such as contains FAPbI3The mixtures of a variety of perovskite materials (at least contain Cs in the mixture+It is right The perovskite material answered), the present invention can achieve the following beneficial effects:
(1) when structure of the mesoporous inside containing bustamentite carbonamidine is applied to solar battery, bustamentite carbonamidine can be used as solar energy The light-absorption layer of battery plays a role;Structure preparation method inside this containing bustamentite carbonamidine, can be simply and effectively by bustamentite carbonamidine Stablize the Perovskite Phase in black, improves the device performance of printable perovskite solar battery.
To contain FAPbI3The precursor liquid of bustamentite carbonamidine perovskite uses DMF/DMSO mixed solvent, contains Cs simultaneously+For (DMSO, that is, dimethyl sulfoxide), passes through Cs+Introducing to reduce FAPbI3The activation energy of inversion of phases, the steam auxiliary of mixed solvent Slow down crystallization while inhibiting the volatilization of iodine carbonamidine (FAI) etc., makes FAPbI3It is stabilized in three layers of mesoporous membrane structure black Form and aspect, device can get 15% photoelectric conversion efficiency.
(2) when preparing solar battery, the blank device with three layers of mesoporous membrane structure specifically can be first prepared, this three layers Mesoporous film can be prepared using silk-screen printing;The present invention is inhaled using the better bustamentite carbonamidine of photoelectric properties as solar battery Photosphere, simple process and low cost, device dark-state with higher and thermal stability, to can print perovskite solar battery Commercially produce offer more may.
(3) when the present invention prepares solar battery with carbon be electrode is avoided at high price instead of noble metal electrode Evaporated device use.And this structure can not need organic cavity transmission layer (such as Spiro-OMeTAD, cuprous sulfocyanide (CuSCN), CuPc (CuPc), nickel oxide (NiO), poly- 3- hexyl thiophene (P3HT), poly- [bis- (4- phenyl) (2,4,6- front threes Base phenyl) amine] (PTAA), poly styrene sulfonate doping the prior arts such as poly- 3,4-rthylene dioxythiophene (PEDOT:PSS) Used in HTM organic cavity transmission layer material), reduce the cost of material, improve the stability of device.
Due to pure bustamentite carbonamidine (FAPbI3) there are yellow phase and black phase, (wherein, black is mutually with good photoelectricity The Perovskite Phase of performance);At room temperature, yellow is mutually stable, and the black phase color generated under high temperature (140-170 DEG C) is under certain humidity It is readily converted to yellow phase.It is particularly due to the limitation by thicker meso-hole structure, generates black mutually more difficult.This is specially Benefit is preferably by introducing into part Cs+Replace FA, using DMSO and DMF mixed solvent as precursor liquid solvent (alternatively, can also adopt With the mixture of DMF, DMSO or both, perhaps for DMSO and chlorobenzene mixture or be that the mixture of DMSO and alcohol is made For precursor liquid solvent), and successfully stablized bustamentite carbonamidine in Perovskite Phase in thicker structure using DMSO steam auxiliary, It can get 15% incident photon-to-electron conversion efficiency and preferable stability.Bustamentite carbonamidine can be stablized the perovskite in black by the present invention Phase is especially applicable in three layers of mesoporous membrane structure of the thickness greater than 13 microns.In slab construction, simply introduce a certain amount of Cs can be by FAPbI3Stablize in black phase, and due to the limitation of meso-hole structure, cause the generation of bustamentite carbonamidine black phase more It is difficult.The present invention obtains being moved back under conditions of introducing Cs using specific annealing atmosphere by change and Optimizing Technical Fire processing (is such as annealed 30 minutes in 100 DEG C of steam containing DMSO), and black bustamentite first can be realized in such device architecture The generation of amidine phase, to promote device performance.
Detailed description of the invention
Fig. 1 is a kind of process flow using bustamentite carbonamidine as solar battery light-absorption layer provided in an embodiment of the present invention Figure.
Fig. 2 is to see in printable solar battery to introduce Cs in Jie without hole transport material based on carbon electrode+, make Use CsxFA1-xPbI3、(CsPbI3)x((FAPbI3)0.85(MAPbBr3)0.15)1-xAs precursor liquid, anneal at 100 DEG C respectively 30min (dotted line), or 30min (solid line) device performance obtained of annealing in the solvent atmosphere containing DMSO 100 DEG C. Respectively correspond embodiment 3-4,7-8.
Fig. 3 is to see in printable solar battery be not introduced into Cs in Jie without hole transport material based on carbon electrode+Under conditions of, FAPbI is used respectively3、(FAPbI3)0.85(MAPbBr3)0.15Prepare device.Wherein, a figure gives in Fig. 3 FAPbI3At DMF (a) and DMF/DMSO (b) atmosphere, 150 DEG C of annealing 30min;And (FAPbI3)0.85(MAPbBr3)0.15? Under DMF (c) and DMF/DMSO (d) atmosphere, the device of 100 DEG C of annealing 30min preparations, the photograph of the device captured by the glass surface Piece is in yellow phase.Respectively correspond embodiment 1-2,5-6.B figure, c figure are set forth in N in Fig. 32Glove box and air atmosphere In enclosing, by above-mentioned technique prepare the corresponding J-V curve of device, it can be seen that these techniques preparation device photoelectric performance compared with Difference.In addition, b schemes in Fig. 3, the perovskite group of (e) is divided into FA in c figure0.81MA0.15PbI2.51Br0.45 [1], (f) group is divided into FAPbI3 (FACl)[2], under DMF/DMSO atmosphere, the device of 100 DEG C of annealing 30min preparations.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below Not constituting a conflict with each other can be combined with each other.
As shown in Figure 1, using bustamentite carbonamidine as the technique of solar battery light-absorption layer in the present invention, in short, including Following steps:
(1) it is sequentially prepared transparency conducting layer, charge transport layer, insulating layer and carbon electrode layer on substrate (for example, charge passes Defeated layer can be TiO2, insulating layer can be ZrO2), wherein charge transport layer, insulating layer and carbon electrode layer are mesoporous layer, from And prepare the blank device with three layers of mesoporous membrane structure;
(2) preparation of the precursor liquid of perovskite: according to target the chemical dosage ratio of perovskite material matches raw material PbI2, PbBr2 And CsI, FAI, MABr, and dissolve them in a certain amount of DMF, DMSO, it stirs evenly, obtains the forerunner of clear Liquid;Aimed perovskite material can be FAPbI3, or contain FAPbI3A variety of perovskite materials mixture, such as CsxFA1- xPbI3、(CsPbI3)x((FAPbI3)0.85(MAPbBr3)0.15)1-xIt can be 0~0.15 Deng, x;
(3) a certain amount of precursor liquid is filled in the blank device of silk-screen printing, is stood, after annealing under solvent atmosphere Complete preparation.
The present invention is to prepare device by first preparing blank device (such as thickness can be greater than 13 microns), then using drop-coating.
Invention further contemplates the annealing process of three kinds of routes, to be dissolved in the FAI/PbI in DMF/DMSO2It prepares Precursor liquid for, route I (technique used by the embodiment of the present invention 1,2) be 150 DEG C at annealing obtain δ-FAPbI3, route II (technique used by the embodiment of the present invention 3,7) is to have Cs in introducing+In the case where anneal at 100 DEG C, route III (this Technique used by inventive embodiments 4,8) it is then to have Cs in introducing+In the case where at a temperature of 100 DEG C, auxiliary atmosphere in Annealing obtains α-FAPbI3
Present invention process is simple, it is low in cost, can be effectively by FAPbI3Stablize in black Perovskite Phase, is promoted cell performance Energy.
The following are specific embodiments:
Embodiment 1
(1) transparency conducting layer, TiO are sequentially prepared on FTO substrate2(such as NR18, NR30, P25) charge transport layer, insulation Layer (ZrO2) and carbon electrode layer, prepare the blank device with three layers of mesoporous membrane structure;
(2) preparation of the precursor liquid of perovskite: PbI2And CsI, FAI are dissolved in a certain amount of DMF, are stirred evenly, and are obtained Obtain clear, the precursor liquid FAPbI that perovskite content is 1M3
(3) precursor liquid of 3 μ L is filled in the blank device of silk-screen printing, is stood, containing DMF and without DMSO Preparation is completed after the lower 150 DEG C of annealing 30min of atmosphere.
Embodiment 2
(1) transparency conducting layer, TiO are sequentially prepared on FTO substrate2(NR18, NR30, P25) charge transport layer, insulating layer (ZrO2) and carbon electrode layer, prepare the blank device with three layers of mesoporous membrane structure;
(2) preparation of the precursor liquid of perovskite: PbI2With FAI be dissolved in a certain amount of DMF/DMSO (volume ratio be 6/1~ 4/1) it in, stirs evenly, obtains clear, the precursor liquid FAPbI that perovskite content is 1M3
(3) precursor liquid of 3 μ L is filled in the blank device of silk-screen printing, is stood, in the solvent atmosphere containing DMSO Under (i.e. under the steam atmosphere containing DMSO) after 150 DEG C of annealing 30min complete preparation.
Embodiment 3
(1) transparency conducting layer, TiO are sequentially prepared on FTO substrate2(NR18, NR30, P25) charge transport layer, insulating layer (ZrO2) and carbon electrode layer, prepare the blank device with three layers of mesoporous membrane structure;
(2) preparation of the precursor liquid of perovskite: PbI2And CsI, FAI are dissolved in a certain amount of DMF, are stirred evenly, and are obtained Obtain clear, the precursor liquid Cs that perovskite content is 1MxFA1-xPbI3(x=0-0.15);
(3) precursor liquid of 3 μ L is filled in the blank device of silk-screen printing, is stood, it is complete after 100 DEG C of annealing 30min At preparation.
Embodiment 4
(1) transparency conducting layer, TiO are sequentially prepared on FTO substrate2(NR18, NR30, P25) charge transport layer, insulating layer (ZrO2) and carbon electrode layer, prepare the blank device with three layers of mesoporous membrane structure;
(2) preparation of the precursor liquid of perovskite: PbI2And CsI, FAI are dissolved in a certain amount of DMF/DMSO (volume ratio are 6/1~4/1) it in, stirs evenly, obtains clear, the precursor liquid Cs that perovskite content is 1MxFA1-xPbI3(x=0- 0.15);
(3) precursor liquid of 3 μ L is filled in the blank device of silk-screen printing, is stood, in the solvent atmosphere containing DMSO Under (i.e. under the steam atmosphere containing DMSO) after 100 DEG C of annealing 30min complete preparation.
Embodiment 5
(1) transparency conducting layer, TiO are sequentially prepared on FTO substrate2(NR18, NR30, P25) charge transport layer, insulating layer (Al2O3) and carbon electrode layer, prepare the blank device with three layers of mesoporous membrane structure;
(2) preparation of the precursor liquid of perovskite: PbI2, PbBr2And FAI, MABr are dissolved in a certain amount of DMF, stirring is equal It is even, obtain clear, the precursor liquid (FAPbI that perovskite content is 1M3)0.85(MAPbBr3)0.15
(3) precursor liquid of 3 μ L is filled in the blank device of silk-screen printing, is stood, containing DMF and without DMSO Preparation is completed after the lower 100 DEG C of annealing 30min of atmosphere.
Embodiment 6
(1) transparency conducting layer, TiO are sequentially prepared on FTO substrate2(NR18, NR30, P25) charge transport layer, insulating layer (ZrO2) and carbon electrode layer, prepare the blank device with three layers of mesoporous membrane structure;
(2) preparation of the precursor liquid of perovskite: PbI2, PbBr2And FAI, MABr are dissolved in a certain amount of DMF/DMSO (body Product is than being 6/1~4/1) in, it stirs evenly, obtains clear, the precursor liquid (FAPbI that perovskite content is 1M3)0.85 (MAPbBr3)0.15
(3) precursor liquid of 3 μ L is filled in the blank device of silk-screen printing, is stood, in the solvent atmosphere containing DMSO Under (i.e. under the steam atmosphere containing DMSO) after 100 DEG C of annealing 30min complete preparation.
Embodiment 7
(1) transparency conducting layer, TiO are sequentially prepared on FTO substrate2(NR18, NR30, P25) charge transport layer, insulating layer (ZrO2) and carbon electrode layer, prepare the blank device with three layers of mesoporous membrane structure;
(2) preparation of the precursor liquid of perovskite: PbI2, PbBr2And CsI, FAI, MABr are dissolved in a certain amount of DMF, stirring Uniformly, clear is obtained, the precursor liquid (CsPbI that perovskite content is 1M3)x((FAPbI3)0.85(MAPbBr3)0.15)1-x(x =0-0.15);
(3) precursor liquid of 3 μ L is filled in the blank device of silk-screen printing, is stood, it is complete after 100 DEG C of annealing 30min At preparation.
Embodiment 8
(1) transparency conducting layer, TiO are sequentially prepared on FTO substrate2(NR18, NR30, P25) charge transport layer, insulating layer (Al2O3) and carbon electrode layer, prepare the blank device with three layers of mesoporous membrane structure;
(2) preparation of the precursor liquid of perovskite: PbI2, PbBr2And CsI, FAI, MABr are dissolved in a certain amount of DMF/DMSO It in (volume ratio is 6/1~4/1), stirs evenly, obtains clear, the precursor liquid (CsPbI that perovskite content is 1M3)x ((FAPbI3)0.85(MAPbBr3)0.15)1-x(x=0-0.15);
(3) precursor liquid of 3 μ L is filled in the blank device of silk-screen printing, is stood, in the solvent atmosphere containing DMSO Under (i.e. under the steam atmosphere containing DMSO) after 100 DEG C of annealing 30min complete preparation.
Embodiment 9
With CsxFA1-xPbI3For middle x=0.1, Cs that above-described embodiment 4 is prepared0.1FA0.9PbI3Device saves In the air of relative humidity 30%~50%, every 48h~50h tests a device efficiency.By the test of 300h, device Battery parameter still has the 94.2% of original efficiency there is no apparent variation, device efficiency occurs.
Embodiment 10
The present invention has carried out contrasting detection to the performance of embodiment 3-4,7-8 obtained device, as a result as shown in Figure 2.For into One step demonstrate,proves influence of the annealing atmosphere to device performance, and the present invention is also in N2Embodiment 1- is repeated under atmosphere and air atmosphere respectively 2,5-6, as a result as shown in Figure 3.Also, the mature technology that the present invention also refers to other laboratories is prepared for respectively FA0.81MA0.15PbI2.51Br0.45 [1]、FAPbI3(FACl)[2]In the device of 100 DEG C of annealing 30min preparations under DMF/DMSO atmosphere Part, test results are shown in figure 3.
The present invention is also prepared for group with the mature technology in other laboratories and is divided into MAPbI3Device[3].Test device exists (RH=45%~55%) is tested in 100 DEG C of thermostabilization, MAPbI3It is yellow by original brown stain, illustrates in device MAPbI3Decomposed is PbI2, device efficiency is down to 1.02% by 8.95%;And by Cs0.1FA0.9PbI3The device of preparation Part, device are always maintained at grey black, and decline slightly only occurs for device efficiency, are down to 13.85% by 14.23%.
And following table 1 to table 4 lists the device performance obtained under different condition of the present invention.
Table 1 utilizes Cs0.1FA0.9PbI3, printable Jie that route III is prepared using different slurries sees perovskite solar-electricity The battery parameter in pond
Table 2 utilizes Cs0.1FA0.9PbI3, route III, ZrO with different thickness2The battery parameter of layer device
Table 3 utilizes Cs0.1FA0.9PbI3, route III, by mesoporous Al2O3And ZrO2It is seen respectively as Jie of wall preparation Perovskite solar battery battery parameter
Table 4Cs0.1FA0.9PbI3(a) and (CsPbI3)0.1((FAPbI3)0.85(MAPbBr3)0.15)0.9(b), route III system The battery parameter of standby device
Above-mentioned extinction layer material of the invention can be wide with good low temperature meltability and good photoelectric properties It is general be applied to each field of photovoltaic materials, be not limited solely to the preparation of solar battery, apply also for photodetector etc. its In its electronic component.
For precursor liquid, based on the present invention, other than using the specific solvent occurred in above-described embodiment, the present invention is applicable in Solvent can also be DMF, DMSO or both mixture (as DMF and DMSO be by volume 6/1~4/1 be mixed to get Mixture), perhaps for DMSO and chlorobenzene mixture or be the mixture of DMSO and alcohol.It is molten in subsequent anneal atmosphere Agent ingredient can be not quite identical with the solvent composition in precursor liquid, annealing atmosphere have to containing DMSO (such as single DMSO, Or the mixture of DMSO and DMF, the mixture of DMSO and chlorobenzene, or the mixture for DMSO and alcohol).Annealing temperature can also To be other temperature not less than 75 DEG C.
The mature technology in other laboratories used by the embodiment of the present invention 10 is in particular with reference to following documents:
[1]Huang F,Dkhuissi Y,Huang W,et al.Gas-assisted preparation of lead iodide perovskite films consisting of a monolayer of single crystalline grains for high efficiency planar solar cells[J].Nano Energy,2014,10:10-18.
[2]Wang Z,Zhou Y,Pang S,et al.Additive-modulated evolution of HC(NH2)2PbI3black polymorph for mesoscopic perovskite solar cells[J].Chemistry of Materials,2015,27(20):7149-7155.
[3]Ku Z,Rong Y,Xu M,et al.Full printable processed mesoscopic CH3NH3PbI3/TiO2heterojunction solar cells with carbon counter electrode[J] .Scientific reports,2013,3:3132.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include Within protection scope of the present invention.

Claims (10)

1. a kind of structure preparation method of inside containing bustamentite carbonamidine, which comprises the following steps:
(1) meso-hole structure is prepared;
(2) contain FAPbI3The preparation of the precursor liquid of bustamentite carbonamidine perovskite: will include PbI2, the raw material including FAI press chemical dose Than proportion, it is then dissolved in solvent, stirs evenly, obtain the precursor liquid of clear;
The solvent is the mixture of DMF, DMSO or both, perhaps for DMSO and chlorobenzene mixture or be DMSO and wine The mixture of essence;
(3) precursor liquid that the step (2) obtains is filled in the meso-hole structure that the step (1) obtains, it is quiet It sets, then annealing can be obtained and internal contain bustamentite carbonamidine under the solvent atmosphere containing DMSO or simultaneously containing DMSO and DMF Structure.
2. the internal structure preparation method containing bustamentite carbonamidine as described in claim 1, which is characterized in that for the step (2) precursor liquid obtained, the corresponding presoma solute of the precursor liquid be include FAPbI3Polycalcium titanium including perovskite The mixture of pit wood material contains Cs in the mixture+Corresponding perovskite material, the mixture are preferably CsxFA1-xPbI3Or (CsPbI3)x((FAPbI3)0.85(MAPbBr3)0.15)1-x, wherein x meets x=0~0.15;
When the presoma solute is CsxFA1-xPbI3Or (CsPbI3)x((FAPbI3)0.85(MAPbBr3)0.15)1-xWhen, the original Material further includes accordingly CsI, PbBr2, at least one of MAI and MABr.
3. the internal structure preparation method containing bustamentite carbonamidine as claimed in claim 2, which is characterized in that the step (2) To the precursor liquid in, the concentration of the presoma solute is 1M, Cs+Content in 0~0.15M;
In the step (3), precursor liquid described in 2.5~3.1 μ L is filled specifically into the meso-hole structure, is preferably filled Precursor liquid described in 3.0 μ L.
4. the internal structure preparation method containing bustamentite carbonamidine as described in claim 1, which is characterized in that in the step (2), The solvent is DMF, or be DMF and DMSO is by volume 6/1~4/1 mixture being mixed to get.
5. the internal structure preparation method containing bustamentite carbonamidine as described in claim 1, which is characterized in that in the step (3), The annealing is carried out under DMSO atmosphere;
Preferably, annealing temperature used in the annealing is not less than 75 DEG C, and annealing temperature is more preferably 100 DEG C, annealing time For 30~60min, more preferably 30min.
6. the structure for containing bustamentite carbonamidine using the inside that the preparation method as described in claim 1-5 any one is prepared.
7. application of the internal structure containing bustamentite carbonamidine in solar battery or photodetector as claimed in claim 6.
8. a kind of preparation method of the solar battery using bustamentite carbonamidine as solar battery light-absorption layer, which is characterized in that packet Include following steps:
(1) it is sequentially prepared transparency conducting layer, charge transport layer, insulating layer and carbon electrode layer on substrate, the charge transport layer, The insulating layer and the carbon electrode layer all have meso-hole structure, thus obtain the blank device with three layers of mesoporous membrane structure;
(2) contain FAPbI3The preparation of the precursor liquid of bustamentite carbonamidine perovskite: will include PbI2, the raw material including FAI press chemical dose Than proportion, it is then dissolved in solvent, stirs evenly, obtain the precursor liquid of clear;
The solvent is the mixture of DMF, DMSO or both, perhaps for DMSO and chlorobenzene mixture or be DMSO and wine The mixture of essence;
(3) precursor liquid that the step (2) obtains is filled in the blank device that the step (1) obtains, it is quiet It sets, then annealing can be obtained and internal contain bustamentite carbonamidine under the solvent atmosphere containing DMSO or simultaneously containing DMSO and DMF Solar battery, the solar battery i.e. using bustamentite carbonamidine as the solar battery of solar battery light-absorption layer.
9. preparation method as described in claim 1, which is characterized in that for the precursor liquid that the step (2) obtains, before this Driving the corresponding presoma solute of liquid to be includes FAPbI3The mixture of a variety of perovskite materials including perovskite, in the mixture Contain Cs+Corresponding perovskite material, the mixture are preferably CsxFA1-xPbI3Or (CsPbI3)x((FAPbI3)0.85 (MAPbBr3)0.15)1-x, wherein x meets x=0~0.15;
When the presoma solute is CsxFA1-xPbI3Or (CsPbI3)x((FAPbI3)0.85(MAPbBr3)0.15)1-xWhen, the original Material further includes accordingly CsI, PbBr2, at least one of MAI and MABr.
10. preparation method as described in claim 1, which is characterized in that in the step (1), the substrate is glass, the electricity Lotus transport layer is TiO2Nanometer crystal film, ZnO nano epitaxial, BaSnO3Nanometer crystal film or SnO2Nanometer crystal film, the insulating layer are ZrO2Insulating layer, SrTiO3Insulating layer, Al2O3Insulating layer or BaTiO3Insulating layer.
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