CN107887513A - A kind of solar cell based on ternary inorganic flat type hetero-junction thin-film and preparation method thereof - Google Patents

A kind of solar cell based on ternary inorganic flat type hetero-junction thin-film and preparation method thereof Download PDF

Info

Publication number
CN107887513A
CN107887513A CN201710995180.5A CN201710995180A CN107887513A CN 107887513 A CN107887513 A CN 107887513A CN 201710995180 A CN201710995180 A CN 201710995180A CN 107887513 A CN107887513 A CN 107887513A
Authority
CN
China
Prior art keywords
film
thin
cuins
solar cell
tio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710995180.5A
Other languages
Chinese (zh)
Other versions
CN107887513B (en
Inventor
陈王伟
王命泰
齐娟娟
董超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hefei Institutes of Physical Science of CAS
Original Assignee
Hefei Institutes of Physical Science of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hefei Institutes of Physical Science of CAS filed Critical Hefei Institutes of Physical Science of CAS
Priority to CN201710995180.5A priority Critical patent/CN107887513B/en
Publication of CN107887513A publication Critical patent/CN107887513A/en
Application granted granted Critical
Publication of CN107887513B publication Critical patent/CN107887513B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/42Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture
    • H01L51/4253Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture comprising bulk hetero-junctions, e.g. interpenetrating networks
    • H01L51/426Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture comprising bulk hetero-junctions, e.g. interpenetrating networks comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0001Processes specially adapted for the manufacture or treatment of devices or of parts thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2251/00Indexing scheme relating to organic semiconductor devices covered by group H01L51/00
    • H01L2251/30Materials
    • H01L2251/301Inorganic materials
    • 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

Abstract

The present invention provides a kind of solar cell based on ternary inorganic flat type hetero-junction thin-film, and anode, ternary inorganic flat type hetero-junction thin-film, organic cavity transmission layer, negative electrode have been sequentially depositing on glass lined base;Described ternary inorganic flat type hetero-junction thin-film is by TiO2Nano thin-film, CdS nano thin-films and CuInS2Nano thin-film forms, TiO2Nano thin-film, CdS nano thin-films and CuInS2Nano thin-film, it is sequentially deposited on solar cell anode.The technical progress and innovation point of the present invention is mainly reflected in following aspect:(1)In terms of core material, crucial CuInS2The preparation method of film layer and prior art are entirely different, and our preparation method is more easy to realize prepared by large area;(2)In battery structure and aspect of performance, we use organic cavity transmission layer in the battery, are effectively prevented from caused short circuit phenomenon in Au atomic deposition process, and battery has higherV oc

Description

A kind of solar cell and its preparation based on ternary inorganic flat type hetero-junction thin-film Method
Technical field
The present invention relates to solar cell field, more particularly to a kind of sun based on ternary inorganic flat type hetero-junction thin-film Battery.
Background technology
Electric energy is converted solar energy into, realizes photovoltaic generation, is a kind of important way using regenerative resource.Photovoltaic is sent out It is crucial that the device of capture and conversion solar energy, i.e. solar cell in electric system.Solar cell in practical application needs Meet two basic demands:Higher efficiency (>And stable battery performance (service life 10%)>20 years).Solar cell Photoactive layer is region caused by light absorbs and free charge, generally by n-type semiconductor and p-type semiconductor group into heterogeneous membrane Knot is formed, and is had decisive role to the photoelectric conversion process of battery, is the critical material part of solar cell.Inorganic semiconductor material Material, there is the advantages of charge mobility height and good Stability Analysis of Structures.At present, the higher solar cell of most of efficiency and stability, Mainly or based on inorganic heterogeneous device (Prog.Photovolt:Res.Appl.2016,24,3-11);Wherein, commodity The solar cell of change is main or forms monocrystalline silicon battery of the photoactive layer as representative, its energy conversion using monocrystalline silicon p/n conjunctivas Efficiency (η) is up to 25%.Generally, inorganic heterogeneous solar cell be by physical vapour deposition (PVD) and chemical vapour deposition technique come (the Prog.Photovolt prepared:Res.Appl.2004,12,69-92;Front.Phys.2011,6,177-196).Although The inorganic material and efficient solar cell device that quality is good, crystallinity is higher, but these gas-phase deposition process for preparing can be obtained It is commonly present technology and equipment complexity, high energy consumption (needing high vacuum, 400-1400 DEG C of high temperature), the deficiencies of spillage of material is big, simultaneously High purity raw material supply is also limited;The presence that these are insufficient, cause battery cost very high, be unfavorable for large-scale application.Establish Novel inorganic hetero-junction thin-film photoelectric conversion material system, and inexpensive preparation is realized, efficient solar cell is obtained, is inorganic The significant challenge faced in thin film solar cell development.
Prepared by the solwution method of thin-film material, refer to deposit and component film material using certain solvent as filming medium.Often Solwution method mainly includes chemical baths and predecessor method.Chemical baths are mainly technically characterized by:Lining base is placed in preparation In the solution of the reactant of thin-film material, the reaction product in solution deposits on lining base, obtains predominantly amorphous or part is tied Brilliant film, generally need to obtain crystalline film's material in certain temperature (general≤500 DEG C) annealing noncrystal membrane at ambient pressure Material.Predecessor method is mainly technically characterized by:First with solution processing technology (e.g., spin coating, blade coating, silk-screen printing, inkjet printing, Impregnating) the pre-deposition film of predecessor is made under normal temperature, normal pressure, then often depress lower temperature (general≤500 DEG C) Subsequent heat treatment, make to occur, about chemical reaction and crystallization process, to obtain crystalline film's material in predecessor pre-deposition film. Crystallize CuInS2With the narrow (E of band gapg=1.5eV), light abstraction width wide (300-900nm) and it is environmentally friendly the features such as, be a kind of to have very much The solar cell light absorbing material of potentiality.(J.Am.Chem.Soc.2010,132,22-23) such as Li in 2010, passes through predecessor Method, CuInS is sequentially depositing on ITO electro-conductive glass2With CdS nanometer particle films, it has been made by CuInS2, CdS composition binary Plate hetero-junction thin-film, the open-circuit voltage (V of the solar cell based on the hetero-junction thin-filmoc), short circuit current (Jsc), filling The factor (FF) and energy conversion efficiency (η) respectively reach 0.59V, 12.38mA/cm2, 54.80% and 3.99%.2017 Cheshmekhavar etc. (Mater.Chem.Phys.2017,186,446-455), by predecessor method, in TiO2Dense film On be sequentially depositing In2S3And CuInS2Nanometer particle film, it has been made by TiO2、In2S3And CuInS2The ternary of composition is plate Hetero-junction thin-film, the V of the thin film solar cell based on the hetero-junctionsoc、Jsc, FF and η respectively reached 0.52V, 10.90mA/ cm2, 46% and 2.62%.Golobostanfard in 2017 etc. (Sol.Energy.Mater.Sol.Cells 2017,164, 1-6), first in TiO2CdS nanometer particle films are deposited with chemical baths in dense film, then pass through nanometer in CdS film layers The electrophoresis process and H of particle2S atmosphere subsequent heat treatment prepares CuInS2Nanometer particle film, it has been made by TiO2, CdS and CuInS2The plate hetero-junction thin-film of ternary of composition, the V of the thin film solar cell based on the hetero-junctionsoc、Jsc, FF and η difference 0.59V, 14.90mA/cm are reached2, 61% and 5.31%.
The content of the invention
In view of the deficienciess of the prior art, the invention provides a kind of based on ternary inorganic flat type hetero-junction thin-film Solar cell and preparation method thereof.In the present invention, we use chemical baths and predecessor method respectively, in TiO2In dense film according to Secondary deposition CdS and CuInS2Nanometer particle film, it is prepared for by TiO2, CdS and CuInS2The three of three kinds of nanometer particle film compositions The plate hetero-junction thin-film of member (referred to as, TiO2/CdS/CuInS2Hetero-junction thin-film);By TiO2/CdS/CuInS2Hetero-junction thin-film It is compound with organic hole transport material, establish the solar cell based on ternary inorganic flat type hetero-junction thin-film (referred to as, TiO2/CdS/CuInS2Solar cell) and preparation method thereof, the efficiency of solar cell has reached η=5.78%.
The present invention is achieved by the following technical solutions:
A kind of solar cell based on ternary inorganic flat type hetero-junction thin-film, sun has been sequentially depositing on glass lined base Pole, ternary inorganic flat type hetero-junction thin-film, organic cavity transmission layer, negative electrode;Described ternary inorganic flat type hetero-junctions is thin Film is by TiO2Nano thin-film, CdS nano thin-films and CuInS2Nano thin-film forms, TiO2Nano thin-film, CdS nano thin-films and CuInS2Nano thin-film, it is sequentially deposited on solar cell anode.
Described solar cell anode is ITO layer, TiO2Nano thin-film by 20-30nm TiO2Nano particle forms, CdS Nano thin-film is made up of 10-20nm CdS nano particles, CuInS2Nano thin-film by 10-20nm CuInS2Nano particle group Into;Described organic cavity transmission layer is Spiro-OMeTAD films, and the negative electrode is Au films.
The thickness of described ITO layer is 100-300nm, TiO2The thickness of nano thin-film is 50-150nm, CdS nano thin-films Thickness is 50-100nm, CuInS2Nano film thickness is 100-500nm, and Spiro-OMeTAD film thicknesses are 100-200nm, Au film thicknesses are 60-120nm.
Described Spiro-OMeTAD films are made by Spiro-OMeTAD, LiTFSI and TBP, Spiro-OMeTAD, LiTFSI and TBP mol ratio is 1-3:1:5-7.
The preparation method of the described solar cell based on inorganic flat type hetero-junction thin-film, comprises the following steps:
(1) anode ITO electro-conductive glass is etched into slice with concentrated hydrochloric acid and Zn powder, then through acetone, isopropanol, ultrapure moisture Not Chao Shengqingxi 4-6 minutes, dry after, obtain the ITO electro-conductive glass after over etching;Sunk on ITO electro-conductive glass after etching Product TiO2It is standby after nano thin-film;
(2) configuration concentration is the 0.4-0.6g/L cadmium sulfate aqueous solution, adds the ammonia that concentration is 25%-28% thereto Water, and dissolved in 60-70 DEG C of stirred in water bath;Configuration concentration is 50-60g/L thiourea solution;The cadmium sulfate aqueous solution:Ammonia Water:Thiourea solution volume ratio is 340-360:54-58:43-47;Deposition there is into TiO2The ITO electro-conductive glass of film hangs vertically Sky leaching is placed in the cadmium sulfate of stirring and the mixed aqueous solution of ammoniacal liquor, is added thiourea solution, is continued in 60-70 DEG C of water-bath Middle progress 8-12min reactive depositions, obtain TiO2With the plate hetero-junction thin-film of binary of two kinds of nano thin-film compositions of CdS;
(3) at room temperature by InCl3It is dissolved in DMF, stirs 0.5-1.5 hours, be configured to 145- 147g/L solution, then adds CuI, continues to stir 0.5-1.5 hours, adds thiocarbamide, stirs 15-30 hours at room temperature, Obtain CuInS2Pre-reaction material solution, wherein InCl3:CuI:The mol ratio of thiocarbamide is 1:1:6-10;
By CuInS2Reactant precursor solution is added drop-wise on the plate hetero-junction thin-film of binary of gained and spin-coating film, Spin coating 2 times is repeated, obtains CuInS2Pre-reaction material film;The pre-reaction material film of gained is placed on 65 DEG C of vacuum drying chambers After middle drying, it is placed in the thermal station under inert gas shielding, thermal station temperature is first risen to 120-180 DEG C and is kept for 4-6 minutes, so 200-300 DEG C is continuously heating to afterwards and the heat treatment of 5-15 minutes is carried out to sample in this temperature;After heat treatment terminates, sample is natural Room temperature is cooled to, obtains crystallinity CuInS2Embryophoric membrane;Repeat to CuInS2The thickness of nano thin-film is up to standard, obtains TiO2、 CdS and CuInS2The plate hetero-junction thin-film of ternary of three kinds of nano thin-film compositions;
(4) on the plate hetero-junction thin-film of ternary obtained by step (3), one layer of concentration of spin coating is 60-90mg/mL's Spiro-OMeTAD, LiTFSI and TBP mixture solution, in atmosphere 50-150 DEG C of heat treatment 5-15 minute, obtain Spiro- OMeTAD film hole transmission layers;
(5) on the Spiro-OMeTAD film hole transmission layers obtained by step (4), Au is deposited by thermal evaporation method Film, obtain the solar cell based on ternary inorganic flat type hetero-junction thin-film;
(6) solar cell made from step (5) is encapsulated under inert gas shielding and obtains solar cell product.
Chemical bath method described in step (2) can be replaced with spin-coating method.
The preferred chlorobenzene of solvent of Spiro-OMeTAD solution described in step (4).
Spin coating operation described in step (3), (4), it can be replaced with silk screen print method or scraping blade method or ink-jet printing process.
The preferred nitrogen of inert gas described in step (3), (6).
Beneficial effects of the present invention are:
In the present invention, we are in TiO2On/CdS heterofilms, pass through precursor solution (InCl3, CuI, thiocarbamide, N, N- bis- The mixture of NMF) solwution method, to prepare CuInS2Nanometer particle film, TiO is made2/CdS/CuInS2It is heterogeneous Tie film;In TiO2/CdS/CuInS2On hetero-junction thin-film, Spiro- is deposited respectively with solwution method and thermal evaporation deposition method OMeTAD organic holes transmission film and Au membrane electrodes, it is TiO to obtain structure2/CdS/CuInS2/ Spiro-OMeTAD/Au's Solar cell.Utilize CuInS2The absorbing properties of nanometer realize solar cell in 300-900nm wide spectral ranges to too The absorption of sunlight, makes photo-generated carrier spatially sufficiently be separated using the locus effect of CdS nano thin-films, And TiO2Nano thin-film causes solar cell to have efficient electronic selection transmission channel;So that efficiency of solar cell reaches 5.78% (wherein, Voc=0.77V, Jsc=11.60mA/cm2, FF=64%).
The technical progress and innovation point of the present invention is mainly reflected in following aspect:(1) it is crucial in terms of core material CuInS2The preparation method of film layer is compared with prior art (Sol.Energy.Mater.Sol.Cells2017,164,1-6) Entirely different, our preparation method is more easy to realize prepared by large area;(2) in battery structure and aspect of performance, we are in battery In used organic cavity transmission layer, be effectively prevented from caused short circuit phenomenon in Au atomic deposition process, battery has higher Voc.Our battery critical material and the preparation method of battery device are easy, low for equipment requirements, are adapted to extensive preparation, There is very big application value in the field such as photovoltaic material and low price solar cell device
Brief description of the drawings
Fig. 1 is the structural representation of the thin film solar cell of the present invention based on ternary flat board hetero-junctions;Accompanying drawing mark Note is as follows:(1) Au films negative electrode, (2) Spiro-OMeTAD films, (3) CuInS2Nano thin-film, (4) CdS nano thin-films, (5) TiO2Nano thin-film, (6) ito anode, (7) glass lined base.
Fig. 2 is TiO of the present invention2The XRD characterization results of film.
Fig. 3 is TiO of the present invention2The SEM characterization results of film.
Fig. 4 is TiO of the present invention2The XRD characterization results of/CdS hetero-junction thin-films.
Fig. 5 is TiO of the present invention2The SEM characterization results of/CdS hetero-junction thin-films.
Fig. 6 is TiO of the present invention2The UV-vis absorption spectrum characterization results of/CdS hetero-junction thin-films.
Fig. 7 is TiO of the present invention2/CdS/CuInS2The XRD characterization results of hetero-junction thin-film.
Fig. 8 is TiO of the present invention2/CdS/CuInS2The SEM characterization results of hetero-junction thin-film.
Fig. 9 is TiO of the present invention2/CdS/CuInS2The UV-vis absorption spectrum characterization results of hetero-junction thin-film.
Figure 10 is TiO of the present invention2/CdS/CuInS2The IPCE characterization results of solar cell.
Figure 11 is TiO of the present invention2/CdS/CuInS2The J-V performance characterization results of solar cell.
Embodiment
Embodiment
1、TiO2The preparation of film.
The etching of (1-1) ITO electro-conductive glass and cleaning:
By ITO electro-conductive glass, (size is 3 × 3cm2, 15 Ω/) and volume ratio is used as 1:The mixture of 1 dense HCl- water and Ito film layer on ITO electro-conductive glass is etched into 4 16 × 4mm by Zn powder2Slice, after being etched ITO electro-conductive glass lining Base;It is cleaned by ultrasonic respectively 5 minutes through acetone, isopropanol, ultra-pure water again, obtains the ITO electro-conductive glass lining base after the etching of cleaning, It is standby after drying.
(1-2)TiO2The preparation of film:
Absolute ethyl alcohol, tetrabutyl titanate, glacial acetic acid are pressed 4:1:0.1 volume ratio is mixed, and is made into uniform colorless TiO2Precursor sol liquid.By 150 μ L TiO2(2000 revs/min of spin coating on the ITO electro-conductive glass of precursor sol drop after etching Clock, 30 seconds), continuous spin coating twice, obtains TiO2Dissolved glue film;By TiO2Dissolved glue film relative humidity be 50% moisture maintainer in After preserving 12 hours at room temperature, then it is placed in the Muffle furnace of air atmosphere, with 1 DEG C/min of heating rate by Muffle furnace Temperature rise to 550 DEG C, and keep carrying out TiO in 30 minutes at such a temperature2The sintering of sol pellicle;After terminating, horse is allowed Not stove is cooled to room temperature with 1 DEG C/min of speed, obtains TiO2Nano thin-film.TiO2The thickness of nano thin-film is by spin coating time numerical control System.
The sign of (1-3) product:
TiO2The sign of nano thin-film is shown in accompanying drawing 2 and 3.XRD results show:Gained TiO2Film layer belongs to anatase crystal formation (JCPDS 083-2243), in addition to the diffraction maximum of ITO lining bases, the presence of other impurity peaks is had no, illustrate gained TiO2Film is pure Degree and crystallinity are very high.SEM results show:Prepared TiO2Nano thin-film by 20-30nm TiO2Nano particle forms, thin The thickness of film is 120nm;TiO2Film surface is smooth, very in wide area without notable pin hole or seminess, compactness It is very high.
2、TiO2The preparation of/CdS hetero-junction thin-films.
The etching of (2-1) ITO electro-conductive glass and cleaning:Step 1.
(2-2)TiO2The preparation of film:Step 1.
(2-3)TiO2The preparation of/CdS hetero-junction thin-films:
Take two clean beakers standby.First configuration concentration is 0.48g/L CdSO in beaker 14·8/3H2The O aqueous solution 350mL, the ammoniacal liquor that 56mL concentration is 25%-28% is then added, the mixed aqueous solution is persistently stirred in 65 DEG C of water-baths. Configuration concentration is 55g/L thiourea solution 45mL in beaker 2.Deposition there is into TiO2The ITO electro-conductive glass of film vertically put by leaching In the CdSO of the stirring of beaker 14In ammoniacal liquor mixed solution;The thiourea solution in beaker 2 is added dropwise to burning after 1 minute In cup 1,65 DEG C of stirred in water bath are continued at after dripping and carry out reactive deposition within 10 minutes;After the completion of deposition, band TiO is taken out2It is thin The ITO electro-conductive glass of film, dried up several times and with nitrogen with deionized water elution, it is small to be then placed in 65 DEG C of vacuum drying chamber 3 When, fully to remove residual moisture, obtain by TiO2With the plate hetero-junctions of binary of two kinds of nano particle dense film compositions of CdS Film (that is, TiO2/ CdS hetero-junction thin-films).
The sign of (2-4) product:
TiO2The sign of/CdS hetero-junction thin-films is shown in accompanying drawing 4,5 and 6.XRD results show:The film CdS crystal formations of gained are Emission in Cubic (JCPDS 80-0019), has no the presence at other impurities peak, illustrates that gained CdS film purity and crystallinity are very high; SEM results show:Gained TiO2In/CdS hetero-junction thin-films, CdS film is made up of 10-20nm CdS nano particles and it is thick Spend for 80nm;CdS film surfacing, very high without notable pin hole or seminess, compactness very in wide area.Absorb Spectrum shows:TiO2The main absorption spectrum ranges of film layer ultra-violet (UV) band (<400nm), it is substantially transparent in limit of visible spectrum , and TiO2There is CdS absorption in 400-550nm spectral regions in/CdS hetero-junction thin-films.
3、TiO2/CdS/CuInS2The preparation of hetero-junction thin-film.
The etching of (3-1) ITO electro-conductive glass and cleaning:Step 1.
(3-2)TiO2The preparation of film:Step 1.
(3-3)TiO2The preparation of/CdS hetero-junction thin-films:Step 2.
(3-4)TiO2/CdS/CuInS2The preparation of hetero-junction thin-film:
1.46g InCl are added in 10mL N,N-dimethylformamide3·4H2O is simultaneously stirred 1 hour at room temperature, is obtained To InCl3Solution;In InCl30.95g CuI is added in solution and continues stirring 1 hour at room temperature, obtains InCl3And CuI Mixture solution;Thiocarbamide 3.04g is added in resulting mixture solution, stirs 20 hours at room temperature, obtains CuInS2 Pre-reaction material solution, wherein InCl3,:CuI:The mol ratio of thiocarbamide is 1:1:8.The CuInS2Pre-reaction material solution is colourless It is bright and very stable.
By 150 μ L CuInS2Reactant precursor solution is added drop-wise to TiO2Simultaneously spin coating (3000 on/CdS hetero-junction thin-films Rev/min, 20 seconds) film forming, spin coating 2 times is repeated, obtains CuInS2Pre-reaction material film;By the pre-reaction material film of gained It is placed in 65 DEG C of vacuum drying chambers and dries 15 minutes, is then placed on again in the thermal station under inert gas shielding, with 20 DEG C/min Thermal station temperature is risen to 150 DEG C and kept for 5 minutes by heating rate heating, to promote solvent to volatilize, then with 20 DEG C/min of heating Thermal station temperature is risen to 250 DEG C and carries out the heat treatment of 10 minutes to sample in this temperature by speed heating;After heat treatment terminates, sample Product naturally cool to room temperature, obtain being deposited on TiO2Crystallinity CuInS on/CdS hetero-junction thin-films2Embryophoric membrane.Often complete once this Crystallinity CuInS2The preparation process of embryophoric membrane is a CuInS2Crystallize the growth course of embryophoric membrane.TiO2On/CdS hetero-junction thin-films CuInS2The thickness of film, by crystallinity CuInS2Growth course number (n) control of embryophoric membrane.Repeat the crystallinity CuInS of n times2 After the growth course of embryophoric membrane, certain thickness CuInS is completed2Film is in TiO2Growth in situ on/CdS hetero-junction thin-films, is obtained By TiO2、CdS、CuInS2Plate hetero-junction thin-film (that is, the TiO of ternary of three kinds of nano particle dense film compositions2/CdS/ CuInS2Hetero-junction thin-film).In the present embodiment, n=2 is controlled.
The sign of (3-5) product:
TiO2/CdS/CuInS2The sign of hetero-junction thin-film is shown in that accompanying drawing 7,8 and 9, XRD result show:Except ITO, TiO2With Outside CdS diffraction maximum, TiO2/CdS/CuInS2Hetero-junction thin-film shows chalcopyrite crystal formation CuInS2(JCPDS 85-1575's) Crystal diffraction peak, but exist without other miscellaneous peaks, the CuInS of gained2Film purity is higher.SEM results show:As n=2, institute The TiO obtained2/CdS/CuInS2CuInS in hetero-junction thin-film2The thickness of film is about 210nm, and CuInS2Film is by 10-20nm CuInS2Nano particle forms;Although CuInS2Certain fluctuating be present in film surface, but in nothing very in wide area significantly Pin hole or seminess, compactness are higher.UV-vis absorption spectrums show:TiO2/CdS/CuInS2Hetero-junction thin-film is in 300- There is preferable absorption in 900nm spectral region.
4、TiO2/CdS/CuInS2The preparation of solar cell.
The cleaning of (4-1) ITO electro-conductive glass and etching:Step 1.
(4-2)TiO2The preparation of film:Step 1.
(4-3)TiO2The preparation of/CdS hetero-junction thin-films:Step 2.
(4-4)TiO2/CdS/CuInS2The preparation of hetero-junction thin-film:Step 3
The preparation of (4-5) Spiro-OMeTAD chlorobenzene solutions:
73mg Spiro-OMeTAD powder is added in 1mL chlorobenzenes, stirs 2 hours, obtains lurid at room temperature Spiro-OMeTAD chlorobenzene solutions.In Spiro-OMeTAD chlorobenzene solutions, 19 μ L LiTFSI acetonitrile solutions are sequentially added (520mg/mL) and 29 μ L tert .-butylpyridine (TBP), and stirring 1 hour at room temperature, obtain it is transparent it is light yellow by The mol ratio of the chlorobenzene solution of Spiro-OMeTAD, LiTFSI and TBP mixture, wherein Spiro-OMeTAD/LiTFSI/TBP About 1.88/1/6.25.
(4-6)TiO2/CdS/CuInS2The preparation of solar cell:
65 μ L Spiro-OMeTAD chlorobenzene solutions are added dropwise in TiO2/CdS/CuInS2On ternary heterojunction film, carry out Spin coating (3000 revs/min, 30 seconds);It is heat-treated 10 minutes at 100 DEG C in atmosphere, it is about 100nm's to obtain thickness Spiro-OMeTAD film hole transmission layers.
Sun electricity is used as by the Au films that vacuum thermal evaporation methods evaporation thickness is 100nm on Spiro-OMeTAD films The negative electrode in pond, the position of Au films are located at directly over ITO layer;The size of Au electrodes is 1 × 4mm by template contral2, and it is used as battery Effective area;Evaporation condition is as follows:It is 5 × 10 to evaporate chamber pressure-4Pa, evaporation rate be 0.5 angstroms per second (preceding 50nm) and 1 angstrom/ Second (rear 50nm).Cell package is carried out in the glove box of nitrogen protection, is obtained based on the plate hetero-junction thin-film of ternary too Positive electricity pond (that is, TiO2/CdS/CuInS2Solar cell), shown in battery structure as accompanying drawing 1.
The performance characterization of (4-7) solar cell:
The performance of solar cell is characterized by IPCE spectrums and current-voltage (J-V) curve, sees accompanying drawing 10 and 11.J-V and IPCE Test is completed in atmospheric environment and at room temperature.IPCE spectrums show, in 300-900nm spectral region, TiO2/CdS/ CuInS2There is solar cell good photoelectric current to produce performance, this and TiO2/CdS/CuInS2The absorption spectrum of hetero-junction thin-film Performance is consistent.The J-V tests of battery, that utilize is the simulated solar irradiations of AM 1.5 (light intensity Pin=100mW/cm2), the energy of battery Efficiency eta is by open-circuit voltage (Voc), short circuit current (Jsc) and fill factor, curve factor (FF) be calculated, i.e. η=Jsc·Voc·FF/ Pin.In J-V test process, battery illuminating area by shielding window control and it is in the same size with Au electrodes.J-V result tables Bright, the energy conversion efficiency of battery has reached 5.78%.

Claims (9)

  1. A kind of 1. solar cell based on ternary inorganic flat type hetero-junction thin-film, it is characterised in that:On glass lined base successively Deposition has anode, ternary inorganic flat type hetero-junction thin-film, organic cavity transmission layer, negative electrode;Described ternary inorganic flat type Hetero-junction thin-film is by TiO2Nano thin-film, CdS nano thin-films and CuInS2Nano thin-film forms, TiO2Nano thin-film, CdS nanometers Film and CuInS2Nano thin-film, it is sequentially deposited on solar cell anode.
  2. 2. the solar cell according to claim 1 based on ternary inorganic flat type hetero-junction thin-film, it is characterised in that:Institute The solar cell anode stated is ITO layer, TiO2Nano thin-film by 20-30nm TiO2Nano particle form, CdS nano thin-films by 10-20nm CdS nano particles composition, CuInS2Nano thin-film by 10-20nm CuInS2Nano particle forms;Described has Machine hole transmission layer is Spiro-OMeTAD films;The negative electrode is Au films.
  3. 3. the solar cell according to claim 2 based on ternary inorganic flat type hetero-junction thin-film, it is characterised in that:Institute The thickness for the ITO layer stated is 100-300nm, TiO2The thickness of nano thin-film is 50-150nm, and CdS nano film thickness is 50- 100nm, CuInS2Nano film thickness is 100-500nm, and Spiro-OMeTAD film thicknesses are 100-200nm, Au film thicknesses For 60-120nm.
  4. 4. the solar cell according to claim 2 based on ternary inorganic flat type hetero-junction thin-film, it is characterised in that:Institute The Spiro-OMeTAD films stated are made by Spiro-OMeTAD, LiTFSI and TBP, Spiro-OMeTAD, LiTFSI and TBP's Mol ratio is 1-3:1:5-7.
  5. 5. the preparation of the solar cell based on ternary inorganic flat type hetero-junction thin-film according to claim any one of 1-4 Method, it is characterised in that:Comprise the following steps:
    (1) anode ITO electro-conductive glass is etched into slice with concentrated hydrochloric acid and Zn powder, then surpassed respectively through acetone, isopropanol, ultra-pure water Sound cleans 4-6 minutes, after drying, obtains the ITO electro-conductive glass after over etching;Deposited on ITO electro-conductive glass after etching TiO2It is standby after nano thin-film;
    (2) configuration concentration is the 0.4-0.6g/L cadmium sulfate aqueous solution, adds the ammoniacal liquor that concentration is 25%-28% thereto, and Dissolved in 60-70 DEG C of stirred in water bath;Configuration concentration is 50-60g/L thiourea solution;The cadmium sulfate aqueous solution:Ammoniacal liquor:Thiocarbamide Aqueous solution volume ratio is 340-360:54-58:43-47;Deposition there is into TiO2Vacantly leaching is placed in the ITO electro-conductive glass of film vertically In the cadmium sulfate of stirring and the mixed aqueous solution of ammoniacal liquor, thiourea solution is added, continues to carry out 8- in 60-70 DEG C of water-bath 12min reactive depositions, obtain TiO2With the plate hetero-junction thin-film of binary of two kinds of nano thin-film compositions of CdS;
    (3) at room temperature by InCl3It is dissolved in DMF, stirs 0.5-1.5 hours, be configured to 145-147g/L's Solution, CuI is then added, continue to stir 0.5-1.5 hours, add thiocarbamide, stir 15-30 hours at room temperature, obtain CuInS2Pre-reaction material solution, wherein InCl3:CuI:The mol ratio of thiocarbamide is 1:1:6-10;
    By CuInS2Reactant precursor solution is added drop-wise on the plate hetero-junction thin-film of binary of gained and spin-coating film, repeats Spin coating 2 times, obtains CuInS2Pre-reaction material film;The pre-reaction material film of gained is placed in 65 DEG C of vacuum drying chambers and done After dry, it is placed in the thermal station under inert gas shielding, thermal station temperature is first risen to 120-180 DEG C and keeps 4-6 minutes, Ran Houji It is continuous to be warming up to 200-300 DEG C and the heat treatment of 5-15 minutes is carried out to sample in this temperature;After heat treatment terminates, sample natural cooling To room temperature, crystallinity CuInS is obtained2Embryophoric membrane;Repeat to CuInS2The thickness of nano thin-film is up to standard, obtains TiO2, CdS and CuInS2The plate hetero-junction thin-film of ternary of three kinds of nano thin-film compositions;
    (4) on the plate hetero-junction thin-film of ternary obtained by step (3), one layer of concentration of spin coating is 60-90mg/mL Spiro- OMeTAD, LiTFSI and TBP mixture solution, in atmosphere 50-150 DEG C of heat treatment 5-15 minute, obtain Spiro-OMeTAD Film hole transmission layer;
    (5) on the Spiro-OMeTAD film hole transmission layers obtained by step (4), Au films is deposited by thermal evaporation method, obtained To the solar cell based on ternary inorganic flat type hetero-junction thin-film;
    (6) solar cell made from step (5) is encapsulated under inert gas shielding and obtains solar cell product.
  6. 6. the preparation method of the solar cell according to claim 5 based on ternary inorganic flat type hetero-junction thin-film, its It is characterised by:Chemical bath method described in step (2) can be replaced with spin-coating method.
  7. 7. the preparation method of the solar cell according to claim 5 based on ternary inorganic flat type hetero-junction thin-film, its It is characterised by:The solvent of Spiro-OMeTAD solution described in step (4) is chlorobenzene.
  8. 8. the preparation method of the solar cell according to claim 5 based on ternary inorganic flat type hetero-junction thin-film, its It is characterised by:Spin coating operation described in step (3), (4), it can be replaced with silk screen print method or scraping blade method or ink-jet printing process.
  9. 9. the preparation method of the solar cell according to claim 5 based on ternary inorganic flat type hetero-junction thin-film, its It is characterised by:Inert gas described in step (3), (6) is nitrogen.
CN201710995180.5A 2017-10-23 2017-10-23 Solar cell based on ternary inorganic flat heterojunction thin film and preparation method thereof Active CN107887513B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710995180.5A CN107887513B (en) 2017-10-23 2017-10-23 Solar cell based on ternary inorganic flat heterojunction thin film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710995180.5A CN107887513B (en) 2017-10-23 2017-10-23 Solar cell based on ternary inorganic flat heterojunction thin film and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107887513A true CN107887513A (en) 2018-04-06
CN107887513B CN107887513B (en) 2020-10-16

Family

ID=61782052

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710995180.5A Active CN107887513B (en) 2017-10-23 2017-10-23 Solar cell based on ternary inorganic flat heterojunction thin film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107887513B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109256468A (en) * 2018-07-31 2019-01-22 中国科学院合肥物质科学研究院 A kind of hydridization solar cell and preparation method thereof integrated based on a variety of hetero-junctions performances

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070184A (en) * 2010-12-01 2011-05-25 同济大学 Preparation method of CuInS2 nanoparticles
CN103253698A (en) * 2013-05-28 2013-08-21 江苏科技大学 Method for preparing CuInS2 nanocrystals by mixed solvent thermal process
CN107093641A (en) * 2017-04-26 2017-08-25 中国科学院合肥物质科学研究院 A kind of thin film solar cell based on inorganic flat hetero-junctions and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070184A (en) * 2010-12-01 2011-05-25 同济大学 Preparation method of CuInS2 nanoparticles
CN103253698A (en) * 2013-05-28 2013-08-21 江苏科技大学 Method for preparing CuInS2 nanocrystals by mixed solvent thermal process
CN107093641A (en) * 2017-04-26 2017-08-25 中国科学院合肥物质科学研究院 A kind of thin film solar cell based on inorganic flat hetero-junctions and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MOHAMMAD REZA GOLOBOSTANFARD等: ""Solution processable wurtzite CuInS2 inverted type solar cell"", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 *
唐明华等: ""铜铟硫(CuInS2)薄膜太阳能电池的制备与光电性能研究"", 《万方:硕士论文》 *
赵琴等: ""反应介质对溶剂热法合成CuInS2纳米晶体的影响"", 《武汉理工大学学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109256468A (en) * 2018-07-31 2019-01-22 中国科学院合肥物质科学研究院 A kind of hydridization solar cell and preparation method thereof integrated based on a variety of hetero-junctions performances

Also Published As

Publication number Publication date
CN107887513B (en) 2020-10-16

Similar Documents

Publication Publication Date Title
Yuan et al. Efficient planar antimony sulfide thin film photovoltaics with large grain and preferential growth
CN102646745B (en) Photovoltaic device and solar battery
CN103367512B (en) A kind of solar cell based on inorganic bulk heterojunction and preparation method thereof
CN103474575B (en) A kind of be electron transfer layer hybrid solar cell and the preparation thereof of sulphur zinc oxide
JP2010512647A (en) Doping technology for IBIIIAVIA group compound layer
CN107093641A (en) A kind of thin film solar cell based on inorganic flat hetero-junctions and preparation method thereof
CN104795456B (en) Electrodeposition process prepares the method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials
CN103824902B (en) A kind of FeS2Film and preparation method thereof
CN103137868B (en) Organic/ inorganic hybridization solar battery based on ternary nanometer array and preparation method thereof
Saadi et al. Recent developments and applications of nanocomposites in solar cells: a review
CN107403853A (en) A kind of ZTO ZnO/CBS GSs flexible thin-film solar cells and preparation method thereof
CN107732014B (en) Solar cell based on ternary inorganic body type heterojunction thin film and preparation method thereof
CN108305948B (en) Perovskite material multi-quantum well structure regulation method and application and device thereof
CN105470338B (en) A kind of flexible overlapping solar cell and preparation method
Zhao et al. Atmospheric preparation of ZnO thin films by mist chemical vapor deposition for spray-coated organic solar cells
CN107887513A (en) A kind of solar cell based on ternary inorganic flat type hetero-junction thin-film and preparation method thereof
CN109671848B (en) CuPbSbS3Novel thin-film solar cell and preparation method thereof
CN102024858B (en) Ink, thin film solar cell and manufacturing methods thereof
CN107369729B (en) A kind of nano ordered interpenetrating total oxygen compound hetero-junction thin-film solar cell and preparation method thereof
Peksu et al. Synthesis of ZnO nanowires and their photovoltaic application: znO nanowires/AgGaSe2 thin film core-shell solar cell
CN110844936A (en) Preparation method of antimony trisulfide nanorod array and solar cell based on antimony trisulfide nanorod array
CN110676385A (en) Carbon-based perovskite solar cell based on multifunctional interface modification layer
CN109216560A (en) A kind of inorganic perovskite preparation method of solar battery and products thereof with indium sulfide thin film
CN106601873B (en) A kind of spin coating device for CZTS films and the method for preparing CZTS batteries
CN111599881B (en) Single crystal cuprous oxide composite semiconductor nano generator and manufacturing method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant