CN106277051A - A kind of crystallinity Sb2s3the solution preparation for processing of thin film - Google Patents

A kind of crystallinity Sb2s3the solution preparation for processing of thin film Download PDF

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CN106277051A
CN106277051A CN201610578506.XA CN201610578506A CN106277051A CN 106277051 A CN106277051 A CN 106277051A CN 201610578506 A CN201610578506 A CN 201610578506A CN 106277051 A CN106277051 A CN 106277051A
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thin film
crystallinity
solution
reaction material
crystallization
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陈俊伟
王命泰
齐娟娟
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Hefei Institutes of Physical Science of CAS
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Hefei Institutes of Physical Science of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C01G30/008—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3464—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide
    • C03C17/347—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide comprising a sulfide or oxysulfide
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a kind of crystallinity Sb2S3The solution preparation for processing of thin film.At room temperature simple compounds is dissolved in mixed organic solvents the Sb that preparation is stable, transparent and homogeneous2S3Pre-reaction material solution, is serving as a contrast on base, by the heat treatment of precursor film is prepared crystallinity Sb that crystallite dimension is big, compactness is high, thickness is controlled, specific absorbance is big by solution processing technology by pre-reaction material thin film deposition under normal temperature and pressure2S3Thin film.Technology of preparing of the present invention has that method is simple, low cost and solvent for use low toxicity and the advantage of safety, overcomes that equipment requirements of the prior art is high, preparation condition is complicated, use high toxicity solvent and Sb2S3The shortcomings such as film crystal unity is low, have important using value in fields such as photoelectric material, photovoltaic material and devices.

Description

A kind of crystallinity Sb2S3The solution preparation for processing of thin film
Technical field
The present invention relates to semiconductor film material preparation method field, be exactly a kind of crystallinity Sb2S3Thin film molten Liquid preparation for processing.
Background technology
Antimonous sulfide (Sb2S3) it is a kind of direct band-gap semicondictor material, there is high refractive index, better photosensitivity, excellence Pyroelectricity, good photoconductivity and electric conductivity, at television camera, microwave device, switching device and various opto-electronic device Etc. aspect there is important application [J.Non-Cryst.Solids2005,351,987-992；Appl.Surf.Sci.2008, 254,3200-3206；Opt.Mater.2015,46,536-541；Mater.Sci.Semicond.Proc.2015,40,643- 649].Because it has the band gap width matched with solar spectrum maximum photon range of flow 600-800nm (1.55-2.07eV) (Eg=1.7-1.8eV) and the bigger absorption coefficient of light (105cm-1), Sb2S3It is considered as that a kind of effective solar cell light is inhaled Receive material [Thin Solid Films 2009,517,2503-2507；Nano Lett.2010,10,2609-2612；Nano Lett.2011,11,4789-4793；Nano Lett.2012,12,1863-1867；Chem.Commun.2012,48,2818- 2820；Appl.Phys.Lett.2012,100,243102；Int.J.Hydrogen Energy,2013,38,16749- 16754；Thin Solid Films 2014,569,28-34；Nano Energy 2015,12,686-697； Phys.Chem.Chem.Phys.2015,17,12328-12339]。
Crystallinity Sb at present2S3The conventional preparation method of thin film is described below.(1) vacuum thermal evaporation sedimentation, its technology is special Point is: in high vacuum conditions by Sb2S3Heating evaporation also deposits to serve as a contrast on base, Sb2S3The degree of crystallinity of thin film is typically by lining base temperature Degree controls, and Sb2S3The thickness of thin film is then controlled by sedimentation rate and time；When serving as a contrast base temperature deficiency, also need thermal evaporation The Sb of deposition2S3Thin film carries out heat treatment at a temperature of 100-400 DEG C, to improve Sb further2S3The degree of crystallinity of thin film and photoelectricity Performance [Cryst.Res.Technol.2006,41,474-480；Cryst.Res.Technol.2007,42,281-285； Cryst.Res.Technol.2008,43,964-969；J.Phys.D:Appl.Phys.2007,40,2440-2444； Chalcogenide Lett.2010,7,217-225；Chalcogenide Lett.2010,7,701-706； Curr.Appl.Phys.2013,13,262-266；Thin Solid Films 2014,569,28-34； Appl.Surf.Sci.2015,350,19-24].Vacuum thermal evaporation sedimentation, relates to fine vacuum and the control system of lining base temperature The application of system, device and preparation technology is more complicated and energy consumption is high, it is unfavorable for prepared by large area.(2) radio-frequency magnetron sputter method, its skill Art feature is: in high vacuum conditions, utilizes rf magnetron sputtering by Sb2S3Target material deposition to lining base on, Sb2S3The thickness of thin film Degree is then controlled by sputter rate and time, the Sb of sputtering sedimentation2S3Thin film need to carry out heat treatment at a temperature of 200-400 DEG C and carry Its degree of crystallinity high and photoelectric properties [Thin Solid Films 2007,515,7171-7176].Radio-frequency magnetron sputter method, relates to More complicated to the application of fine vacuum, device and preparation technology and energy consumption is high, it is unfavorable for prepared by large area.(3) chemical bath (CBD) sinks Area method, its technical characterstic is: lining base is placed in preparation Sb2S3Reactant solution in, lining base obtains predominantly amorphous Sb2S3Thin film, then at a temperature of 100-400 DEG C, annealing obtains crystallinity Sb2S3Thin film, Sb2S3The thickness of thin film is mainly by CBD Sedimentation time controls, and Sb2S3The degree of crystallinity of thin film depends on follow-up annealing temperature [Semicond.Sci.Technol.1994,9,1234-1241；Appl.Surf.Sci.2008,254,3200-3206； J.Ovonic Res.2009,5,145-156；Chalcogenide Lett.2010,7,101-109；J.Phys.D: Appl.Phys.2010,43,075404；Chalcogenide Lett.2011,8,571-577；J.Mater.Sci.2011, 46,700-706；Opt.Mater.2015,46,536-541；Phys.Chem.Chem.Phys.2015,17,12328- 12339].Chemical bath deposition method energy consumption is relatively low, but the thin film that subsequent thermal annealing obtains exists serious pin-hole phenomena so that Crystallinity Sb finally given2S3The compactness of thin film is poor.(4) spray pyrolysis, its technical characterstic is: will prepare Sb2S3's Pre-reaction material solution, deposits on high temperature lining base with Sprayable, and reactant decomposes on lining base and reaction obtains Sb2S3Thin Film；Wherein, Sb2S3The degree of crystallinity of thin film is controlled by serving as a contrast base temperature, and Sb2S3The thickness of thin film is then by spray rate and time Control [J.Phys.Chem.Solids 2000,61,561-568；Mater.Chem.Phys.2000,63,263-269； Mater.Sci.Semicond.Proc.2014,26,593-602；Mater.Sci.Semicond.Proc.2015,40,867- 872].The Sb that spray pyrolysis obtains2S3The degree of crystallinity of thin film is relatively low and compactness is poor.(5) chemical vapour deposition technique, its skill Art feature is: in high vacuum conditions, and deposits to serve as a contrast on base by gas evaporation by the organic compound containing Sb and S, Sb2S3The degree of crystallinity of thin film is typically controlled by lining base temperature, and Sb2S3The thickness of thin film is then controlled by sedimentation rate and time [Mater.Sci.Semicond.Proc.2015,40,643-649].Chemical vapour deposition technique, relates to fine vacuum and lining base temperature The application of control system of degree, device and preparation technology is more complicated and energy consumption is high, it is unfavorable for prepared by large area.(6) before reactant Driving liquid sedimentation, its technical characterstic is: by certain stoichiometric proportion, Sb powder and S powder are dissolved in hydrazine prepared Sb2S3Reaction Thing precursor liquid, deposits to this precursor liquid (such as, by the method for spin coating) under room temperature obtain precursor film on lining base, then exists At a temperature of 100-300 DEG C, precursor film is annealed, make predecessor generation chemical reaction obtain crystallinity Sb2S3Thin film [Sci.Rep.2015,5,10978].Reactant precursor liquid sedimentation, solvent used is hydrazine, has high toxicity, absorbs water by force Property and inflammability, must be prevented from the volatilization of hydrazine and the harm to operator, generally in its reactant precursor liquid film forming procedure The Special-purpose enclosed protection equipment of the waterproof oxygen of nitrogen protection is carried out.
In the present invention, we utilize the mixed organic solvents of low toxicity and safety to dissolve SbCl3Sb is prepared with thiourea2S3Anti- Answer thing precursor liquid, establish a kind of new reactant precursor liquid preparation for processing to prepare Sb2S3Crystallite dimension is big, compactness Crystallinity Sb high, extinction absorptance is big and thickness is controlled2S3Thin film.
Summary of the invention
The present invention relates to semiconductor film material preparation method field, be exactly a kind of crystallinity Sb2S3Thin film molten Liquid preparation for processing.Obtained crystallinity Sb2S3Thin film has Sb2S3Crystallite dimension is big, compactness is high, extinction absorbs system The feature that number is big and thickness is controlled.
The technical solution adopted in the present invention is:
A kind of crystallinity Sb2S3The solution preparation for processing of thin film, it is characterised in that: by thiourea and SbCl under room temperature3Molten Solution, in the mixed organic solvents that DMF and glycerol form, obtains Sb2S3Pre-reaction material solution, will Sb2S3Pre-reaction material solution film forming on lining base prepares Sb2S3Pre-reaction material thin film, by Sb2S3Pre-reaction material is thin The heat treatment of film makes Sb2S3Crystallization embryophoric membrane, passes through Sb2S3The growth course of crystallization embryophoric membrane obtains crystallinity Sb2S3Thin film.
Described a kind of crystallinity Sb2S3The solution preparation for processing of thin film, it is characterised in that comprise the following steps:
(1) being dissolved in DMF by thiourea under room temperature, stir 0.5-1 hour, obtaining concentration is 0.5- The thiourea solution of 2.0mol/L clarification；Then, obtained thiourea solution adds SbCl3, wherein SbCl3With rubbing of thiourea Your ratio is 1:1.6-2, and under room temperature, stirring obtains thiourea and SbCl for 0.5-1 hour3Mixture solution；Finally, molten at this mixture Adding glycerol in liquid, wherein the volume ratio of DMF and glycerol is 2-3:1, stirs 5-15 minute, obtains SbCl3Concentration is the Sb of 1.0-1.5mol/L2S3Pre-reaction material solution；
(2) by institute Sb2S3Pre-reaction material solution is added drop-wise to serve as a contrast on base, after standing the 10-30 second, with continuous two-stage spin-coating method Film forming, repeats spin coating 2-4 time, obtains Sb2S3Pre-reaction material thin film；By the Sb of gained2S3Pre-reaction material thin film is done in vacuum In dry case dry 10-20 minute in 60-80 DEG C；By dry Sb2S3Pre-reaction material thin film forwards the thermal station of inert gas shielding to On, within 5-10 minute, carry out heat treatment 300-360 DEG C of holding, obtain Sb2S3Crystallization embryophoric membrane, often completes a Sb2S3Crystallization embryophoric membrane Preparation process be a Sb2S3The growth course of crystallization embryophoric membrane, repeated several times Sb2S3After the growth course of crystallization embryophoric membrane, To crystallinity Sb2S3Thin film.
Described a kind of crystallinity Sb2S3The solution preparation for processing of thin film, it is characterised in that: described lining base is permissible It is FTO electro-conductive glass or TiO2Thin film.
Described a kind of crystallinity Sb2S3The solution preparation for processing of thin film, it is characterised in that: the company described in step (2) Continuous two-stage spin-coating method can replace with silk screen print method or scraping blade method or ink-jet printing process.
Described a kind of crystallinity Sb2S3The solution preparation for processing of thin film, it is characterised in that: the company described in step (2) The spin coating of continuous two-stage spin-coating method requires: first order spin coating rotating speed is 800-1200 rev/min and spin-coating time is 10 seconds；The second level Rotating speed for 2000-3000 rev/min and spin-coating time is 30 seconds.
Described a kind of crystallinity Sb2S3The solution preparation for processing of thin film, it is characterised in that: lazy described in step (2) The property preferred nitrogen of gas.
The principle of the present invention is:
The present invention utilizes simple compound to be dissolved in mixed organic solvents preparation Sb at room temperature2S3Pre-reaction material Solution, utilizes Sb2S3Pre-reaction material solution prepares Sb by solution processing technology2S3Pre-reaction material thin film, former through normal pressure Position heat-induced chemical reactions and crystallization process, obtain Sb2S3Crystallization embryophoric membrane, by carrying out certain Sb2S3The growth of crystallization embryophoric membrane Process obtains crystallinity Sb2S3Thin film.Crystallinity Sb2S3The thickness of thin film is by Sb2S3Crystallization embryophoric membrane growth course number of times and Sb2S3The concentration of pre-reaction material solution controls.
The invention have the benefit that
1, a kind of new Sb is established2S3Reactant precursor liquid solution preparation for processing prepares crystallinity Sb2S3Thin Film.Prepared crystallinity Sb2S3Thin film has Sb2S3Crystallite dimension is big, compactness is high, extinction absorptance big and thickness can The feature of control, wherein Sb2S3Crystal grain mostly with crystallinity Sb2S3The thickness of thin film is suitable；Prepared crystallinity Sb2S3Thin film has There is EgThe band gap of=1.60-1.70eV, and have 10 in 350-650nm absorbing light wave-length coverage5cm-1Specific absorbance.
2, the innovative point of the present invention has: utilize the mixed organic solvents of low toxicity and safety to dissolve SbCl3With thiourea preparation all One, transparent and stable Sb2S3Pre-reaction material solution；Utilize solution processing technology by Sb under room temperature2S3Pre-reaction material thin film Deposit to serve as a contrast on base, by Sb on lining base under normal pressure2S3The heat-induced chemical reactions of pre-reaction material and crystallization process, prepare Sb2S3Crystallization embryophoric membrane, utilizes Sb2S3Crystallinity Sb is prepared in the growth of crystallization embryophoric membrane2S3Thin film.
3, the present invention prepares Sb2S3The Comparision close with other people that work of pre-reaction material solution.Technological layer: he People [Sci.Rep.2015,5,10978] by being dissolved in hydrazine preparation Sb by Sb powder and S powder2S3Reactant precursor liquid, institute Solvent hydrazine there is high toxicity and inflammability, reactant precursor liquid film forming procedure need to enter in Special-purpose enclosed protection equipment OK, to prevent the volatilization of hydrazine and to prevent the impact of water and oxygen.In the present invention, DMF and glycerol is utilized to mix Bonding solvent dissolves SbCl3Sb is prepared with thiourea2S3Reactant precursor liquid, mixed solvent low toxicity used and safety, reactant Precursor liquid film forming procedure can complete in conventional ventilating kitchen, it is not necessary to the most waterproof and oxygen；Technology of preparing is simple and safe, if Low for requiring.Product structure aspect: crystallinity Sb prepared by other people technology2S3There is serious pin-hole phenomena in thin film, makes thin film The most poor；Crystallinity Sb obtained in the present invention2S3Thin film has Sb2S3Crystallite dimension is big, compactness is high, extinction absorbs system The feature that number is big and thickness is controlled.
Accompanying drawing explanation
Fig. 1 is FTO/Sb of the present invention2S3The XRD characterization result of-1.0 thin film (n=2).
Fig. 2 is FTO/Sb of the present invention2S3The SEM characterization result of-1.0 thin film (n=2)；Wherein, (a) surface picture, (b) cross section picture.
Fig. 3 is FTO/Sb of the present invention2S3The optical property characterization result of-1.0 thin film (n=2)；Wherein, (a) UV- Vis absorption spectrum, (b) specific absorbance and the dependency of wavelength.
Fig. 4 is FTO/TiO of the present invention2The SEM characterization result of thin film；Wherein (a) surface picture, (b) cross section picture.
Fig. 5 is FTO/TiO of the present invention2The XRD characterization result of thin film.
Fig. 6 is FTO/TiO of the present invention2/Sb2S3The XRD characterization result of-1.0 thin film (n=2).
Fig. 7 is FTO/TiO of the present invention2/Sb2S3The SEM characterization result of-1.0 thin film (n=2)；Wherein, (a) table Image surface, (b) cross section picture.
Fig. 8 is FTO/TiO of the present invention2/Sb2S3The optical property characterization result of-1.0 thin film (n=2)；Wherein, (a) UV-vis absorption spectrum, (b) specific absorbance and the dependency of wavelength.
Fig. 9 is FTO/TiO of the present invention2/Sb2S3-1.5 thin film (n=2) and FTO/TiO2/Sb2S3-1.5 thin film (n =4) XRD characterization result.
Figure 10 is FTO/TiO of the present invention2/Sb2S3-1.5 thin film (n=2) and FTO/TiO2/Sb2S3-1.5 thin film (n=4) SEM characterization result；Wherein, (a, b) n=2, (c, d) n=4, (a, c) surface picture, (b, d) cross section picture.
Figure 11 FTO/TiO of the present invention2/Sb2S3-1.5 thin film (n=2) and FTO/TiO2/Sb2S3-1.5 thin film (n =4) optical property characterization result；Wherein, the dependency of (a) UV-vis absorption spectrum, (b) specific absorbance and wavelength.
Detailed description of the invention
Crystallinity Sb on embodiment 1:FTO electro-conductive glass lining base2S3The preparation of thin film
(1) cleaning of FTO electro-conductive glass:
FTO electro-conductive glass, through acetone, isopropanol, ultra-pure water ultrasonic cleaning 5 minutes respectively, obtains clean FTO conduction glass Glass lining base, the most standby.
(2)SbCl3Concentration is the Sb of 1.0mol/L2S3The preparation of pre-reaction material solution:
By SbCl under room temperature3Being dissolved in DMF, stir 0.5 hour, obtaining concentration is that 1.0mol/L is clear Clear SbCl3Solution；Then, at obtained SbCl3Solution adds thiourea, wherein SbCl3It is 1 with the mol ratio of thiourea: 1.8, under room temperature, stirring obtains the SbCl of clarification for 0.5 hour3Mixture solution with thiourea；Finally, in this mixture solution Adding glycerol, wherein the volume ratio of DMF and glycerol is 2.5:1, stirs 10 minutes, obtains SbCl3Dense Degree is the Sb of 1.0mol/L2S3Pre-reaction material solution.This Sb2S3Pre-reaction material solution is faint yellow, homogeneous transparent, and surely Fixed.
(3) crystallinity Sb on FTO electro-conductive glass2S3The preparation of thin film:
By SbCl3Concentration is the Sb of 1.0mol/L2S3Pre-reaction material solution is added drop-wise on FTO lining base, after standing 20 seconds, By continuous two-stage spin-coating method spin-coating film, (first order spin coating rotating speed is 1000 revs/min and spin-coating time is 10 seconds；The second level is revolved Rotating speed is 2500 revs/min and spin-coating time is 30 seconds), repeat spin coating 3 times, obtain Sb2S3Pre-reaction material thin film；By gained Sb2S3Pre-reaction material thin film is dried 15 minutes in 70 DEG C in vacuum drying oven；By dry Sb2S3Pre-reaction material is thin Film forwards in the thermal station of inert gas shielding, within 7 minutes, carries out heat treatment 330 DEG C of holdings；After heat treatment terminates, membrane sample is natural It is cooled to room temperature, obtains Sb2S3Crystallization embryophoric membrane.Often complete a Sb2S3The preparation process of crystallization embryophoric membrane is a Sb2S crystallizes embryo The growth course of film.Crystallinity Sb2S3The thickness of thin film is by Sb2S3Growth course number of times (n) of crystallization embryophoric membrane controls.Repeat n= The Sb of 2 times2S3After the growth course of crystallization embryophoric membrane, obtain crystallinity Sb being deposited on FTO lining base2S3Thin film (is called for short, FTO/ Sb2S3-1.0 thin film).
(4) sign of sample:
FTO/Sb2S3The characterization result of-1.0 thin film is shown in accompanying drawing 1-3.XRD result shows, Sb in the thin film of gained2S3Belong to Rhombic form stibnite structure (JCPDS 42-1393), Sb2S3Peak crystallization very sharp-pointed, have no the existence of other impurity peaks；By This is visible, the Sb on lining base2S3Pre-reaction material there occurs chemical reaction in heat treatment process and crystallizes into Sb2S3Thin film, and Prepared Sb2S3Film layer purity and degree of crystallinity are the highest；SEM result shows, prepared crystallinity Sb2S3Thin film is the biggest Without notable pin hole or seminess in areal extent, compactness is the highest, Sb in film2S3Crystallite dimension the most greatly and mostly with thickness phase When；As n=2, crystallinity Sb of gained2S3The thickness of thin film is 280nm；Optical performance test shows, prepared crystallinity Sb2S3Thin film has EgThe band gap of=1.60eV, and absorption coefficient alpha is 0.84-in 400-650nm absorbing light wave-length coverage 1.25×105cm-1。
Embodiment 2:TiO2Crystallinity Sb on film lining base2S3The preparation of thin film
(1) cleaning of FTO electro-conductive glass: with embodiment 1.
(2)TiO2The preparation of film lining base:
Dehydrated alcohol, tetrabutyl titanate, glacial acetic acid are mixed by the volume ratio of 20:5:0.5, is made into uniform, colourless And transparent TiO2Precursor sol liquid.Then, by TiO2Precursor sol liquid be spin-coated on cleaning FTO electro-conductive glass on (2500 turns/ Minute, 30 seconds), obtain TiO2Dissolved glue film；By TiO2Dissolved glue film preserves 12 in the moisture maintainer that relative humidity is 50% at room temperature After hour, then it is placed in the Muffle furnace of air atmosphere, with the heating rate of 1 DEG C/min, the temperature of Muffle furnace is risen to 550 DEG C, and keep at such a temperature carrying out TiO in 30 minutes2The sintering of sol pellicle；After terminating, allow Muffle furnace with 1 DEG C/min Speed be cooled to room temperature, obtain TiO2Film lining base (is called for short, FTO/TiO2Thin film).
(3)SbCl3Concentration is the Sb of 1.0mol/L2S3The preparation of pre-reaction material solution: with embodiment 1.
(4)TiO2Crystallinity Sb on film lining base2S3Film preparation:
By SbCl3Concentration is the Sb of 1.0mol/L2S3Pre-reaction material solution is added drop-wise to FTO/TiO2On film lining base, quiet After putting 20 seconds, by continuous two-stage spin-coating method spin-coating film, (first order spin coating rotating speed is 1000 revs/min and spin-coating time is 10 Second；The second level rotates speed and is 2500 revs/min and spin-coating time is 30 seconds), repeat spin coating 3 times, obtain Sb2S3Pre-reaction material Thin film；By the Sb of gained2S3Pre-reaction material thin film is dried 15 minutes in 70 DEG C in vacuum drying oven；By dry Sb2S3Instead Answer precursor film to forward in the thermal station of inert gas shielding, within 7 minutes, carry out heat treatment 330 DEG C of holdings；After heat treatment terminates, Membrane sample naturally cools to room temperature, obtains Sb2S3Crystallization embryophoric membrane.Repeat the Sb of n=2 time2S3After the growth course of crystallization embryophoric membrane, Obtain being deposited on TiO2Crystallinity Sb on film lining base2S3Thin film (is called for short, FTO/TiO2/Sb2S3-1.0 thin film).
(5) sign of thin film:
FTO/TiO2The characterization result of film lining base is shown in attached Figure 4 and 5.SEM result shows, prepared TiO2Film surface Smooth, without notable pin hole or seminess in very wide area, compactness is the highest；TiO2The thickness of film layer is 90nm, TiO2 A diameter of 10-20nm of granule.XRD result shows, TiO2Film layer belongs to anatase crystal formation (JCPDS 083-2243), not See the existence of other impurity peaks.As can be seen here, prepared TiO2Film layer purity and compactness are the highest.
FTO/TiO2/Sb2S3The characterization result of-1.0 thin film is shown in accompanying drawing 6-8.XRD result shows, Sb in the thin film of gained2S3 Belong to rhombic form stibnite structure (JCPDS 42-1393), Sb2S3Peak crystallization very sharp-pointed, have no depositing of other impurity peaks ?；As can be seen here, the Sb on lining base2S3Pre-reaction material there occurs chemical reaction in heat treatment process and crystallizes into Sb2S3Thin Film, and prepared Sb2S3Film layer purity and degree of crystallinity are the highest.SEM result shows, prepared crystallinity Sb2S3Thin film exists Very free of pinholes in wide area or seminess, compactness is the highest, and Sb in film2S3Crystallite dimension the most greatly and mostly with thickness Quite；Crystallinity Sb2S3Thin film is by regular Sb2S3Crystal grain forms, and shows TiO2Surface is to Sb2S3Crystallization have induction make With；As n=2, crystallinity Sb of gained2S3The thickness of thin film is 300nm；Optical property test shows, prepared crystallinity Sb2S3Thin film has EgThe band gap of=1.65eV, and the absorption coefficient alpha in 350-650nm absorbing light wave-length coverage is 0.68- 1.31×105cm-1。
Embodiment 3:TiO2Crystallinity Sb on film lining base2S3The preparation of thin film
(1) cleaning of FTO electro-conductive glass: with embodiment 1.
(2)TiO2The preparation of film lining base: with embodiment 2.
(3)SbCl3Concentration is the Sb of 1.5mol/L2S3The preparation of pre-reaction material solution:
By SbCl under room temperature3Being dissolved in DMF, stir 0.5 hour, obtaining concentration is that 1.5mol/L is clear Clear SbCl3Solution；Then, at obtained SbCl3Solution adds thiourea, wherein SbCl3It is 1 with the mol ratio of thiourea: 1.8, under room temperature, stirring obtains the SbCl of clarification for 0.5 hour3Mixture solution with thiourea；Finally, in this mixture solution Adding glycerol, wherein the volume ratio of DMF and glycerol is 2.5:1, stirs 10 minutes, obtains SbCl3Dense Degree is the Sb of 1.5mol/L2S3Pre-reaction material solution.This Sb2S3Pre-reaction material solution is faint yellow, homogeneous transparent, and surely Fixed.
(4)TiO2Crystallinity Sb on film lining base2S3The preparation of thin film:
Utilize SbCl3Concentration is the Sb of 1.5mol/L2S3Pre-reaction material solution, at FTO/TiO2Prepare on film lining base Sb2S3Crystallize embryophoric membrane and carry out Sb2S3The growth course of crystallization embryophoric membrane；Sb2S3The preparation of crystallization embryophoric membrane and growth course are taked Method and steps with embodiment 2.Repeat the Sb of n=2 and 42S3After the growth course of crystallization embryophoric membrane, obtain being deposited on TiO2Thin Crystallinity Sb on film lining base2S3Thin film (is called for short, FTO/TiO2/Sb2S3-1.5 thin film).
(5) sign of thin film:
FTO/TiO2/Sb2S3The characterization result of-1.5 thin film is shown in accompanying drawing 9-11.XRD result shows, in the thin film of gained Sb2S3Belong to rhombic form stibnite structure (JCPDS 42-1393), Sb2S3Peak crystallization very sharp-pointed, have no other impurity peaks Existence；As can be seen here, the Sb on lining base2S3Pre-reaction material there occurs chemical reaction in heat treatment process and crystallizes into Sb2S3Thin film, and prepared Sb2S3Film layer purity and degree of crystallinity are the highest；With the increase of n, Sb2S3Peak crystallization strengthen, table Bright Sb2S3Thicknesses of layers is increasing.SEM result shows, prepared crystallinity Sb2S3Thin film is obvious in very wide area Free of pinholes or seminess, compactness is the highest, Sb in film2S3Crystallite dimension is the most greatly and mostly suitable with thickness；Crystallinity Sb2S3 Thin film is by regular Sb2S3Crystal grain forms, and shows TiO2Surface is to Sb2S3Crystallization have inducing action；With the increase of n, knot Crystalline substance Sb2S3The thickness of film layer is big, crystallinity Sb of gained as n=2 and 42S3The thickness of thin film be respectively 400nm and 590nm, shows at Sb2S3Crystallinity Sb when reactant Concentration of precursor solution is constant2S3The thickness of thin film can be by Sb2S3Crystallization embryophoric membrane Growth course number of times controls；Optical property test shows, prepared crystallinity Sb2S3Thin film is respectively provided with Eg=1.65eV and EgThe band gap of=1.70eV, the absorption coefficient alpha in 350-650nm absorbing light wave-length coverage is respectively 0.70-0.82 × 105cm-1With 0.68-0.78 × 105cm-1.It addition, from FTO/TiO2/Sb2S3-1.0 (n=2) and FTO/TiO2/Sb2S3-1.5 (n=2) Sb in sample2S3The difference of thicknesses of layers understands, crystallinity Sb2S3The thickness of thin film also can be by Sb2S3Reactant precursor liquid dense Degree controls.

Claims (6)

1. crystallinity Sb2S3The solution preparation for processing of thin film, it is characterised in that: by thiourea and SbCl under room temperature3Dissolve In the mixed organic solvents that DMF and glycerol form, obtain Sb2S3Pre-reaction material solution, by Sb2S3 Pre-reaction material solution film forming on lining base prepares Sb2S3Pre-reaction material thin film, by Sb2S3Pre-reaction material thin film Heat treatment makes Sb2S3Crystallization embryophoric membrane, passes through Sb2S3The growth course of crystallization embryophoric membrane obtains crystallinity Sb2S3Thin film.
A kind of crystallinity Sb the most according to claim 12S3The solution preparation for processing of thin film, it is characterised in that include Following steps:
(1) being dissolved in DMF by thiourea under room temperature, stir 0.5-1 hour, obtaining concentration is 0.5-2.0 The thiourea solution of mol/L clarification；Then, obtained thiourea solution adds SbCl3, wherein SbCl3Mol ratio with thiourea For 1:1.6-2, under room temperature, stirring obtains thiourea and SbCl for 0.5-1 hour3Mixture solution；Finally, in this mixture solution Adding glycerol, wherein the volume ratio of DMF and glycerol is 2-3:1, stirs 5-15 minute, obtains SbCl3 Concentration is the Sb of 1.0-1.5 mol/L2S3Pre-reaction material solution；
(2) by the Sb of gained2S3Pre-reaction material solution is added drop-wise to serve as a contrast on base, after standing the 10-30 second, with continuous two-stage spin-coating method Film forming, repeats spin coating 2-4 time, obtains Sb2S3Pre-reaction material thin film；By the Sb of gained2S3Pre-reaction material thin film is done in vacuum In dry case dry 10-20 minute in 60-80 DEG C；By dry Sb2S3Pre-reaction material thin film forwards the heat of inert gas shielding to On platform, within 5-10 minute, carry out heat treatment 300-360 DEG C of holding, obtain Sb2S3Crystallization embryophoric membrane, often completes a Sb2S3Crystallization The preparation process of embryophoric membrane is a Sb2S3The growth course of crystallization embryophoric membrane, repeated several times Sb2S3The growth course of crystallization embryophoric membrane After, obtain crystallinity Sb2S3Thin film.
A kind of crystallinity Sb the most according to claim 12S3The solution preparation for processing of thin film, it is characterised in that: described Lining base can be FTO electro-conductive glass or TiO2Thin film.
A kind of crystallinity Sb the most according to claim 22S3The solution preparation for processing of thin film, it is characterised in that: step (2) the continuous two-stage spin-coating method described in can replace with silk screen print method or scraping blade method or ink-jet printing process.
A kind of crystallinity Sb the most according to claim 22S3The solution preparation for processing of thin film, it is characterised in that: step (2) spin coating of the continuous two-stage spin-coating method described in requires: first order spin coating rotating speed is 800-1200 rev/min and spin-coating time is 10 seconds；It is 30 seconds that the second level rotates speed for 2000-3000 rev/min and spin-coating time.
A kind of crystallinity Sb the most according to claim 22S3The solution preparation for processing of thin film, it is characterised in that: step (2) the preferred nitrogen of noble gas described in.
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CN114774891A (en) * 2022-04-21 2022-07-22 南京卡巴卡电子科技有限公司 Sb2O3Thin film material and preparation of Sb based on sol-gel method2O3Method and application of thin film material

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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
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CN109037034A (en) * 2018-07-26 2018-12-18 深圳清华大学研究院 Selenizing Sb film and preparation method thereof, the solar battery using it
CN110379874A (en) * 2019-07-25 2019-10-25 中国科学技术大学 A kind of solar film battery and preparation method thereof
CN110676331A (en) * 2019-08-30 2020-01-10 中山大学 Preparation method of antimony sulfide thin film based on alcohol solvent and application of antimony sulfide thin film in solar cell
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CN111893512A (en) * 2020-08-10 2020-11-06 浙江大学 Antimony sulfide-based heterojunction photocathode and preparation method and application thereof
CN111893512B (en) * 2020-08-10 2021-08-06 浙江大学 Antimony sulfide-based heterojunction photocathode and preparation method and application thereof
CN114774891A (en) * 2022-04-21 2022-07-22 南京卡巴卡电子科技有限公司 Sb2O3Thin film material and preparation of Sb based on sol-gel method2O3Method and application of thin film material
CN114774891B (en) * 2022-04-21 2024-01-16 南京卡巴卡电子科技有限公司 Sb 2 O 3 Thin film material and Sb prepared based on sol-gel method 2 O 3 Method and use of film materials

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