CN106449882B - A kind of preparation method and applications for adulterating anthracene class organic compound thin film - Google Patents

A kind of preparation method and applications for adulterating anthracene class organic compound thin film Download PDF

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CN106449882B
CN106449882B CN201610962964.3A CN201610962964A CN106449882B CN 106449882 B CN106449882 B CN 106449882B CN 201610962964 A CN201610962964 A CN 201610962964A CN 106449882 B CN106449882 B CN 106449882B
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pcbm
abmg
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CN106449882A (en
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颜步
颜步一
姚冀众
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Hangzhou Qianna Optoelectronics Technology Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02Details
    • H01L31/0216Coatings
    • H01L31/02161Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • 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
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to a kind of preparation method and applications for adulterating anthracene class organic compound thin film, introduce a kind of new conductive anthracene compound for being suitable for PCBM doping, ABMG has good electric conductivity, therefore its melting concn in PCBM can reach 10% 15% electronic transmission performances without reducing PCBM, be mixed with that PCBM film forming after ABMG is also more smooth, covering is more complete.ABMG of the invention by being mixed into good film-forming property, good conductivity in transmitting layer material PCBM in conditional electronic, highly smooth, the complete electric transmission layer film of covering is obtained.This thin film technique is applied on perovskite solar cell simultaneously so that voltage, fill factor, curve factor and the transformation efficiency of solar cell are all improved, and the efficiency homogeneity and repeatability of more batches of solar cells are also improved.

Description

A kind of preparation method and applications for adulterating anthracene class organic compound thin film
Technical field
The invention belongs to technical field of solar, more particularly to a kind of preparation method for adulterating anthracene class organic compound thin film And its application.
Background technology
Solar cell, photovoltaic cell is also, is a kind of electrooptical device, using the photovoltaic effect of semiconductor by the sun Electric energy can be converted into.From the point of view of global installation amount, solar power generation have become water removal can and wind energy outside the third is most important Regenerative resource.Commercialized solar battery structure is realized around P-N junction at this stage, and P-N junction can will too Electron-hole pair caused by sunlight separates, the loaded work piece for connecting P-N junction both ends.So, solar energy has translated into electricity Energy.Being manufactured into the semi-conducting material used in commercialized solar cell includes monocrystalline silicon, polysilicon, non-crystalline silicon, cadmium telluride, copper Indium gallium selenium etc..
High transformation efficiency, long-term stability and low manufacturing cost are to be commercialized the mesh that solar cell is pursued at this stage Mark.Therefore, a large amount of new materials are developed and studied, to replace solar cell material traditional, costly.It is existing Electron transport layer materials be broadly divided into organic and inorganic two major class.Wherein conventional inorganic material includes zinc oxide (ZnO), two Titanium oxide (TiO2), tin oxide (SnO2) etc., conventional organic material is mainly fullerene and its derivative(Including C60, C70, PC61BM, PC71BM etc.).Inorganic material, which has, prepares the characteristics of simple.But the electric transmission mechanism of inorganic material is to be based on The defects of material internal, state transmitted, in order to improve the ability of electric transmission, it is necessary to introduces lack in the material as much as possible Fall into state.This just brings both sides difficulty, first, to improve and control the density of defect state in preparation process, it is necessary to existing The ripe preparation method having carries out change by a relatively large margin, at the same time, because the essence of these defect states is metallic element It is below or above stoichiometric proportion (Stoichiometric ratio) with the ratio of oxygen element, just must accurately controls and synthesize The ratio of oxygen in journey.Actual preparation process is often reacted under solution state, it is difficult to enter to the oxygen content in environment The accurate control of row, also can not just realize the accurate control to defect state density, cause the property uniformity of products therefrom and can weigh Renaturation is bad;The difficulty of another aspect is more highdensity defect state with higher electron-hole recombinations possibility, especially Its interface zone being in contact in transport layer and calcium titanium ore bed, this non-radiation type it is compound can with the raising of defect state density and Proportional increase, so as to directly result in the decline of device voltage and photoelectric transformation efficiency.Therefore, inorganic electronic transmission layer material, Influenceed by its transporting mechanism, in lifting own electronic conductive performance and lifting perovskite solar cell overall transformation efficiency side There is inborn contradiction in face.
Organic Electron Transport Material, fullerene and its derivative being referred mainly to, their transporting mechanism is different from inorganic material, Lower the defects of under the conditions of the density of states, its electron mobility improves 1 ~ 2 order of magnitude than inorganic material, may be used as calcium titanium Ore deposit solar cell more preferably electron transport material.Common fullerene-based material (C60, C70) etc. is practically insoluble in organic Solvent, the method that physical vapour deposition (PVD) can only be used(Thermal evaporation deposition)Film forming is prepared to use for solar cell.Physical vapor is sunk Requirement of the product to equipment is harsh, and production cost is high, and film forming procedure is time-consuming also longer.Fullerene derivate (PCBM) can then dissolve It is simply efficient using a variety of solwution method film forming such as spin coating, blade coating, slot coated, preparation technology in a variety of organic solvents.But Due to reasons such as surface tension during prepared by large area, simple PCBM films are relatively easy to form rough surface, part is covered The problems such as covering uneven, hole, influence the overall performance of solar cell.
The content of the invention
The technical problems to be solved by the invention are, there is provided a kind of preparation method for adulterating anthracene class organic compound thin film And its application, while solving PCBM film forming problem of non-uniform, and PCBM electron transport property is not influenceed, present invention introduces A kind of new conductive anthracene compound for being suitable for PCBM doping, its full name is fluorine doped molecular glass anthracene(Abbreviation ABMG).ABMG has There is good electric conductivity, therefore its melting concn in PCBM can reach electric transmissions of the 10%-15% without reducing PCBM Performance, is mixed with that PCBM film forming after ABMG is also more smooth, covering is more complete.It is thin with this PCBM for being doped with ABMG The electricity conversion of perovskite solar cell and the homogeneity of device performance of film preparation also get a promotion.
The present invention, which is achieved in that, provides a kind of preparation method for adulterating anthracene class organic compound thin film, including as follows Step:
The first step, PCBM is dissolved,
Under conditions of 25 degrees Celsius of room temperatures and standard atmospheric pressure, PCBM powder is dissolved according to 5 ~ 40mg/mL ratio In solvent U, 60 ~ 90 degrees Centigrades 1 ~ 6 hour, PCBM solution is obtained;
Second step, prepare PCBM/ABMG(ABMG is referred to as fluorine doped molecular glass anthracene)Mixed solution,
ABMG is added in the PCBM solution that the first step is matched somebody with somebody, ABMG:PCBM mass ratio is 5 ~ 30:100, continue Heating stirring, ABMG obtain the required mixed solution for being doped with ABMG after thoroughly dissolving;
3rd step, the electric transmission layer film containing ABMG is prepared,
On the substrate of arbitrary surfaces cleaning, the ABMG/PCBM mixed solutions that second step obtains rapidly and evenly are smeared, For the film thickness of generation between 10 ~ 100 nanometers, the mode of smearing includes spin coating (spin-coating), blade blade coating (blade-coating), bar type coating (bar coating), slit type extrusion pressing type coating (slot-die coating), spraying (spray coating) and ink jet printing (ink-jet printing);
Wherein, solvent U in the first step is in chlorobenzene solvent, o-dichlorohenzene solvent, chloroform solvent or toluene solvant Any one;Substrate in third step includes simple glass substrate, glass/ITO substrate, glass/ITO/ transition zones/calcium titanium Any one in ore deposit substrate.
It is described present invention also offers a kind of application of the preparation method of the anthracene class organic compound thin film of doping as the aforementioned The preparation method of doping anthracene class organic compound thin film is applied during perovskite solar cell is prepared.
Present invention also offers a kind of preparation method using doping anthracene class organic compound thin film as the aforementioned to prepare calcium The method of titanium ore solar cell, comprises the following steps:
(One), cleaning ITO or FTO glass,
It is 100 that ITO or FTO glass first is put into cleaning agent with deionized water volume ratio:Using ultrasound in 1 cleaning solution Ripple mode is cleaned 5 ~ 20 minutes;Then, then with deionized water clean 5 ~ 20 minutes, repeat 3 ~ 4 times in ultrasonic wave;Then use again Acetone solvent cleans 5 ~ 20 minutes in ultrasonic wave;Finally use isopropanol(IPA)Solvent cleans 5 ~ 20 minutes in ultrasonic wave;Clearly After washing, dried up with nitrogen;
(Two), deposition of hole transport layer over transparent conductive layer,
The deposition materials of hole transmission layer include graphene, PEDOT:PSS、PTAA、CuSCN、CuI、MoOx、V2O5、NiO、 Spiro-OMeTAD, its deposition process include vacuum vapor deposition method, electron-beam vapor deposition method, magnetron sputtering method, atomic layer deposition method, light Lithography, chemical vapour deposition technique, silk screen print method, hydro-thermal method, electrochemical deposition method, spin coating (spin-coating), blade are scraped Apply (blade-coating), bar type coating (bar coating), slit type extrusion pressing type coating (slot-die coating), spray Apply (spray coating), ink jet printing (ink-jet printing);
(Three), deposit with the mode of coating 80nm ~ 400nm BX2Initialization layer,
By BX2Certain density organic solution is made into according to 1Mol/L ~ 2Mol/L with anhydrous organic solvent, this is organic molten Liquid is placed on the coating machine that temperature is 60 DEG C ~ 200 DEG C and applied;After drying substrates, required initialization layer is just made;
(Four), on initialization layer deposit thickness be 200nm ~ 1um perovskite thin film,
AX and anhydrous organic solvent are made into certain density organic solvent according to 10 ~ 200mg/mL, are somebody's turn to do a certain amount of Organic solvent is coated on rapidly step(Three)Obtained BX2Preset layer surface, then heat 3 at a temperature of 50 ~ 200 degrees Celsius ~ 60min, obtains ABX3Calcium titanium ore bed;
(Five), on perovskite thin film apply ABMG/PCBM mixed solutions,
In obtained ABX3Calcium titanium ore bed surface, which applies rapidly, utilizes preparation ABMG/PCBM mixed solution methods as the aforementioned The ABMG/PCBM mixed solutions of preparation, 0 ~ 30%ABMG PCBM solution, PCBM 5 ~ 40mg/mL of concentration, obtain thickness 10 ~ Electric transmission layer film between 100nm;The mode of smearing includes spin coating (spin-coating), blade blade coating (blade- Coating), bar type coating (bar coating), slit type extrusion pressing type coating (slot-die coating), spraying (spray Coating), ink jet printing (ink-jet printing);
(Six), using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode;
Wherein, in ABX3In structure, A is at least one of amido, amidino groups or alkali family, B be lead, tin, tungsten, copper, zinc, The cation of at least one of gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X are The anion of at least one of iodine, bromine, chlorine, astatine;Anhydrous organic solvent is gamma-butyrolacton, dimethylformamide and dimethyl Any one in sulfoxide, isopropanol.
Compared with prior art, the preparation method and applications of doping anthracene class organic compound thin film of the invention, pass through The ABMG of good film-forming property, good conductivity is mixed into conditional electronic transmission layer material PCBM, has obtained highly smooth, covering completely Electric transmission layer film.This thin film technique is applied on perovskite solar cell simultaneously so that solar cell Voltage, fill factor, curve factor and transformation efficiency are all improved, and the efficiency homogeneity and repeatability of more batches of solar cells also obtain Improve.
Brief description of the drawings
Fig. 1 is anthracene compound ABMG involved in the present invention chemical structural formula schematic diagram;
Fig. 2 is a kind of PCBM chemical structural formula;
Fig. 3 is the crystal structure of perovskite;
Fig. 4 is that common PCBM films are imaged under an atomic force microscope;
The film that Fig. 5 is the PCBM for being mixed with ABMG is imaged under an atomic force microscope;
Fig. 6 is the efficiency curve schematic diagram using solar cell made of the method for the present invention;
Fig. 7 is to utilize perovskite solar cell schematic construction made of the method for the present invention.
Embodiment
In order that technical problems, technical solutions and advantages to be solved are more clearly understood, tie below Drawings and Examples are closed, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only To explain the present invention, it is not intended to limit the present invention.
The chemical structural formula of the anthracene class organic compound of the present invention for being used to adulterate is as shown in Figure 1.In figure, F is fluorine Ion, N are Nitrogen ion, and the doping anthracene class organic compound title is fluorine doped molecular glass anthracene(Abbreviation ABMG).Its organic Frame structure is provided for good solubility and good film forming uniformity in a variety of organic solvents.The addition of fluorine ion Its conductive characteristic is improved again, makes its electron mobility close with PCBM.
PCBM of the present invention chemical formula structure is as shown in Figure 2.The group of carbon 60 has good electric conductivity, is electronics Conduction provides passage so that PCBM has higher electron mobility;Organic molecule functional group(Such as Fig. 2 benzyl and alkane Base)Certain polarity is provided for PCBM, makes it that there is certain dissolubility in common organic solvents.
The invention discloses a kind of preparation method for adulterating anthracene class organic compound thin film, comprise the following steps:
The first step, dissolve PCBM(Fullerene derivate), will under conditions of 25 degrees Celsius of room temperatures and standard atmospheric pressure PCBM powder is dissolved in solvent U according to 5 ~ 40mg/mL ratio, 60 ~ 90 degrees Centigrades 1 ~ 6 hour, obtains the molten of PCBM Liquid.
Second step, PCBM/ABMG mixed solutions are prepared, anthracene class organic compound will be adulterated(ABMG)It is added in the first step With PCBM solution in, ABMG:PCBM mass ratio is 5 ~ 30:100, continuous heating stirring, ABMG is obtained after thoroughly dissolving The required mixed solution for being doped with ABMG.
3rd step, the electric transmission layer film containing ABMG is prepared, it is rapid uniform on the substrate of arbitrary surfaces cleaning The ABMG/PCBM mixed solutions that second step obtains are smeared on ground, and the film thickness of generation is between 10 ~ 100 nanometers.The mode of smearing Including but not limited to spin coating (spin-coating), blade blade coating (blade-coating), bar type coating (bar coating), Slit type extrusion pressing type coating (slot-die coating), spraying (spray coating) and ink jet printing (ink-jet printing)。
Wherein, solvent U in the first step is in chlorobenzene solvent, o-dichlorohenzene solvent, chloroform solvent or toluene solvant Any one.Substrate in third step includes but is not limited to simple glass substrate, glass/ITO substrate, glass/ITO/ mistakes Cross any one in layer/perovskite-based bottom.
It is described present invention also offers a kind of application of the preparation method of the anthracene class organic compound thin film of doping as the aforementioned The preparation method of doping anthracene class organic compound thin film is applied during perovskite solar cell is prepared.With reference to reality The preparation method for applying the doping anthracene class organic compound thin film that example illustrates the present invention is particularly applicable in and prepares the perovskite sun The process of energy battery.
The invention also discloses a kind of preparation method using doping anthracene class organic compound thin film as the aforementioned to prepare calcium The method of titanium ore solar cell, comprises the following steps:
(One), cleaning ITO or FTO glass, ITO or FTO glass first is put into cleaning agent is with deionized water volume ratio 100:Cleaned 5 ~ 20 minutes using ultrasonic wave mode in 1 cleaning solution.Then, then with deionized water clean 5 in ultrasonic wave ~ 20 minutes, repeat 3 ~ 4 times.Then cleaned again with acetone solvent in ultrasonic wave 5 ~ 20 minutes.Finally use isopropanol(IPA)Solvent Cleaned 5 ~ 20 minutes in ultrasonic wave.After having cleaned, dried up with nitrogen.
(Two), deposition of hole transport layer, the deposition materials of hole transmission layer include but is not limited to stone over transparent conductive layer Black alkene, PEDOT:PSS、PTAA、CuSCN、CuI、MoOx、V2O5, NiO, spiro-OMeTAD, its deposition process includes but unlimited In vacuum vapor deposition method, electron-beam vapor deposition method, magnetron sputtering method, atomic layer deposition method, photoetching process, chemical vapour deposition technique, silk screen Print process, hydro-thermal method, electrochemical deposition method, spin coating (spin-coating), blade blade coating (blade-coating), bar type apply Cloth (bar coating), slit type extrusion pressing type coating (slot-die coating), spraying (spray coating), ink-jet print Brush (ink-jet printing).
(Three), deposit with the mode of coating 80nm ~ 400nm BX2Initialization layer, by BX2With anhydrous organic solvent according to 1Mol/L ~ 2Mol/L is made into certain density organic solution, and the organic solution is placed on into the coating that temperature is 60 DEG C ~ 200 DEG C Applied on machine.After drying substrates, required initialization layer is just made.
(Four), deposit thickness is 200nm ~ 1um perovskite thin film on initialization layer, by AX and anhydrous organic solvent according to 10 ~ 200mg/mL is made into certain density organic solvent, and a certain amount of organic solvent is coated on rapidly into step(Three)Obtain BX2Preset layer surface, 3 ~ 60min is then heated at a temperature of 50 ~ 200 degrees Celsius, obtains ABX3Calcium titanium ore bed.
(Five), on perovskite thin film apply ABMG/PCBM mixed solutions, in obtained ABX3Calcium titanium ore bed surface is rapid The ABMG/PCBM mixed solutions that coating is prepared using ABMG/PCBM mixed solutions method is prepared as the aforementioned, 0 ~ 30%ABMG's PCBM solution, PCBM 5 ~ 40mg/mL of concentration, obtain electric transmission layer film of the thickness between 10 ~ 100nm.The mode of smearing Including but not limited to spin coating (spin-coating), blade blade coating (blade-coating), bar type coating (bar coating), Slit type extrusion pressing type coating (slot-die coating), spraying (spray coating), ink jet printing (ink-jet printing)。
(Six), using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode.
The crystal structure of perovskite thin film is as shown in Figure 3.Wherein, in ABX3In structure, A is amido, amidino groups or alkali family At least one of, B be lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, The cation of at least one of thallium, bismuth, polonium, X are the anion of at least one of iodine, bromine, chlorine, astatine.Anhydrous organic solvent is Any one in gamma-butyrolacton, dimethylformamide and dimethyl sulfoxide (DMSO).A provides structure stand, BX for perovskite3For calcium Titanium ore provides carrier(Electronics and hole)Conduction pathway.
Perovskite solar battery structure schematic diagram of the present invention shown in Fig. 7 is refer to, is included from the bottom to top:1 is Transparent substrates covered with transparency conducting layer, 2 be hole transmission layer, and 3 be calcium titanium ore bed, and 4 is adulterate ABMG PCBM layers, and 5 are Top electrode.Wherein 1 can material selection include FTO glass, ito glass, AZO glass, the transparent plastic covered with FTO/ITO/AZO Film etc.;2 can material selection include graphene, PEDOT:PSS、PTAA、CuSCN、CuI、MoOx、V2O5、NiO、spiro- OMeTAD etc.;3 perovskite chemical formula is ABX3, wherein A is at least one of amido, amidino groups or alkali family, B be lead, tin, The sun of at least one of tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium Ion, X are the anion of at least one of iodine, bromine, chlorine, astatine;5 material includes all metal electrodes and ITO, FTO etc. Transparent conductive electrode.
Specifically, the invention discloses a kind of method for preparing perovskite solar cell, comprise the following steps:
(1), cleaning ITO or FTO glass, it is 100 that ITO or FTO glass first is put into cleaning agent and deionized water volume ratio: Cleaned 20 minutes using ultrasonic wave mode in 1 cleaning solution.Then, then with deionized water cleaned in ultrasonic wave 20 minutes, It is repeated 3 times.Then cleaned again with acetone solvent in ultrasonic wave 20 minutes.Finally use isopropanol(IPA)Solvent is in ultrasonic wave Cleaning 20 minutes.After having cleaned, dried up with nitrogen.
(2), deposition of hole transport layer over transparent conductive layer, the deposition materials PEDOT of hole transmission layer:PSS, it is deposited Method uses spin-coating method, rotating speed 4000rpm, spray time 60s, and spin coating terminates rear 140 degrees Centigrade 10 minutes.
(3), deposit with the mode of coating 300nm BX2Initialization layer, by BX2With solvent dimethylformamide according to 1.5Mol/L is made into organic solution, and the organic solution is placed on the coating machine that temperature is 60 DEG C and applied.After drying substrates, Just required initialization layer is made.
(4), on initialization layer deposit thickness be 600nm perovskite thin film, by AX and isopropanol solvent according to 100mg/ ML is made into organic solvent, and a certain amount of organic solvent is coated on rapidly into step(3)Obtained BX2Preset layer surface, then 20min is heated at a temperature of 100 degrees Celsius, obtains ABX3Calcium titanium ore bed.
(5), on perovskite thin film apply ABMG/PCBM mixed solutions, in obtained ABX3Calcium titanium ore bed surface uses Spraying process applies rapidly PCBM solution, the PCBM concentration 10mg/mL for being mixed with 20%ABMG, and the electronics for obtaining thickness in 20nm passes Defeated layer film.
(6), using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode, obtaining thickness is 100nm metal back electrode aluminium.
Specifically, the invention discloses the method that another kind prepares perovskite solar cell, comprise the following steps:
(1), cleaning ITO or FTO glass, it is 100 that ITO or FTO glass first is put into cleaning agent and deionized water volume ratio: Cleaned 5 minutes using ultrasonic wave mode in 1 cleaning solution.Then, then with deionized water cleaned in ultrasonic wave 5 minutes, weight It is multiple 4 times.Then cleaned again with acetone solvent in ultrasonic wave 5 minutes.Finally use isopropanol(IPA)Solvent cleans in ultrasonic wave 4 minutes.After having cleaned, dried up with nitrogen.
(2), deposition of hole transport layer over transparent conductive layer, the deposition materials CuSCN of hole transmission layer, its deposition process Using silk screen print method, 140 degrees Centigrade 10 minutes after printing terminates.
(3), deposit with the mode of coating 80nm BX2Initialization layer, by BX2With solvent dimethylformamide according to 1Mol/L Organic solution is made into, the organic solution is placed on the coating machine that temperature is 1200 DEG C and applied.After drying substrates, just it is made Required initialization layer.
(4), on initialization layer deposit thickness be 200nm perovskite thin film, by AX and isopropanol solvent according to 10mg/mL Organic solvent is made into, a certain amount of organic solvent is coated on rapidly step(3)Obtained BX2Preset layer surface, Ran Hou 3min is heated at a temperature of 50 degrees Celsius, obtains ABX3Calcium titanium ore bed.
(5), on perovskite thin film apply ABMG/PCBM mixed solutions, in obtained ABX3Calcium titanium ore bed surface uses Blade knife coating applies rapidly PCBM solution, the PCBM concentration 5mg/mL for being mixed with 5%ABMG, obtains electronics of the thickness in 10nm Transmit layer film.
(6), using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode, obtaining thickness is 100nm metal back electrode aluminium.
Specifically, the invention discloses the method that another prepares perovskite solar cell, comprise the following steps:
(1), cleaning ITO or FTO glass, it is 100 that ITO or FTO glass first is put into cleaning agent and deionized water volume ratio: Cleaned 13 minutes using ultrasonic wave mode in 1 cleaning solution.Then, then with deionized water cleaned in ultrasonic wave 13 minutes, It is repeated 3 times.Then cleaned again with acetone solvent in ultrasonic wave 13 minutes.Finally use isopropanol(IPA)Solvent is in ultrasonic wave Cleaning 13 minutes.After having cleaned, dried up with nitrogen.
(2), deposition of hole transport layer, the deposition materials NiO of hole transmission layer, its deposition process are adopted over transparent conductive layer With vacuum vapor deposition method, 140 degrees Centigrade 10 minutes after terminating.
(3), deposit with the mode of coating 400nm BX2Initialization layer, by BX2With solvent dimethylformamide according to 2Mol/L Organic solution is made into, the organic solution is placed on the coating machine that temperature is 200 DEG C and applied.After drying substrates, just it is made Required initialization layer.
(4), on initialization layer deposit thickness be 1um perovskite thin film, by AX and isopropanol solvent according to 200mg/mL Organic solvent is made into, a certain amount of organic solvent is coated on rapidly step(3)Obtained BX2Preset layer surface, Ran Hou 60min is heated at a temperature of 200 degrees Celsius, obtains ABX3Calcium titanium ore bed.
(5), on perovskite thin film apply ABMG/PCBM mixed solutions, in obtained ABX3Calcium titanium ore bed surface uses Bar type rubbing method applies rapidly PCBM solution, the PCBM concentration 40mg/mL for being mixed with 30%ABMG, obtains electricity of the thickness in 100nm Son transmission layer film.
(6), using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode, obtaining thickness is 100nm metal back electrode aluminium.
Fig. 4 is the surface image of PCBM films under an atomic force microscope undoped with ABMG, and Fig. 5 is doping ABMG The surface image of PCBM films under an atomic force microscope.As can be seen that Fig. 4 surface undulations exist from Fig. 4 and Fig. 5 contrast 17nm or so, Fig. 5 surface undulation are less than Fig. 4 in 13.6nm or so, Fig. 5 roughness, illustrate PCBM films that Fig. 5 is obtained more To be smooth.
Fig. 6 is by the J-V performance curves of the ABMG of the PCBM doping various concentrations perovskite solar cells prepared.From figure In it can be seen that be doped with the short circuit current of perovskite solar cell of 10%ABMG PCBM films, open-circuit voltage, filling because Sub and final photoelectric transformation efficiency all be higher than by undoped with PCBM films made of perovskite solar cell.Explanation is mixed Miscellaneous appropriate ABMG PCBM films can improve the overall performance of perovskite solar cell.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.

Claims (6)

1. a kind of preparation method for adulterating anthracene class organic compound thin film, it is characterised in that comprise the following steps:
The first step, PCBM is dissolved,
Under conditions of 25 degrees Celsius of room temperatures and standard atmospheric pressure, PCBM powder is dissolved according to 5 ~ 40mg/mL ratio molten In agent U, 60 ~ 90 degrees Centigrades 1 ~ 6 hour, PCBM solution is obtained;
Second step, prepare PCBM/ABMG(ABMG is referred to as fluorine doped molecular glass anthracene)Mixed solution,
ABMG is added in the PCBM solution that the first step is matched somebody with somebody, ABMG:PCBM mass ratio is 5 ~ 30:100, continuous heating Stirring, ABMG obtain the required mixed solution for being doped with ABMG after thoroughly dissolving;
3rd step, the electric transmission layer film containing ABMG is prepared,
On the substrate of arbitrary surfaces cleaning, the ABMG/PCBM mixed solutions that second step obtains, generation are rapidly and evenly smeared Film thickness between 10 ~ 100 nanometers, the mode of smearing includes spin coating, blade blade coating, bar type coating, slit type extrusion pressing type Coating, spraying and ink jet printing;
Wherein, solvent U in the first step is any in chlorobenzene solvent, o-dichlorohenzene solvent, chloroform solvent or toluene solvant It is a kind of;Substrate in third step includes simple glass substrate, glass/ITO substrate, glass/ITO/ transition zones/perovskite-based Any one in bottom.
A kind of 2. application of the preparation method of doping anthracene class organic compound thin film as claimed in claim 1, it is characterised in that The preparation method of the doping anthracene class organic compound thin film is applied during perovskite solar cell is prepared.
3. a kind of preparation method using doping anthracene class organic compound thin film as claimed in claim 1 prepares the perovskite sun The method of energy battery, it is characterised in that comprise the following steps:
(One), cleaning ITO or FTO glass,
It is 100 that ITO or FTO glass first is put into cleaning agent with deionized water volume ratio:Ultrasonic wave side is used in 1 cleaning solution Formula is cleaned 5 ~ 20 minutes;Then, then with deionized water clean 5 ~ 20 minutes, repeat 3 ~ 4 times in ultrasonic wave;Then acetone is used again Solvent cleans 5 ~ 20 minutes in ultrasonic wave;Finally cleaned with isopropanol solvent in ultrasonic wave 5 ~ 20 minutes;After having cleaned, use Nitrogen dries up;
(Two), deposition of hole transport layer over transparent conductive layer,
The deposition materials of hole transmission layer include graphene, PEDOT:PSS、PTAA、CuSCN、CuI、MoOx、V2O5、NiO、 Spiro-OMeTAD, its deposition process include vacuum vapor deposition method, electron-beam vapor deposition method, magnetron sputtering method, atomic layer deposition method, light Lithography, chemical vapour deposition technique, silk screen print method, hydro-thermal method, electrochemical deposition method, spin coating, blade blade coating, bar type coating, folder The coating of seam extrusion pressing type, spraying, ink jet printing;
(Three), deposit with the mode of coating 80nm ~ 400nm BX2Initialization layer,
By BX2Certain density organic solution is made into according to 1Mol/L ~ 2Mol/L with anhydrous organic solvent, the organic solution is put Put and applied on the coating machine that temperature is 60 DEG C ~ 200 DEG C;After drying substrates, required initialization layer is just made;
(Four), on initialization layer deposit thickness be 200nm ~ 1um perovskite thin film,
AX and anhydrous organic solvent are made into certain density organic solvent according to 10 ~ 200mg/mL, this is organic by a certain amount of Solvent is coated on rapidly step(Three)Obtained BX2Preset layer surface, then at a temperature of 50 ~ 200 degrees Celsius heating 3 ~ 60min, obtain ABX3Calcium titanium ore bed;
(Five), on perovskite thin film apply ABMG/PCBM mixed solutions,
In obtained ABX3Calcium titanium ore bed surface applies rapidly prepares ABMG/PCBM mixed solutions using as claimed in claim 1 ABMG/PCBM mixed solutions prepared by method, 0 ~ 30%ABMG PCBM solution, PCBM 5 ~ 40mg/mL of concentration, obtain thickness and exist Electric transmission layer film between 10 ~ 100nm;The mode of smearing includes spin coating, blade blade coating, bar type coating, slit type extruding Type coating, spraying, ink jet printing;
(Six), using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode;
Wherein, in ABX3In structure, A is at least one of amido, amidino groups or alkali family, B be lead, tin, tungsten, copper, zinc, gallium, The cation of at least one of germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X be iodine, The anion of at least one of bromine, chlorine, astatine;Anhydrous organic solvent is that gamma-butyrolacton, dimethylformamide and dimethyl are sub- Any one in sulfone, isopropanol.
4. the method as claimed in claim 3 for preparing perovskite solar cell, it is characterised in that comprise the following steps:
(1), cleaning ITO or FTO glass,
It is 100 that ITO or FTO glass first is put into cleaning agent with deionized water volume ratio:Ultrasonic wave side is used in 1 cleaning solution Formula is cleaned 20 minutes;Then, then with deionized water clean 20 minutes, be repeated 3 times in ultrasonic wave;Then existed again with acetone solvent Cleaned 20 minutes in ultrasonic wave;Finally cleaned with isopropanol solvent in ultrasonic wave 20 minutes;After having cleaned, dried up with nitrogen;
(2), deposition of hole transport layer over transparent conductive layer,
The deposition materials PEDOT of hole transmission layer:PSS, its deposition process use spin-coating method, rotating speed 4000rpm, spray time 60s, 140 degrees Centigrade 10 minutes after spin coating terminates;
(3), deposit with the mode of coating 300nm BX2Initialization layer,
By BX2Organic solution is made into according to 1.5Mol/L with solvent dimethylformamide, the organic solution is placed on temperature as 60 DEG C coating machine on apply;After drying substrates, required initialization layer is just made;
(4), on initialization layer deposit thickness be 600nm perovskite thin film,
AX and isopropanol solvent are made into organic solvent according to 100mg/mL, by a certain amount of organic solvent rapidly coated on step Suddenly(3)Obtained BX2Preset layer surface, 20min then is heated at a temperature of 100 degrees Celsius, obtains ABX3Calcium titanium ore bed;
(5), on perovskite thin film apply ABMG/PCBM mixed solutions,
In obtained ABX3Calcium titanium ore bed surface applies rapidly PCBM solution, the PCBM concentration for being mixed with 20%ABMG using spraying process 10mg/mL, obtain electric transmission layer film of the thickness in 20nm;
(6), using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode, obtaining thickness is 100nm metal back electrode aluminium.
5. the method as claimed in claim 3 for preparing perovskite solar cell, it is characterised in that comprise the following steps:
(1), cleaning ITO or FTO glass,
It is 100 that ITO or FTO glass first is put into cleaning agent with deionized water volume ratio:Ultrasonic wave side is used in 1 cleaning solution Formula is cleaned 5 minutes;Then, then with deionized water clean 5 minutes, be repeated 4 times in ultrasonic wave;Then again with acetone solvent super Cleaned 5 minutes in sound wave;Finally cleaned with isopropanol solvent in ultrasonic wave 4 minutes;After having cleaned, dried up with nitrogen;
(2), deposition of hole transport layer over transparent conductive layer,
The deposition materials CuSCN of hole transmission layer, 140 degrees Celsius add after its deposition process use silk screen print method, printing terminate Heat 10 minutes;
(3), deposit with the mode of coating 80nm BX2Initialization layer,
By BX2Organic solution is made into according to 1Mol/L with solvent dimethylformamide, the organic solution is placed on temperature as 1200 DEG C coating machine on apply;After drying substrates, required initialization layer is just made;
(4), on initialization layer deposit thickness be 200nm perovskite thin film,
AX and isopropanol solvent are made into organic solvent according to 10mg/mL, by a certain amount of organic solvent rapidly coated on step Suddenly(3)Obtained BX2Preset layer surface, 3min then is heated at a temperature of 50 degrees Celsius, obtains ABX3Calcium titanium ore bed;
(5), on perovskite thin film apply ABMG/PCBM mixed solutions,
In obtained ABX3Calcium titanium ore bed surface applies rapidly PCBM solution, the PCBM for being mixed with 5%ABMG using blade knife coating Concentration 5mg/mL, obtain electric transmission layer film of the thickness in 10nm;
(6), using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode, obtaining thickness is 100nm metal back electrode aluminium.
6. the method as claimed in claim 3 for preparing perovskite solar cell, it is characterised in that comprise the following steps:
(1), cleaning ITO or FTO glass,
It is 100 that ITO or FTO glass first is put into cleaning agent with deionized water volume ratio:Ultrasonic wave side is used in 1 cleaning solution Formula is cleaned 13 minutes;Then, then with deionized water clean 13 minutes, be repeated 3 times in ultrasonic wave;Then existed again with acetone solvent Cleaned 13 minutes in ultrasonic wave;Finally cleaned with isopropanol solvent in ultrasonic wave 13 minutes;After having cleaned, dried up with nitrogen;
(2), deposition of hole transport layer over transparent conductive layer,
The deposition materials NiO of hole transmission layer, its deposition process use vacuum vapor deposition method, and 140 degrees Centigrades 10 divide after terminating Clock;
(3), deposit with the mode of coating 400nm BX2Initialization layer,
By BX2Organic solution is made into according to 2Mol/L with solvent dimethylformamide, the organic solution is placed on temperature as 200 DEG C coating machine on apply;After drying substrates, required initialization layer is just made;
(4), on initialization layer deposit thickness be 1um perovskite thin film,
AX and isopropanol solvent are made into organic solvent according to 200mg/mL, by a certain amount of organic solvent rapidly coated on step Suddenly(3)Obtained BX2Preset layer surface, 60min then is heated at a temperature of 200 degrees Celsius, obtains ABX3Calcium titanium ore bed;
(5), on perovskite thin film apply ABMG/PCBM mixed solutions,
In obtained ABX3Calcium titanium ore bed surface applies rapidly PCBM solution, the PCBM for being mixed with 30%ABMG using bar type rubbing method Concentration 40mg/mL, obtain electric transmission layer film of the thickness in 100nm;
(6), using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode, obtaining thickness is 100nm metal back electrode aluminium.
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