CN104362218A - CIGS thin film preparation method by using supercritical fluid for low-temperature selenizing - Google Patents

CIGS thin film preparation method by using supercritical fluid for low-temperature selenizing Download PDF

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CN104362218A
CN104362218A CN201410597998.8A CN201410597998A CN104362218A CN 104362218 A CN104362218 A CN 104362218A CN 201410597998 A CN201410597998 A CN 201410597998A CN 104362218 A CN104362218 A CN 104362218A
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徐东
仁昌义
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    • H01L31/03923—Semiconductor devices sensitive to infrared 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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
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Abstract

The invention belongs to the field of photoelectric materials and provides a CIGS thin film preparation method by using supercritical fluid for low-temperature selenizing. The method includes: firstly, preparing forbidden-band-adjustable CIGS nanocrystals by a particle method, then preparing a film-coated substrate in gradient distribution by a dip-coating method, and finally, using the supercritical fluid for selenizing the film-coated substrate at a low temperature of 100-400 DEG C so as to obtain a continuous CIGS thin film. The CIGS thin film preparation method has the advantages that a process of using the supercritical fluid for low-temperature selenizing to prepare the CIGS nanocrystal thin film can be conducted at the lower temperature of 100-400 DEG C, thus, film coating performed on the flexible substrate with low bearing temperature is benefited, using high-toxic H2Se is avoided during selenizing by the supercritical fluid, and good selenizing effects can be gained and crystal boundaries can be better eliminated.

Description

The method of CIGS thin film is prepared in the selenizing of a kind of shooting flow body hypothermia
Technical field
The invention belongs to photoelectric material new energy field, particularly relate to the method that CIGS thin film is prepared in the selenizing of a kind of shooting flow body hypothermia.
Background technology
At present, due to the impact of global energy crisis, solar energy becomes the focus of alternative energy source.Copper indium sulphur (CIS) series film solar battery (comprising copper indium sulphur, copper gallium selenium, copper gallium sulphur, Copper Indium Gallium Selenide (hereinafter referred to as CIGS), copper indium gallium sulphur and copper indium gallium sulphur selenium etc.) is acknowledged as one of the most promising third generation photovoltaic material because of its outstanding photoelectric properties and structural stability.Although, the peak efficiency of current CIGS thin film solar cell is created by traditional vacuum technology 20.3%, but, due to traditional vacuum method cannot overcome cost high, high to equipment requirement, to environmental requirement harshness, poor reproducibility, the defects such as uniform large area assembly can not be produced, gradually replace by the adopting non-vacuum process of low cost.
In the past few decades, people have carried out large quantifier elimination to the adopting non-vacuum process of CIGS thin film solar cell.At present, the antivacuum preparation method of following several CIGS thin film solar cell is mainly contained:
First method is selenizing method after splash-proofing sputtering metal predecessor, and this method first on substrate, deposits layer of metal predecessor film by sputtering method, more at high temperature after selenylation reaction, formed CIGS thin film.Chinese patent CN 102386283 A utilizes glass substrate, sputter molybdenum, and sputter copper indium gallium alloy, with H 2se is selenium source (H 2s is sulphur source) afterwards selenium (sulphur) change prepared uniform CIGS thin film; Some researchers pass through in an inert atmosphere the metal precursor of sputtering sedimentation Cu-Ga-In on the glass substrate, then introduce (C 2h 5) 2Se is as selenium source selenizing at 475 ~ 515 DEG C, the efficiency of the CIGS thin film solar cell obtained reaches 13.7%(Ankur A. Kadam; Neelkanth G. Dhere. Solar Energy Materials & Solar Cells 2010,94,738).The SAS legal system of Showa Shell Solar K.K. Corp. of Japan is also similar this method for Cu-In-Ga-Se-S (CIGSS) thin-film solar cells; first sputter one deck Cu-Ga layer on the glass substrate; and then sputter one deck In layer; form CIGS thin film using selenium powder as selenium source selenylation reaction again, being finally placed in vulcanizing treatment under sulphur atmosphere, to obtain peak efficiency be that the active area of 16.0% is up to large area CIGSS thin-film solar cells (the Kushiya K of 841cm2; Kase T; Tachiyuki M; Sugiyama I; Satoh Y; Satoh M; Takeshita H. Proceedings of 25th IEEE Photovoltaic Specialists Conference, 1996,989.); But other researchers think that the rear selenizing of Cu-In-Ga metal precursor is difficult to Ga to be incorporated in CIS form single-phase quaternary CIGS, can only form the mixture film of CIS and CGS, thus can not get the higher CIGS thin film solar cell of efficiency.
Second method is electrochemical deposition method, and CIS is prepared in electro-deposition and CIGS thin film utilizes cation and anion under electric field action, different oxidation-reduction reactions occur and go out required CIS and CIGS thin film at basis material substrates.First be that a certain amount of metal precursor salt is dissolved in deionized water, then to add anion predecessor (be generally H 2seO 3), add a certain amount of complexing agent (as KCN, natrium citricum etc.), then regulate PH, form stable electrolyte, then add electrode by electrochemical oxidation-reduction precursor ions, be co-deposited on substrate and form CIGS thin film.Chinese patent CN 102629632 A discloses on the basis of a kind of cuprous sulfide of being prepared by gas-solid reaction method or copper sulfide nano nanowire arrays, and combined with electrochemical deposition process and heat treatment method, prepare CIGS nanostructure thin-film photovoltaic battery.At present, the efficiency record of electrochemical deposition CIGS thin film solar cell is close to 14%, and module efficiency also reaches 11%(Hibberd, C.J.; Chassaing, E.; Liu, W.; Mitzi, D.B.; Lincot, D.; Tiwari, A.N.. Non-vacuum methods for formation of Cu (In, Ga) (Se, S) 2 thin film photovoltaic absorbers. Prog. Photovolt. Res. Appl. 2010,18,434 – 452.).But electrochemical deposition method is difficult to form fine and close CIGS thin film, and the component of film is wayward.
The third method is sol-gel process, this method is that the organic salt of metal and selenol (mercaptan) are mixed and made into colloidal sol, adopt the method films such as spin-coating method, dip-coating method, hot spray process or ink jet printing method again, organic precursors film forms continuous print CIGS thin film through high annealing.Chinese patent CN102201495 A discloses a kind of whole soln legal system for Copper Indium Gallium Selenide (CIGS) thin-film solar cells, the CIGS active layer of CIGS solar cell makes on conductive substrates by solwution method, thickness is 0.1-10 micron, and finally under the environment of 200-1000 DEG C, high annealing forms continuous print CIGS film.
4th kind of method is " particulate method ", namely first CIGS nano powder is prepared, prepare CIGS again and receive brilliant ink, and then adopt the method films such as spin-coating method, dip-coating method, hot spray process or ink jet printing method, predecessor selenized annealing at 450-550 DEG C forms continuous print CIGS thin film.Chinese patent CN101944556 A uses the copper of variable grain size, indium, gallium, selenium or their binary, ternary or quaternary alloy nano particle to make marking ink, use simple multilayer spray printing method to prepare thin-film solar cells CuInGaSe absorbed layer, and adopt rapid thermal treatment to the uniformity of the grainiess and film forming that improve film.Some researchers under an inert atmosphere; TBP(tributylphosphine is injected by heat in the oleyl amine solution of metal precursor): Se solution; it is nanocrystalline that temperature reaction certain hour forms copper indium diselenide (CIS); purified dispersion is again made CIS and is received brilliant ink, then the peak efficiency of the CIS absorbed layer thin-film solar cells made through hot spray process film is 3.1%(V.A. Akhavan; M.G. Panthani; B.W. Goodfellow; D.K. Reid; B.A. Korgel, Energy Express 2010,18, A411 – A420.).This method Problems existing is that CIGS receives the brilliant particle surfactant that CIGS receives on brilliant particle in traditional selenizing atmosphere and not easily removes, and easily between crystal boundary, carbon remains, and causes not easily forming larger CIGS particle and forming continuous print CIGS thin film.
At present, CIGS/CIS/CGS/CIGSS film all will carry out selenized annealing process usually, and through the film of selenized annealing process, often transformation efficiency is not poor.Traditional selenized annealing process selenizing temperature higher (400 ~ 550 DEG C), selenium source is probably divided into two kinds: one to be the selenizing of simple substance Se powder evaporation Se steam; Two is adopt H 2se selenizing, Se steam toxicity is little, but effect is poor; And H 2though Se selenizing effect is good, H 2se is high malicious, inflammable and explosive.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, provide a kind of preparation technology simple, be easy to the method that the selenizing of industrialized shooting flow body hypothermia prepares CIGS thin film.
The present invention is achieved in that the method for CIGS thin film is prepared in the selenizing of a kind of shooting flow body hypothermia, comprises the steps:
Add in alkylamine after stannous chloride, inidum chloride, gallium chloride are mixed with selenium powder and react, obtain CIGS nanocrystalline;
Nanocrystalline for described CIGS to mix with organic dissolution is disperseed, obtains the nanocrystalline ink of CIGS, substrate is immersed in the nanocrystalline ink of described CIGS, and Best-Effort request carries out film, after drying, obtain film substrate;
Described film substrate is separated with supercritical fluid solution and is placed in closed environment, heat treated, described supercritical fluid solution evaporation formation supercritical fluid is fully contacted with film substrate and carries out selenylation reaction, obtain CIGS thin film.
Particularly, preparing the nanocrystalline concrete grammar of described CIGS is:
In an inert atmosphere, alkylamine is added after stannous chloride, inidum chloride and gallium chloride being mixed with selenium powder, obtain mixture, except anhydrating and oxygen, after being warming up to 220 ~ 300 DEG C of lower reaction 1 ~ 4h of stirring, being cooled to room temperature, obtaining suspension, separating-purifying is carried out to described suspension, obtains CIGS nanocrystalline.
Particularly, in the step that preparation CIGS is nanocrystalline, described alkylamine is one or more in toluene, hexyl mercaptan, dimethylbenzene, n-hexane, benzene, pyridine.
Particularly, described organic solution is benzene or hexyl mercaptan.
Particularly, in the step preparing film substrate, described CIGS is nanocrystalline is (0.1 ~ 2) g with the proportioning of organic solvent: (10 ~ 100) mL.
Particularly, in the step preparing film substrate, the speed that described Best-Effort request carries out film is 0.5 ~ 15cm/min.
Particularly, in the step of preparation CIGS thin film, described supercritical fluid solution is one or more the mixing in methyl-hydroselenide, ethyl selenomercaptan, benzene selenol.
Particularly, in the step of preparation CIGS thin film, the concentration of described supercritical fluid solution is 1 ~ 50mmol/L.
Particularly, in the step of preparation CIGS thin film, the temperature of described heat treated is 100 ~ 400 DEG C.
The invention provides the method that CIGS thin film is prepared in the selenizing of a kind of shooting flow body hypothermia, the method first uses particulate legal system nanocrystalline for the CIGS that forbidden band is adjustable, the film substrate of gradient distribution is prepared again by dip-coating method, finally utilize supercritical fluid selenization film substrate under the low temperature of 100 ~ 400 DEG C, obtain continuous print CIGS thin film.This preparation method's raw material is easy to get, technique simple, be easy to industrialization, the shooting flow body hypothermia selenidation process of CIGS nano-crystal thin-film prepared by the method can carry out under the low temperature of 100 ~ 400 DEG C, like this, be conducive to plated film on the flexible base, board of low bearing temperature, and the H using high poison is avoided in supercritical fluid selenizing 2se simultaneously, can obtain good selenizing effect and eliminate crystal boundary better, thus obtaining continuous print CIGS thin film.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, be briefly described to the accompanying drawing used required in embodiment below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is that preparation CIGS that the embodiment of the present invention provides receives brilliant ink flow chart.
Fig. 2 is the Best-Effort request film operational flowchart that the embodiment of the present invention provides.
The overcritical selenylation reaction device schematic diagram that Fig. 3 provides for the embodiment of the present invention.
ESEM (SEM) figure of overcritical selenizing low-temperature growth CIGS nano-crystal thin-film of Fig. 4 for providing in the embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described.
Embodiments provide the method that CIGS thin film is prepared in the selenizing of a kind of shooting flow body hypothermia, its preparation method is shown in Figure 1.The method that CIGS thin film is prepared in this shooting flow body hypothermia selenizing comprises the following steps:
S01. add in alkylamine after stannous chloride, inidum chloride, gallium chloride being mixed with selenium powder and react, obtain CIGS nanocrystalline;
S02. by nanocrystalline for CIGS on substrate film: nanocrystalline for described CIGS to mix with organic solvent is disperseed, obtains the nanocrystalline ink of CIGS, substrate is immersed in the nanocrystalline ink of described CIGS, and Best-Effort request carries out film, after drying, obtain film substrate;
S03. the substrate having CIGS nanocrystalline film carries out selenization: described film substrate is separated being placed in closed environment with supercritical fluid solution, heat treated, described supercritical fluid solution evaporation formation supercritical fluid is fully contacted with film substrate and carries out selenylation reaction, obtain CIGS thin film.
Particularly, in above-mentioned steps S01, the nanocrystalline preparation of described CIGS can adopt the existing method in this area, comprises raw material, proportioning and operating parameter.
It is nanocrystalline that embodiment of the present invention employing prepares CIGS with the method for stannous chloride, inidum chloride, gallium chloride, selenium powder and alkylamine.The order of addition of above-mentioned stannous chloride, inidum chloride, gallium chloride, selenium powder and alkylamine is unrestricted, can be inject alkylamine after adding stannous chloride, inidum chloride, gallium chloride, selenium powder successively, also the mixture of stannous chloride, inidum chloride, gallium chloride, selenium powder can be mixed with alkylamine.As concrete preferred embodiment, the copper in described stannous chloride, inidum chloride, gallium chloride, selenium powder, indium, gallium are (0.4 ~ 0.7) mmol:10ml with the amount of substance sum of selenium element and the ratio of the volume of alkylamine.Wherein, described alkylamine is preferably a kind of or arbitrary proportion mixing several of oleyl amine, 1-butylamine, isobutyl amine, dibutyl amine, tri-n-butylamine, ethylenediamine, propane diamine, octadecylamine, dimethyl dodecylamine, hexadecylamine, but is not limited thereto.More preferably, described alkylamine is oleyl amine.
In CIGS film, the ratio of stannous chloride, inidum chloride, gallium chloride directly can affect the application performance of film, thus impact is with the conversion efficiency of the solar cell of this CIGS film preparation.In the embodiment of the present invention, the usage ratio of described stannous chloride, inidum chloride, gallium chloride can carry out choice and optimization according to existing particulate method, the CIGS that preparation forbidden band is adjustable is nanocrystalline, this CIGS is nanocrystalline after following step S02, S03 process, finally can prepare the CIGS film of gradient distribution, significantly improve CIGS thin-film solar cells efficiency.
In this step S01, as preferred embodiment, stannous chloride of the present invention, inidum chloride, gallium chloride and selenium powder react in alkylamine to be prepared the nanocrystalline concrete operations of CIGS and is:
In an inert atmosphere, alkylamine is added after stannous chloride, inidum chloride and gallium chloride being mixed with selenium powder, obtain mixture, except anhydrating and oxygen, after being warming up to 220 ~ 300 DEG C of lower reaction 1 ~ 4h of stirring, being cooled to room temperature, obtaining suspension, separating-purifying is carried out to described suspension, obtains CIGS nanocrystalline.
In aforesaid operations, in order to prevent reactant from oxidation or other side reactions occurring, need carry out isolated air-treatment to aforesaid operations system, the mode of isolated air can adopt carries out in an inert atmosphere, and wherein inert atmosphere is for containing N 2or the environment that other inert gases are full of, meanwhile, need to remove the water existed in reaction system and oxygen.
Described except to anhydrate and the method for oxygen comprises vacuumizing and operates with bubbling, vacuumize and can repeat with bubbling, thus the water fully removed in reaction system and oxygen, particularly, carry out at being included in 60 ~ 100 DEG C except anhydrating with the operation of oxygen, vacuum degree is-0.01 ~-0.1MPa, and the time is 1 ~ 3h, then under stirring condition in 100 ~ 130 DEG C of logical bubbling inert gas 1 ~ 3h.
In the embodiment of the present invention, in the preparation process that described preferred CIGS is nanocrystalline, nanocrystalline in order to obtain highly purified CIGS, separating-purifying process can be carried out to suspension obtained in step S01.As concrete preferred embodiment, the present invention adopts and carry out separation and purification to gained suspension under room temperature or low temperature environment, to remove the impurity in product except CIGS is nanocrystalline, comprise byproduct of reaction, unreacted raw material etc., concrete operations are: products therefrom precipitation reagent after cooling and dispersant are repeated the operation of precipitation-dispersing and dissolving, number of repetition is after 1-4 time, and the sediment obtained is carried out centrifugation, get lower sediment and carry out drying process, obtain CIGS nanocrystalline.Described precipitation-dispersing and dissolving operation comprises precipitation and dispersing and dissolving two steps, particularly, precipitation reagent made by the ethanol adding 1 ~ 50mL in above-mentioned suspension, centrifugal 1 ~ 10min under 10000rpm, outwell supernatant, sediment adds 1 ~ 50mL dispersant, then under 10000rpm centrifugal one minute, supernatant is poured in the clean centrifuge tube of another and continue to employ, abandon sediment; Again ethanol is dropwise joined in supernatant until stillness of night change is muddy, centrifugal 1 ~ 10min under 10000rpm again, outwell supernatant, sediment is dissolved in dispersant again, add as far as possible few ethanol again, last with centrifugation again, outwell supernatant, finally sediment is placed in vacuum drying chamber at 100 ~ 200 DEG C, dries that to obtain pure CIGS nanocrystalline.Wherein, the operating parameter in described precipitation-dispersing and dissolving step is unrestricted, preferably, described centrifugal be centrifugal 1 ~ 10min under 10000rpm/min condition.Described precipitation reagent is do not dissolve the nanocrystalline polar organic solvent of CIGS, the embodiment of the present invention is preferably the mixing of one or more in methyl alcohol, ethanol, acetone, isopropyl alcohol, chloroform, mixed proportion is arbitrary proportion, the consumption of described precipitation reagent can adjust for the consumption of raw material and actual conditions, rear without till Precipitation to add.Described dispersant is non-polar solven, the embodiment of the present invention is preferably one or both the mixture in toluene, hexyl mercaptan, dimethylbenzene, n-hexane, mixed proportion is arbitrary proportion, the consumption of described dispersing and dissolving can adjust for the consumption of raw material and actual conditions, to add till postprecipitation no longer dissolves.In above-mentioned purification process; the method of described drying process is unrestricted; the nanocrystalline drying means of CIGS is can be used for all in protection scope of the present invention in this area; as concrete preferred embodiment; dry process is preferably vacuumize; baking temperature is 100 ~ 200 DEG C, and drying time is 1 ~ 24h.
As preferred embodiment, S01 of the present invention prepares the nanocrystalline concrete steps of CIGS for (shown in accompanying drawing 1): be dissolved in oleyl amine by stannous chloride, inidum chloride, gallium chloride and selenium, continue to vacuumize 1h after being heated to 100 DEG C, then respectively with 130 DEG C after logical nitrogen bubble 1h, 220 DEG C of logical nitrogen bubble 4h, obtain CIGS head product, obtain CIGS through separation and purification nanocrystalline.
In above-mentioned steps S02, in order to be uniformly dispersed, stable dispersion, described CIGS is nanocrystalline is (0.1 ~ 2) g with the proportioning of organic solvent: (10 ~ 100) mL, obtain after mixing that CIGS is nanocrystalline is dispersed in organic solvent the dispersion forming similar ink, be namely called the nanocrystalline ink of CIGS.Wherein, as preferred embodiment, organic solution described in the embodiment of the present invention is benzene or hexyl mercaptan.
As preferred embodiment, after the ultrasonic process of nanocrystalline for CIGS ink, then carry out film, the power of described ultrasonic process is 100 ~ 600W, and the time is 1 ~ 20min.
In this step, the described dip-coating method coating method that film can adopt the art conventional on substrate, adopt the concrete operations of dip-coating method as described in Fig. 2, wherein dip time is 1 ~ 15min, and the rate of pulling is (0.5 ~ 15) cm/min.After film, drying obtains film substrate.Certainly, be understandable that, in this step, described on substrate film also can adopt other conventional coating methods of the art, such as spin-coating method, hot spray process or ink jet printing method etc.
In order to obtain, thickness is suitable, the CIGS film of function admirable, preparation CIGS film often carries out repeatedly film-drying process according to actual needs, to obtain the CIGS film of expection thickness, improve the photoelectric conversion efficiency of CIGS hull cell, thus realize needing with optimizing the property regulation of CIGS film and solar cell.Wherein, described film substrate is unrestricted, and this area is all available for the preparation of the substrate of thin-film solar cells, as specific embodiment, be preferably glass, pottery, metal, plastic base, comprise flexible base, board, it is of a size of the stock size of substrate, as 1cm × 1.5cm.Preferably, through cleaning before described substrate uses, the cleaning method of glass substrate is for use acetone, ethanol and deionized water ultrasonic cleaning 1 ~ 20min successively, and ultrasonic power is 300 ~ 600w.
In above-mentioned steps S02, in order to remove the organic solvent in film substrate, need the film substrate after to film to carry out drying process, as concrete preferred embodiment, described baking temperature is preferably 100 ~ 300 DEG C, and drying time is dry 1 ~ 30min.In order to realize stannous chloride, inidum chloride, gallium chloride fully mix with selenium powder mixed solution, needs to carry out stir process to above-mentioned mixed solution, wherein preferred magnetic agitation.
As preferred embodiment, described S02 by nanocrystalline for CIGS on substrate the concrete steps of film be (see shown in accompanying drawing 2): after soda glass being cut into the substrate of 1cm × 1.5cm size, for subsequent use after using acetone, ethanol, washed with de-ionized water 20min respectively, with Best-Effort request coating method, nanocrystalline for CIGS ink film is formed CIGS wet film on aforesaid substrate, film again after to be dried, obtains film substrate after repeating film-drying several.
In above-mentioned steps S03, in the step of described selenylation reaction, preferably, described supercritical fluid is one or more or more than one the mixing in methyl-hydroselenide, ethyl selenomercaptan, benzene selenol, but is actually not limited thereto, and mixed proportion is arbitrary proportion.
Preferably, described shooting flow bulk concentration is (1 ~ 50) mmol/L.The consumption of described supercritical fluid should adjust according to the amount of reality nanocrystalline ink of the CIGS of film on substrate, with abundant selenizing for target, in specific embodiment, for the film substrate obtaining stock size after carrying out a film, the consumption of supercritical fluid is 1 ~ 10mL, and the volume of closed environment is 10 ~ 100 times of supercritical fluid volume.Make shooting flow evacuator body formation supercritical fluid contact with the substrate scribbling the nanocrystalline ink of CIGS thus and selenylation reaction occurs, thus obtain fine and close CIGS nano-crystal thin-film at a lower temperature.
In specific embodiment, described film substrate and supercritical fluid have to be placed and can carry out according to the device shown in Fig. 3 in closed environment: the substrate scribbling the nanocrystalline ink of CIGS of drying is placed in a glass-lined, then this glass-lined is put into the stainless steel cauldron that another band polytetrafluoroethyllining lining is larger than described glass-lined, space is left between glass-lined and band polytetrafluoroethyllining lining, to adding the certain density supercritical fluid of 1 ~ 10mL between glass-lined and polytetrafluoro liner, ensure that the substrate scribbling the nanocrystalline ink of CIGS does not contact with supercritical fluid.
In above-mentioned steps S03, in order to the steam and film substrate that make supercritical fluid are abundant, even contact, no matter how film substrate and supercritical fluid are placed, all need both guarantees not contact, and the evaporation of supercritical fluid is unrestricted, ensures that film substrate can fully contact with the steam of supercritical fluid, do not covered because of other factors or stopped, such as, require that the band polytetrafluoroethyllining lining of splendid attire supercritical fluid is not airtight or part is not airtight, avoid causing evaporation to have some setbacks.Described glass-lined is put and material with teflon-lined stainless steel cauldron is the conventional high temperature resistant material in this area, and does not react with supercritical fluid, as glass, polytetrafluoroethylene etc.
The reaction temperature of the selenylation reaction in this step S03 is 100 ~ 400 DEG C, and the reaction time is 1 ~ 24h, can regulate according to the amount of real reaction thing.Described selenylation reaction can be described as steam induction selenizing, in course of reaction, supercritical fluid evaporates the gas-liquid mixed steam being formed and have uniform temperature and pressure in the closed environment of a constant volume, contacts selenylation reaction occurs with the CIGS nano-crystal film on film substrate.Wherein, the organic solvent used in supercritical fluid can dissolve the ligand oleyl amine in CIGS precursor film in temperature-rise period, thus eliminate antivacuum legal system in the past for the residual defect of carbon in CIGS thin film solar cell, meanwhile, utilize supercritical fluid selenizing to avoid using the H of high poison 2se achieves good selenizing effect simultaneously, this is because in supercritical fluid, due to the booster action of liquid phase, the reaction on CIGS predecessor film is faster and better compared to traditional dry method selenizing, likely better eliminate crystal boundary, form continuous print monocrystalline CIGS thin film.
Compared with the prior art, tool of the present invention has the following advantages and beneficial effect:
1) this preparation method can obtain adjustable nanocrystalline in forbidden band in particulate method, can prepare the CIGS thin film of gradient distribution, thus significantly improves CIGS thin film solar battery efficiency;
2) the CIGS thin film solar cell prepared under this preparation method, the organic solvent used in supercritical fluid can dissolve the ligand oleyl amine in CIGS precursor film in temperature-rise period, thus eliminates antivacuum legal system in the past for the residual defect of carbon in CIGS thin film solar cell;
3) CIGS thin film prepared of the method, utilizes supercritical fluid selenizing to avoid using the H of high poison 2se achieves good selenizing effect simultaneously, this is because in supercritical fluid, due to the booster action of liquid phase, the reaction on CIGS predecessor film is faster and better compared to traditional dry method selenizing, likely better eliminate crystal boundary, form continuous print monocrystalline CIGS thin film.
Illustrate that the method for CIGS thin film is prepared in the selenizing of above-mentioned shooting flow body hypothermia below by way of multiple embodiment.
Embodiment 1
A method for CIGS thin film is prepared in the selenizing of shooting flow body hypothermia, comprises the steps:
(1) preparation that CIGS is nanocrystalline: at rich N 2glove box in, take 10mmolCuCl, 7mmolInCl 3, 3mmolGaCl 3the 250mL there-necked flask of a band condenser pipe and piston is placed in 20mmol Se; After closure piston, device is shifted out glove box, immediately the piston mouth of device is connected with history Ranque tube.Flask is wrapped with silica wool and is placed in heating collar, then the oleyl amine of 100ml is injected in flask.Open piston and at 100 DEG C, vacuumize 1h to remove water in device and oxygen; Following reaction thing is at N 2at 130 DEG C of lower magnetic force stirring reaction 1h under bubbling.Then be warming up to 220 DEG C, under strong stirring, react 4h, then heating collar is removed, reactant is cooled to room temperature.
The concrete operations of separating-purifying are: precipitation reagent made by the ethanol adding 50mL in above-mentioned suspension, centrifugal 10min under 10000rpm, outwell supernatant, sediment adds the dispersion of 50mL toluene, under 10000rpm centrifugal one minute again, supernatant is poured in the clean centrifuge tube of another and continue to employ, abandon sediment; Again ethanol is dropwise joined in supernatant until stillness of night change is muddy, centrifugal 10min under 10000rpm again, outwell supernatant, sediment is dissolved in toluene again, add as far as possible few ethanol again, last with centrifugation again, outwell supernatant, finally sediment is placed in vacuum drying chamber at 100 DEG C, dries that to obtain pure CIGS nanocrystalline.
(2) prepare the nanocrystalline ink of CIGS and film: nanocrystalline by CIGS is 2g: 100mL with the proportioning of toluene, choose the nanocrystalline and toluene of CIGS, join in toluene by nanocrystalline for CIGS, mix, obtain the nanocrystalline ink of CIGS.
The beaker of nanocrystalline for CIGS ink is positioned in ultrasonic device, ultrasonic process 20min.
Under the nanocrystalline ink of CIGS after ultrasonic is placed in Best-Effort request machine, select glass to be substrate, size is 1cm × 1.5cm simultaneously, and thickness is 1mm; Cleaned glass substrate is clipped on the fixture of Best-Effort request machine, slowly extend in the nanocrystalline ink of CIGS, stop when glass substrate reaches below liquid level 1cm, substrate is soaked 15 min in the nanocrystalline ink of CIGS, and substrate is shifted out solution by the speed with 0.5cm/min after terminating.
Then be that the electric hot plate of 120 DEG C is dried, to remove toluene at design temperature by the substrate scribbling the nanocrystalline ink of CIGS.
The substrate scribbling the nanocrystalline ink of CIGS of drying is placed in a glass-lined, then this liner is put into the stainless steel cauldron that another band polytetrafluoroethyllining lining is larger than described glass-lined.
(3) CIGS thin film Making programme is as follows: stainless steel cauldron structure as shown in Figure 3, to the supercritical fluid solution adding 10mL 50mmol/L between glass-lined and polytetrafluoro liner, ensure that the substrate scribbling the nanocrystalline ink of CIGS does not contact with supercritical fluid solution.
After reactor is sealed, reactor is put into baking oven and be heated to 100 DEG C, keep 24 hours, supercritical fluid solution evaporation formation supercritical fluid is contacted with the substrate scribbling the nanocrystalline ink of CIGS selenylation reaction occurs, thus obtain the CIGS thin film of densification as shown in Figure 4 at a lower temperature.
Embodiment 2
A method for CIGS thin film is prepared in the selenizing of shooting flow body hypothermia, comprises the steps:
(1) preparation that CIGS is nanocrystalline: at rich N 2glove box in, take 2mmolCuCl, 0.18mmolInCl 3, 0.2mmolGaCl 3the 100mL there-necked flask of a band condenser pipe and piston is placed in 4mmolSe; After closure piston, device is shifted out glove box, immediately the piston mouth of device is connected with history Ranque tube.Flask is wrapped with silica wool and is placed in heating collar, then the oleyl amine of 10ml is injected in flask.Open piston and at 100 DEG C, vacuumize 1h to remove water in device and oxygen; Following reaction thing is at N 2at 130 DEG C of lower magnetic force stirring reaction 1h under bubbling.Then be warming up to 220 DEG C, under strong stirring, react 3h, then heating collar is removed, reactant is cooled to room temperature.
The concrete operations of separating-purifying are: precipitation reagent made by the ethanol adding 10mL in above-mentioned suspension, centrifugal 10min under 10000rpm, outwell supernatant, sediment adds the dispersion of 10mL toluene, under 10000rpm centrifugal one minute again, supernatant is poured in the clean centrifuge tube of another and continue to employ, abandon sediment; Again ethanol is dropwise joined in supernatant until stillness of night change is muddy, centrifugal 5min under 10000rpm again, outwell supernatant, sediment is dissolved in toluene again, add as far as possible few ethanol again, last with centrifugation again, outwell supernatant, finally sediment is placed in vacuum drying chamber at 100 DEG C, dries that to obtain pure CIGS nanocrystalline.
Nanocrystalline by CIGS is 0.1g: 10mL with the proportioning of toluene, chooses the nanocrystalline and toluene of CIGS, joins in toluene, mix, obtain the nanocrystalline ink of CIGS by nanocrystalline for CIGS.
The beaker of nanocrystalline for CIGS ink is positioned in ultrasonic device, ultrasonic process 10min;
Under the nanocrystalline ink of CIGS after ultrasonic is placed in Best-Effort request machine, select glass to be substrate, size is 1cm × 1.5cm simultaneously, and thickness is 1mm; Cleaned glass substrate is clipped on the fixture of Best-Effort request machine, slowly extend in the nanocrystalline ink of CIGS, stop when glass substrate reaches below liquid level 1cm, substrate is soaked 51min in the nanocrystalline ink of CIGS.Substrate is shifted out solution by the speed with 15cm/min after end.
Then be that the electric hot plate of 120 DEG C is dried, to remove toluene at design temperature by the substrate scribbling the nanocrystalline ink of CIGS.
The substrate scribbling the nanocrystalline ink of CIGS of drying is placed in a glass-lined, then this liner is put into the stainless steel cauldron that another band polytetrafluoroethyllining lining is larger than described glass-lined;
(3) CIGS thin film Making programme is as follows: stainless steel cauldron structure as shown in Figure 3, to the supercritical fluid solution adding 10mL 50mmol/L between glass-lined and polytetrafluoro liner, ensure that the substrate scribbling the nanocrystalline ink of CIGS does not contact with supercritical fluid solution.
After reactor is sealed, reactor is put into baking oven and be heated to 100 DEG C, keep 24 hours, supercritical fluid solution evaporation formation supercritical fluid is contacted with the substrate scribbling the nanocrystalline ink of CIGS selenylation reaction occurs, thus obtain the CIGS nano-crystal thin-film of densification as shown in Figure 4 at a lower temperature.
Embodiment 3
A method for CIGS nano-crystal thin-film is prepared in the selenizing of shooting flow body hypothermia, and it comprises the steps:
1) preparation that CIGS is nanocrystalline: at rich N 2glove box in, take 0.1mmolCuCl, 10mmolInCl 3, 10mmolGaCl 3the 100mL there-necked flask of a band condenser pipe and piston is placed in 0.2mmolSe; After closure piston, device is shifted out glove box, immediately the piston mouth of device is connected with history Ranque tube.Flask is wrapped with silica wool and is placed in heating collar, then the oleyl amine of 10ml is injected in flask.Open piston and at 100 DEG C, vacuumize 2h to remove water in device and oxygen; Following reaction thing is at N 2at 130 DEG C of lower magnetic force stirring reaction 2h under bubbling.Then be warming up to 220 DEG C, under strong stirring, react 1h, then heating collar is removed, reactant is cooled to room temperature.
The concrete operations of separating-purifying are: precipitation reagent made by the ethanol adding 20mL in above-mentioned suspension, centrifugal 10min under 10000rpm, outwell supernatant, sediment adds the dispersion of 20mL toluene, under 10000rpm centrifugal one minute again, supernatant is poured in the clean centrifuge tube of another and continue to employ, abandon sediment; Again ethanol is dropwise joined in supernatant until stillness of night change is muddy, centrifugal 10min under 10000rpm again, outwell supernatant, sediment is dissolved in toluene again, add as far as possible few ethanol again, last with centrifugation again, outwell supernatant, finally sediment is placed in vacuum drying chamber at 100 DEG C, dries that to obtain pure CIGS nanocrystalline.
(2) prepare the nanocrystalline ink of CIGS and film: nanocrystalline by CIGS is 1g: 60mL with the proportioning of toluene, choose the nanocrystalline and toluene of CIGS, join in toluene by nanocrystalline for CIGS, mix, obtain the nanocrystalline ink of CIGS.
The beaker of nanocrystalline for CIGS ink is positioned in ultrasonic device, ultrasonic process 1min.
Under the nanocrystalline ink of CIGS after ultrasonic is placed in Best-Effort request machine, select glass to be substrate, size is 1cm × 1.5cm simultaneously, and thickness is 1mm; Cleaned glass substrate is clipped on the fixture of Best-Effort request machine, slowly extend in the nanocrystalline ink of CIGS, stop when glass substrate reaches below liquid level 1cm, substrate is soaked 3 min in the nanocrystalline ink of CIGS.Substrate is shifted out solution by the speed with 2cm/min after end.
Then be that the electric hot plate of 120 DEG C is dried, to remove toluene at design temperature by the substrate scribbling the nanocrystalline ink of CIGS.
(3) CIGS thin film Making programme is as follows: stainless steel cauldron structure as shown in Figure 3, the substrate scribbling the nanocrystalline ink of CIGS of drying is placed in a glass-lined, then this liner is put into the stainless steel cauldron that another band polytetrafluoroethyllining lining is larger than described glass-lined.
To the supercritical fluid solution adding 8mL 10mmol/L between glass-lined and polytetrafluoro liner, ensure that the substrate scribbling the nanocrystalline ink of CIGS does not contact with supercritical fluid solution.
After reactor is sealed, reactor is put into baking oven and be heated to 300 DEG C, keep 12 hours, supercritical fluid solution evaporation formation supercritical fluid is contacted with the substrate scribbling the nanocrystalline ink of CIGS selenylation reaction occurs, thus obtain the CIGS nano-crystal thin-film as Fig. 4 densification at a lower temperature.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (9)

1. a method for CIGS thin film is prepared in the selenizing of shooting flow body hypothermia, it is characterized in that, comprises the following steps:
Add in alkylamine after stannous chloride, inidum chloride, gallium chloride are mixed with selenium powder and react, obtain CIGS nanocrystalline;
Nanocrystalline for described CIGS to mix with organic solvent is disperseed, obtains the nanocrystalline ink of CIGS, substrate is immersed in the nanocrystalline ink of described CIGS, and Best-Effort request carries out film, after drying, obtain film substrate;
Described film substrate is separated with supercritical fluid solution and is placed in closed environment, heat treated, described supercritical fluid solution evaporation formation supercritical fluid is fully contacted with film substrate and carries out selenylation reaction, obtain CIGS thin film.
2. the method for CIGS thin film is prepared in shooting flow body hypothermia according to claim 1 selenizing, it is characterized in that, prepares the nanocrystalline concrete grammar of described CIGS to be:
In an inert atmosphere, alkylamine is added after stannous chloride, inidum chloride and gallium chloride being mixed with selenium powder, obtain mixture, except anhydrating and oxygen, after being warming up to 220 ~ 300 DEG C of lower reaction 1 ~ 4h of stirring, being cooled to room temperature, obtaining suspension, separating-purifying is carried out to described suspension, obtains CIGS nanocrystalline.
3. the method for CIGS thin film is prepared in shooting flow body hypothermia according to claim 1 selenizing, it is characterized in that, in the step that preparation CIGS is nanocrystalline, described alkylamine is one or more in toluene, hexyl mercaptan, dimethylbenzene, n-hexane, benzene, pyridine.
4. the method for CIGS thin film is prepared in shooting flow body hypothermia according to claim 1 selenizing, it is characterized in that, in the step preparing film substrate, described organic solution is benzene or hexyl mercaptan.
5. the method for CIGS thin film is prepared in shooting flow body hypothermia according to claim 1 selenizing, it is characterized in that, in the step preparing film substrate, described CIGS is nanocrystalline is (0.1 ~ 2) g with the proportioning of organic solvent: (10 ~ 100) mL.
6. the method for CIGS thin film is prepared in shooting flow body hypothermia according to claim 1 selenizing, it is characterized in that, in the step preparing film substrate, the speed that described Best-Effort request carries out film is 0.5 ~ 15cm/min.
7. the method for CIGS thin film is prepared in shooting flow body hypothermia according to claim 1 selenizing, it is characterized in that, in the step of preparation CIGS thin film, described supercritical fluid solution is one or more the mixing in methyl-hydroselenide, ethyl selenomercaptan, benzene selenol.
8. the method for CIGS thin film is prepared in shooting flow body hypothermia according to claim 1 selenizing, it is characterized in that, in the step of preparation CIGS thin film, the concentration of described supercritical fluid solution is 1 ~ 50mmol/L.
9. the method for CIGS thin film is prepared in shooting flow body hypothermia according to claim 1 selenizing, it is characterized in that, in the step of preparation CIGS thin film, the temperature of described heat treated is 100 ~ 400 DEG C.
CN201410597998.8A 2014-10-31 2014-10-31 CIGS thin film preparation method by using supercritical fluid for low-temperature selenizing Pending CN104362218A (en)

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