CN106000705B - A kind of full-automatic Pulse Spraying device and spraying method being used to prepare film - Google Patents
A kind of full-automatic Pulse Spraying device and spraying method being used to prepare film Download PDFInfo
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- CN106000705B CN106000705B CN201610545198.0A CN201610545198A CN106000705B CN 106000705 B CN106000705 B CN 106000705B CN 201610545198 A CN201610545198 A CN 201610545198A CN 106000705 B CN106000705 B CN 106000705B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/02—Spray pistols; Apparatus for discharge
- B05B7/04—Spray pistols; Apparatus for discharge with arrangements for mixing liquids or other fluent materials before discharge
- B05B7/0416—Spray pistols; Apparatus for discharge with arrangements for mixing liquids or other fluent materials before discharge with arrangements for mixing one gas and one liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B13/00—Machines or plants for applying liquids or other fluent materials to surfaces of objects or other work by spraying, not covered by groups B05B1/00 - B05B11/00
- B05B13/02—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work
- B05B13/0278—Arrangement or mounting of spray heads
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/02—Spray pistols; Apparatus for discharge
- B05B7/12—Spray pistols; Apparatus for discharge designed to control volume of flow, e.g. with adjustable passages
- B05B7/1209—Spray pistols; Apparatus for discharge designed to control volume of flow, e.g. with adjustable passages the controlling means for each liquid or other fluent material being manual and interdependent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0218—Pretreatment, e.g. heating the substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- Engineering & Computer Science (AREA)
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- Application Of Or Painting With Fluid Materials (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The present invention provides a kind of full-automatic Pulse Spraying devices and spraying method being used to prepare film.The device includes spray gun, air pump, controller, container and heating plate.Spray gun is placed vertically, and upper part is the body of a gun, and lower end is nozzle；Air pump is connected by gas-guide tube with the body of a gun of spray gun, for providing high-pressure working gas into spray gun body；Air valve switch is equipped on gas-guide tube；Controller is used to control the open and close of air valve switch, and high-pressure working gas is provided into spray gun body to control air pump；Container is for holding precursor liquid；Heating plate is for heating substrate thereon；Under the action of high-pressure working gas, the precursor liquid in container can be entered in the body of a gun of spray gun and is atomized by catheter, be finally sprayed on high temperature substrate by nozzle.The present invention only need to be good by each parameter setting, so that it may automatic running voluntarily stops, and convenience and high-efficiency is easy to operate, and can prepare large area, thickness is controllable, film of even compact.
Description
Technical field
The present invention relates to the preparing technical field of film, specifically a kind of full-automatic pulse spray being used to prepare film
Coating device and spraying method.
Background technology
Copper zinc tin sulfur selenium（Cu2ZnSn(S1-xSex)4, write a Chinese character in simplified form：CZTSSe）Because its environmental-friendly characteristic, the abundant earth's crust contain
Amount and the good characteristics such as good photoelectric properties and the extensive concern for being increasingly subject to people.The energy gap of CZTSSe is 1.5
Best energy gap required by eV, with semiconductor solar cell is coincide, and it is direct band-gap semicondictor, is had larger
The absorption coefficient of light（>104cm-1）, therefore required CZTSSe absorber thickness is smaller in solar cells, greatly reduces group
The size of part.Since it possesses many excellent characteristics, within short several years, CZTSSe film photovoltaic technologies are rapidly sent out
Exhibition, the photoelectric conversion efficiency of battery were increased to 6.7% in 2008 from 0.66% in 1996, then to Solar in 2013
The 12.6% of Frontier companies.But since CZTSSe is multi-element compounds, stoichiometry is more difficult to control, stoichiometric ratio
Control it is bad just easily generate binary, ternary it is miscellaneous, such as：Cu2S、ZnS、SnS、SnS2、Cu2SnS3Deng being unfavorable for battery
Photoelectric properties.
Currently, the preparation method of CZTSSe has vacuum method and antivacuum method.Vacuum method includes mainly thermal evaporation, electron beam
Evaporation, sputtering method, molecular beam epitaxy etc..These technologies need harsh film growth conditions, film growth rate it is relatively slow,
Yield is relatively low, causes CZTSSe film costs higher and is difficult to prepare broad area device.Antivacuum method is generally chemical solution method,
Mainly there are sol-gal process, nanocrystalline heat injection, the solution particles method etc. based on hydrazine.The highest method of efficiency is namely based at present
The solution particles method of hydrazine, this illustrates antivacuum method in terms of preparing CZTSSe films with incomparable excellent of some vacuum methodes
Gesture, but hydrazine is a kind of toxic solvent, there is the health spoken sarcastically.Film made from sol-gal process is too thin, often needs multiple
Spin coating obtains required film thickness, and is not easy uniformly by multiple spin coating film surface, and thickness is unable to control, also unfavorable
It is prepared in large area.
Invention content
An object of the present invention is just to provide a kind of full-automatic Pulse Spraying device being used to prepare film, using the dress
Set can prepare large area, thickness is controllable, film of even compact, be particularly suitable for preparing the CZTSSe in solar cell
Film.
The second object of the present invention is just to provide a kind of full-automatic Pulse Spraying method being used to prepare film, party's legal system
Standby simple process and low cost, and can prepare that large area, thickness is controllable, film of even compact.
What an object of the present invention was realized in：A kind of full-automatic Pulse Spraying device being used to prepare film, packet
It includes：
Spray gun, vertical to place, upper part is the body of a gun, and lower end is nozzle；
Air pump is connected by gas-guide tube with the body of a gun of the spray gun, for providing high pressure into the body of a gun of the spray gun
Working gas；Air valve switch is equipped on the gas-guide tube；
Controller connects with the air valve switch on gas-guide tube, the open and close for controlling the air valve switch, to
Control air pump provides high-pressure working gas into spray gun body；
Container, the precursor liquid for holding film to be prepared, the body of a gun phase that the container passes through catheter and the spray gun
Connection；Under the action of high-pressure working gas, the precursor liquid in container can be entered in the body of a gun of spray gun and is atomized by catheter,
Finally sprayed by nozzle；And
Heating plate is arranged in the lower section of the spray gun；Be provided with substrate in the heating plate, the heating plate for pair
Substrate thereon is heated；The precursor liquid gone out by the nozzles spray of the spray gun is sprayed in the form of mist in substrate, repeatedly
Spraying can prepare required film in substrate.
The spray gun is arranged on a movable supporting frame, adjusts the upper and lower position of the movable supporting frame, it can be achieved that adjusting
The distance between the whole spray gun and substrate.
It is provided with adjusting pressuring knob on the spray gun, the atomization pressure in spray gun body is adjusted by the adjusting pressuring knob
By force.
The pressure of the high-pressure working gas provided by the air pump is 400 ~ 600KPa.
The precursor liquid held in the container is by CuCl2Alcoholic solution, ZnCl2Alcoholic solution, SnCl2Wine
It is formed after these four solution mixing of the alcoholic solution of smart solution and thioacetamide.
Full-automatic Pulse Spraying device provided by the present invention, is contained with precursor liquid, container passes through catheter in container
It is connected with spray gun body；Air pump is for providing high-pressure working gas into spray gun body, and high-pressure working gas is into spray gun
The body of a gun can form in a flash negative pressure, which causes the precursor liquid in container to enter in spray gun body by catheter, and preceding
Driving liquid can be atomized under the action of high-pressure working gas, and the precursor liquid after atomization is sprayed by spray tip, is finally sprayed on height
In warm substrate.By the open and close of the air valve switch on controller control gas-guide tube, when air valve switch is closed, air pump can be to spray
High-pressure working gas is provided in the rifle body of a gun, when air valve switch disconnects, air pump will no longer provide high-pressure work gas into spray gun body
Body.Only when there is high-pressure working gas, spray tip can just spray misty precursor liquid, therefore, gas be controlled by controller
The open and close of threshold switch is, it can be achieved that control to spray gun spraying precursor liquid, you can time that control sprays every time sprays twice
The time interval of painting and spraying number etc., film even compact that is final that the thickness of film is easily controlled, and preparing.
As long as in addition spraying film parameters are set on the controller, it will automatic running, voluntarily stop, convenience and high-efficiency is easy
Operation, and can be prepared with large area, it is advantageously implemented industrialization.
The second object of the present invention is to what is be achieved：A kind of full-automatic Pulse Spraying method being used to prepare film, packet
Include following steps：
A, the precursor liquid needed for film to be prepared is configured, and the precursor liquid configured is poured into container；
B, it is closed by the air valve switch on controller control gas-guide tube, so that air pump is passed through gas-guide tube and carried into the body of a gun of spray gun
For high-pressure working gas；
C, under the action of high-pressure working gas, precursor liquid in container is from the body of a gun that catheter flows into spray gun and mist
Change；
D, the precursor liquid after atomization is sprayed by the nozzle of spray gun, and is sprayed on high temperature substrate；
E, it is disconnected by the air valve switch on controller control gas-guide tube, primary spraying terminates；
F, after certain interval of time, step b ~ e is repeated, is sprayed again on high temperature substrate；Until in high temperature substrate
Film needed for upper formation.
It in step f, is sprayed once at interval of 20 ~ 40s, each spray time is 1 ~ 2s, is sprayed 50 ~ 150 times altogether.
High temperature substrate is to be heated and formed to substrate by heating plate；The temperature of high temperature substrate is 200 ~ 300 DEG C.
Prepared precursor liquid is by CuCl in step a2Alcoholic solution, ZnCl2Alcoholic solution, SnCl2Alcohol it is molten
It is formed after these four solution mixing of the alcoholic solution of liquid and thioacetamide.
After step f, makes to be formed by film on high temperature substrate and carry out vulcanization or selenizing in tube furnace, it finally can shape
At copper zinc tin sulfur selenium film.
Full-automatic Pulse Spraying method provided by the present invention belongs to antivacuum method, and preparing film first using this method needs
Precursor liquid is prepared, therefore each stoichiometric ratio for preparing film is controllable.It can especially be prepared in solar cell using this method
Copper zinc tin sulfur selenium film, the precursor liquid of copper zinc tin sulfur selenium film is specifically：By the metal chloride containing Cu, Zn, Sn（Or vinegar
Hydrochlorate）With thioacetamide（Or thiocarbamide）It is dissolved in alcohol in certain proportion, obtains the solution of yellow transparent；Due to solvent
It is alcohol, therefore obtained solution is safe and non-toxic.Precursor liquid is poured into container, container passes through catheter and spray gun body phase
Connection, high-pressure working gas is provided into spray gun body from air pump, and under the action of high-pressure working gas, precursor liquid is from catheter
It in into spray gun body and is atomized, is finally sprayed on high temperature substrate by nozzle.Due to spraying obtained film quality
There is relationship with many parameters, and these parameters are all controllable, therefore pass through the temperature of adjusting substrate, spray time, interval
Time, spraying number, spraying flow etc., can be obtained that thickness is controllable and the preferable film of uniformity, and the film repeatability sprayed
It is relatively high.
Method and process flow in the present invention is simple, easy to operate, at low cost, and can prepare large area, thickness it is controllable,
The film of even compact.Using this method other than it can prepare copper zinc tin sulfur selenium film, can also prepare perovskite thin film,
CZTS（That is copper-zinc-tin-sulfur）Film, the CIS film of quantum dot（That is copper-indium-sulfur film）Equal solar battery obsorbing layers film, also may be used
To prepare the film of the other materials such as NiO, ZnO.
Description of the drawings
Fig. 1 is the structural schematic diagram for the full-automatic Pulse Spraying device that film is used to prepare in the present invention.
Fig. 2 is the relational graph sprayed in the embodiment of the present invention between number and CZTS film thicknesses.
Fig. 3 is the XRD test charts that CZTS films are front and back in vulcanization annealing in the embodiment of the present invention.
Fig. 4 is the Raman test charts that CZTS films are front and back in vulcanization annealing in the embodiment of the present invention.
Fig. 5 is SEM figure of the CZTS films before vulcanization is annealed in the embodiment of the present invention.
Fig. 6 is SEM figure of the CZTS films after vulcanization is annealed in the embodiment of the present invention.
Specific implementation mode
As shown in Figure 1, the full-automatic Pulse Spraying device provided by the present invention for being used to prepare film includes spray gun 1, holds
Device 2, air pump 3, controller 4 and heating plate 5.
Spray gun 1 is vertically arranged on a movable supporting frame.The major part of spray gun 1 is the hollow body of a gun, under the body of a gun
End is nozzle.Container 2 is similarly disposed on movable supporting frame, and container 2 is located at the top of spray gun 1.Be contained in container 2 for
Prepare the precursor liquid of film.2 bottom end of container connects one end of catheter 7（That is inlet）, the other end of catheter 7（It is liquid
Mouthful）It stretches into the body of a gun of spray gun 1.Pressure is suitable with pressure in 1 body of a gun of spray gun in container 2, under natural conditions, in container 2 before
Driving liquid will not be flowed into the body of a gun of spray gun 1 by catheter 7.
Air pump 3 is connected by gas-guide tube 8 with the body of a gun of spray gun 1, i.e.,：One end of gas-guide tube 8（That is air inlet）With 3 phase of air pump
It connects, the other end（That is gas outlet）It stretches into the body of a gun of spray gun 1.And gas-guide tube 8 stretches into one end in 1 body of a gun of spray gun and catheter 7
The one end stretched into 1 body of a gun of spray gun is adjacent and is aligned, i.e., the two is in same level.Air pump 3 can be to spray by gas-guide tube 8
It is filled with high-pressure working gas in 1 body of a gun of rifle.When high-pressure working gas enters 1 body of a gun of spray gun in the gas outlet by gas-guide tube 8
Interior moment can be formed about negative pressure, since the gas outlet of gas-guide tube 8 goes out liquid close to catheter 7 in the gas outlet of gas-guide tube 8
Mouthful, therefore negative pressure is also formed at the liquid outlet of catheter 7, which can make the precursor liquid in container 2 enters along catheter 7 to spray
In 1 body of a gun of rifle.Due to there is the presence of high-pressure working gas, the precursor liquid into the liquid in 1 body of a gun of spray gun can be by mist
Change, the precursor liquid after atomization is finally sprayed by nozzle.There is no the high-pressure working gas that air pump 3 is provided, precursor liquid not to enter
In 1 body of a gun of spray gun, the precursor liquid after atomization would not be also sprayed by nozzle；The pressure of high-pressure working gas is too low, equally cannot
Precursor liquid is set to be atomized and spray；The pressure of high-pressure working gas is too high, then the misty precursor liquid of ejection can be made to rebound, to cause
Cross spray.Therefore the pressure of general control high-pressure working gas is 400 ~ 600Kpa（Or 58 ~ 87Psi）.High-pressure working gas can be with
For nitrogen or air etc..Adjusting pressuring knob can be set on spray gun 1, the atomization in 1 body of a gun of spray gun is adjusted by adjusting pressuring knob
Pressure, and then adjustable nozzles spray the flow of misty precursor liquid.
Air valve switch 9 is provided on gas-guide tube 8, air valve switch 9 connects with controller 4, and controller 4 can control air valve to open
Close 9 open and close.When air valve switch 9 is closed, air pump 3 can be filled with high-pressure work by gas-guide tube 8 into 1 body of a gun of spray gun
Gas；When air valve switch 9 disconnects, air pump 3 cannot be filled with high-pressure working gas into 1 body of a gun of spray gun.And in 1 body of a gun of spray gun
Only when being filled with high-pressure working gas, misty precursor liquid could be sprayed by nozzle.Therefore, controller 4 is opened by controlling air valve
9 open and close is closed, controllable spray gun 1 sprays misty precursor liquid.
Substrate 6 is arranged in the lower section of spray gun 1, and the misty precursor liquid sprayed by 1 nozzle of spray gun is sprayed directly in substrate 6.
Substrate 6 can be Mo electrodes, FTO, ITO or silicon chip etc..By adjusting movable supporting frame upper and lower position, it can be achieved that adjustment spray gun
The distance between 1 and substrate 6.Misty precursor liquid when spraying basad 6 direction from nozzle and falling, in solvent can gradually steam
Hair finally forms a thin layer film layer in substrate 6.Therefore, after spraying one layer, it is necessary to stop spraying, so that misty precursor liquid
It air-dries, shape in substrate 6.After certain interval of time, spray again.Repeatedly, required thickness is finally prepared in substrate 6
The film of degree.The open and close for controlling air valve switch 9 in the present invention by controller 4, can be controlled in substrate 6 and sprays every time
Time, interval time for spraying twice and spraying number etc..Further include alarm unit in controller 4, when spray gun spraying
When number reaches setting value, alarm unit can send out the entire program operation of warning reminding and complete.
In order to accelerate the evaporation of solvent, substrate 6 is heated by the way that heating plate 5 is arranged in the present invention, it is molten to accelerate
The evaporation of agent accelerates the molding of film.Heating plate 5 is located at 6 lower section of substrate, i.e.,：Substrate 6 is directly placed in heating plate 5.Generally
The heating temperature that heating plate 5 is arranged is 220 ~ 300 DEG C.
In order to obtain without the cracking preferable film of uniformity, the amount sprayed every time wants small, spraying interval time will be grown, repeatedly
Spraying；If expecting, a thickness is 1-2 μm of film, needs 1-2 hour, and the device in the present invention be it is full automatic,
Precursor liquid need to be configured, be poured into the container of device, spraying pressure, spraying number, each spray time, spray it twice
Between the parameter settings such as interval time, temperature of heating plate it is good, it can voluntarily work, and can voluntarily stop after spraying,
And alarm has sprayed completion, convenience and high-efficiency.
Using the device in the present invention can be used to prepare perovskite thin film, the film of CZTS quantum dots, CZTSSe films,
Other solar battery obsorbing layer films such as CIS film, can also be used to the film for preparing the other materials such as NiO, ZnO.
The full-automatic Pulse Spraying method provided by the present invention for being used to prepare film is introduced with reference to specific example.
The first step：First, in accordance with connecting components shown in Fig. 1, to build full-automatic Pulse Spraying device.
Second step：Clean glass.
It by the size of glass-cutting to 20*20cm, and cleans, is then rinsed with deionized water dry in semiconductor cleaning agent
Only, then N is used2It dries up spare.
Third walks：Sputter Mo electrodes.
Using sputtering equipment, the Mo of about 800nm thickness is sputtered on glass, and the Mo electrodes sputtered are cut, are cut into
Then the slice, thin piece of 3.5*3.5cm sizes is cleaned with semiconductor cleaning agent, is dried up with nitrogen.
4th step：The generation of CZTS films.
1, CZTS precursor liquids are configured：
1., weigh 0.56mmol CuCl2·2H2O measures 30 μ L ethanol amines（MEA）, 10mL absolute ethyl alcohols are measured, make three
Person mixes, and forms bottle-green solution.
2., weigh 0.38mmol ZnCl2·2H2O measures 30 μ L ethanol amines（MEA）, 10mL absolute ethyl alcohols are measured, make three
Person mixes, and forms the solution of water white transparency.
3., weigh 0.32mmol SnCl2·2H2O measures 30 μ L ethanol amines（MEA）, 10mL absolute ethyl alcohols are measured, make three
Person mixes, and forms white opacity solution.
4., weigh 2.08mmol thioacetamides（TAA）, 10mL absolute ethyl alcohols are measured, the two is made to mix, are formed colourless
Bright solution.
5., with pipettor aspiration step 3. in solution, and in the solution during step is added dropwise 1., in the process of dropwise addition
In, lasting to stir, solution gradually becomes light green color by bottle green；Again by step 2. in solution be added dropwise in above-mentioned solution,
Solution colour is without significant change；Finally by step 4. in solution be added dropwise in above-mentioned mixed solution, solution gradually becomes clear
Clear yellow solution, here it is the final required CZTS precursor liquids containing Cu, Zn, Sn, S.
Previous step 1. ~ 4. in, absolute ethyl alcohol is solvent, and absolute ethyl alcohol is compared to other organic solvents, safer no danger
Evil, and cost is relatively low；MEA is additive.Source metal used in the present embodiment is chloride, and cost is relatively low, soluble；Other
Acetate can also be used in embodiment.Thioacetamide can also be replaced by thiocarbamide.
2, CZTS precursor liquids are sprayed.
CZTS precursor liquids are poured into container.There is the glass of Mo electrodes to put on hot plate sputtering, heating plate is set
Heating temperature is 250 DEG C.Distance of the spray tip apart from substrate of glass is 15cm.The atomization pressure for adjusting spray gun is 450 Kpa.
By controller, each parameter in spraying process is set：Each spray time is 1s, and spraying number 100 times is adjacent to spray twice
Interval time 30s.Parameter regulation can start to spray well, and since solvent is alcohol, volatilization process is nontoxic relatively to pacify
Entirely.The dropping process of precursor liquid shown in right side arrow in Fig. 1, as CZTS precursor liquids are falling to substrate of glass process by nozzle
The schematic diagram of middle spirit solvent volatilization.
The thickness of film, curve obtained such as Fig. 2 institutes are measured after spraying 30 times, 50 times, 70 times, 90 times and 100 times respectively
Show.As seen from Figure 2, with the increase of spraying number, the thickness of film gradually increases, and film thickness and spraying number are in
Linear relationship, it is fixed that this, which turns out the primary thickness of every spraying, and the thickness for often spraying a film increases 9nm or so, this
Sample can be very good the thickness of control film.
After spraying 100 times, CZTS films have been made on Mo electrodes.XRD and Raman is carried out to manufactured CZTS films to survey
Examination, acquired results are shown in Fig. 3 and Fig. 4；SEM tests are carried out to manufactured CZTS films, acquired results are shown in Fig. 5.
3, it anneals：
1., preannealing：So that the film that spraying is got well first is carried out 300 DEG C of preannealings on hot plate, spirit solvent is made thoroughly to wave
Hair falls.
2., tubular type pan vulcanization annealing：Weigh the glass putty of 100mg sulphur and 5mg（Glass putty is used as replenishers herein, with more
Mend the loss of tin in CZTS films）It is put into graphite, and the substrate of glass for being coated with CZTS films is put into graphite, seal
It closes, is put into tube furnace, be raised to 300 DEG C in 60min using temperature program, 30min is kept at 300 DEG C；Exist later
It is warming up to 580 DEG C in 28min, and the pressure in stove is made to be maintained at 0.05MPa or so；40min is kept at 580 DEG C, later certainly
So cooling.
XRD and Raman tests are carried out to the CZTS films after annealing, acquired results are shown in Fig. 3 and Fig. 4.It can by Fig. 3 and Fig. 4
To find out, CZTS is formd before and after vulcanization annealing, and without miscellaneous, but crystal structure obviously increases after vulcanizing annealing
By force.
SEM tests are carried out to the CZTS films after annealing, acquired results are shown in Fig. 6.Using this it can be seen from Fig. 5 and Fig. 6
CZTS films prepared by method in invention have the characteristics that uniformity is good, coverage is high etc..
Selenized annealing can also be carried out in other embodiment in tube furnace, to form CZTSSe films.When selenized annealing
Selenium powder need to only be weighed and replace sulphur.
The present invention prepares film using full-automatic Pulse Spraying method, is adsorbed compared to traditional spin coating or continuous ionic layer
Etc. antivacuum methods, film prepared by this method is relatively uniform and element ratio is controllable, and crystallinity is relatively good after vulcanization, preparation process letter
Single easy to operate, favorable repeatability, cost is relatively low, safety non-pollution, realizes that the CZTSSe batteries of efficient stable provide to be following
A kind of method of feasibility.
Claims (7)
1. a kind of full-automatic Pulse Spraying device being used to prepare film, characterized in that including：
Spray gun, vertical to place, upper part is the body of a gun, and lower end is nozzle；
Air pump is connected by gas-guide tube with the body of a gun of the spray gun, and one end of the gas-guide tube connects with air pump, and the other end is stretched
Enter in the body of a gun of spray gun；The air pump is for providing the high-pressure work gas that pressure is 400 ~ 600KPa into the body of a gun of the spray gun
Body；Air valve switch is equipped on the gas-guide tube；
Controller connects with the air valve switch on gas-guide tube, the open and close for controlling the air valve switch, to control
Air pump provides high-pressure working gas into spray gun body；
Container, the precursor liquid for holding film to be prepared, the container are connected by catheter with the body of a gun of the spray gun；
One end of the container bottom end connection catheter, the other end of the catheter stretch into the body of a gun of spray gun；The catheter is stretched
Both it is adjacent with one end that the gas-guide tube stretches into spray gun body and be aligned to enter one end in spray gun body, i.e., is in same water
In plane；Pressure is suitable with pressure in spray gun body in the container, and under natural conditions, the precursor liquid in container will not be by leading
Liquid pipe flows into the body of a gun of spray gun；Under the action of high-pressure working gas, the precursor liquid in container can enter spray by catheter
It in the body of a gun of rifle and is atomized, is finally sprayed by nozzle；And
Heating plate is arranged in the lower section of the spray gun；Substrate is provided in the heating plate, the heating plate is used for thereon
Substrate heated；The precursor liquid gone out by the nozzles spray of the spray gun is sprayed in the form of mist in substrate, is repeatedly sprayed
Required film can be prepared in substrate.
2. the full-automatic Pulse Spraying device according to claim 1 for being used to prepare film, characterized in that the spray gun is set
Set on a movable supporting frame, adjust the upper and lower position of the movable supporting frame, it can be achieved that adjust the spray gun and substrate it
Between distance.
3. the full-automatic Pulse Spraying device according to claim 1 for being used to prepare film, characterized in that in the spray gun
On be provided with adjusting pressuring knob, pass through the adjusting pressuring knob be adjusted spray gun body in atomization pressure.
4. the full-automatic Pulse Spraying device according to claim 1 for being used to prepare film, characterized in that in the container
The precursor liquid held is by CuCl2Alcoholic solution, ZnCl2Alcoholic solution, SnCl2Alcoholic solution and thioacetamide
The mixing of alcoholic solution these four solution after formed.
5. a kind of full-automatic Pulse Spraying method being used to prepare film, characterized in that include the following steps：
A, the precursor liquid needed for film to be prepared is configured, and the precursor liquid configured is poured into container；
B, it is closed by the air valve switch on controller control gas-guide tube, so that air pump is passed through gas-guide tube and height is provided into the body of a gun of spray gun
Press working gas；
C, under the action of high-pressure working gas, the precursor liquid in container from the body of a gun that catheter flows into spray gun and is atomized；
D, the precursor liquid after atomization is sprayed by the nozzle of spray gun, and is sprayed on high temperature substrate；
E, it is disconnected by the air valve switch on controller control gas-guide tube, primary spraying terminates；
F, after certain interval of time, step b ~ e is repeated, is sprayed again on high temperature substrate；Until the shape on high temperature substrate
At required film；
It in step f, is sprayed once at interval of 20 ~ 40s, each spray time is 1 ~ 2s, is sprayed 50 ~ 150 times altogether；
High temperature substrate is to be heated and formed to substrate by heating plate；The temperature of high temperature substrate is 200 ~ 300 DEG C.
6. the full-automatic Pulse Spraying method according to claim 5 for being used to prepare film, characterized in that institute in step a
The precursor liquid of preparation is by CuCl2Alcoholic solution, ZnCl2Alcoholic solution, SnCl2Alcoholic solution and thioacetamide
It is formed after alcoholic solution these four solution mixing.
7. the full-automatic Pulse Spraying method according to claim 6 for being used to prepare film, characterized in that step f it
Afterwards, make to be formed by film on high temperature substrate and carry out vulcanization or selenizing in tube furnace, can finally form copper zinc tin sulfur selenium film.
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| JP2018113327A (en) * | 2017-01-11 | 2018-07-19 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing apparatus |
| CN109148625A (en) * | 2018-05-17 | 2019-01-04 | 中国科学院物理研究所 | Copper zinc tin sulfur selenium thin-film solar cells and preparation method thereof |
| CN108816566A (en) * | 2018-08-02 | 2018-11-16 | 李彦利 | A kind of Plastic film surface spray equipment |
| CN110424693B (en) * | 2019-07-12 | 2020-12-08 | 博兴战新产业发展有限公司 | Coating spraying equipment based on pulse differential pressure principle |
| CN112588491B (en) * | 2020-12-22 | 2022-12-23 | 百琪达智能科技（宁波）股份有限公司 | Pulse type dry-wet mixed type mold release agent spraying system |
| CN113275173A (en) * | 2021-05-16 | 2021-08-20 | 西北工业大学 | Electrostatic spraying device and method for preparing large-area thin film by adopting same |
| CN114260112A (en) * | 2022-01-07 | 2022-04-01 | 郑州大学 | Non-contact light heating auxiliary matrix spraying device and matrix spraying method |
| CN115957947B (en) * | 2022-11-29 | 2023-08-29 | 北京大学长三角光电科学研究院 | Coating printing method and apparatus |
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