CN103325886B - It is a kind of that there is the Cu-In-Al-Se that can be distributed with gradient（CIAS）The preparation method of film - Google Patents
It is a kind of that there is the Cu-In-Al-Se that can be distributed with gradient（CIAS）The preparation method of film Download PDFInfo
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Abstract
There is provided a kind of preparation method with the copper indium aluminum selenium membrane that can be distributed with gradient suitable for Photovoltaic new energy field of material technology by the present invention.This method comprises the following steps：Synthesize copper and indium aluminium sulphur nano particle；Prepare the nanocrystalline ink of copper and indium aluminium sulphur；The preparation of Cu-In-Al-Se presoma prefabricated membrane；The preparation of copper indium aluminum selenium membrane.Present invention process is simple, easy to operate, with low cost, can prepare large area uniform film layer, promotes the raising of solar film battery conversion ratio.
Description
Technical field
Have and can be distributed with gradient the invention belongs to the preparation field of photovoltaic solar battery light absorbent, more particularly to one kind
Copper indium aluminum selenium membrane preparation method.
Background technology
Solar energy is a kind of cleaning, the renewable new energy of environmental protection.It can replace part fossil fuel, main as future
Want one of energy.The Land use systems of current solar energy have two kinds of photothermal deformation and opto-electronic conversion.Wherein photothermal conversion mode is wide
General application, and most have the photoelectric conversion mode of application prospect, but because prepared by the light absorption layer material and its device of solar cell
Cost is higher, can only be applied in the field of some particular/special requirements.Accordingly, it would be desirable to develop a kind of cheap, efficient film
The preparation technology and technology of solar cell.
At present, CIGS (CIGS) thin-film solar cells is that most have one of solar cell of application prospect, still
The preparation of CIGS thin film solar cell light absorption layer needs to use the rare metals such as substantial amounts of In, Ga, and this causes CIGS thin film
The large-scale popularization and application of battery are very restricted in terms of raw material supply, with increasingly disappearing for these rare metal raw materials
Consumption, the cost of CIGS hull cell will also increased.Therefore, some researchers look for a kind of cheap, reserves
High metal Al replaces Ga, is prepared into copper indium aluminum selenium membrane battery.
The preparation method of current copper indium aluminum selenium membrane mainly has two kinds of magnetron sputtering method and electrodeposition process, and magnetron sputtering method is needed
Vacuum equipment is wanted, input cost is high, and metal Al is easily oxidized so that more or less alumina can be contained in the film of preparation
Compound.And film compactness and attached type prepared by electrodeposition process is all poor, and the transformation efficiency of battery is relatively low.
The content of the invention
The purpose of the embodiment of the present invention is to provide a kind of Cu-In-Al-Se (CIAS) film that has and can be distributed with gradient
Preparation method, it is intended to solve in the prior art that complex operation, high cost, purity is low, film compactness and attached type is poor, Yi Jiguang
The problem of electric conversion ratio is low.
The embodiment of the present invention is achieved in that a kind of preparation side for the copper indium aluminum selenium membrane that has and can be distributed with gradient
Method, comprises the following steps：
Copper source compound, aluminum source compound, indium source compound, sulphur source and oleyl amine are mixed, synthesis copper and indium aluminium sulphur nanometer
Grain；
The copper and indium aluminium sulphur nano particle is scattered in organic solvent, it is configured to the nanocrystalline ink of copper and indium aluminium sulphur；
Copper and indium aluminium sulphur nanometer ink is coated on plating bilayer Mo matrix, Cu-In-Al-Se presoma is formed prefabricated
Film, wherein, the matrix of the plating bilayer Mo has pure Mo layers and the Mo layers for mixing aluminium matrix for deposition respectively；
The Cu-In-Al-Se presoma prefabricated membrane is obtained into copper indium aluminum selenium membrane by selenizing, annealing.
Preparation method of the present invention with the copper indium aluminum selenium membrane that can be distributed with gradient, using relatively inexpensive calorize
Compound is as raw material, the problem of solving rare raw material and easily oxidized metallic aluminium.In addition, the present invention is a kind of antivacuum film
Technology, it not only improves the energy band distribution of film, widen the light abstraction width of film, promote absorption and profit of the film to light
With, and the copper indium aluminum selenium membrane being distributed with gradient is prepared using the Mo layers for mixing aluminium, electricity conversion is improved, also simultaneously
The manufacturing cost of solar cell is greatly reduced, is conducive to the preparation of the uniform copper indium aluminum selenium membrane of large area.
Embodiment
In order that technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention, is not intended to limit the present invention.
The embodiments of the invention provide a kind of solution manufacturing method for the copper indium aluminum selenium membrane that has and can be distributed with gradient, bag
Include following steps：
S01. copper and indium aluminium sulphur nano particle is synthesized：By copper source compound, aluminum source compound, indium source compound, sulphur source and oil
Amine is mixed, and synthesizes copper and indium aluminium sulphur nano particle；
S02. the nanocrystalline ink of copper and indium aluminium sulphur is prepared：The copper and indium aluminium sulphur nano particle is disperseed to prepare in organic solvent
Into the nanocrystalline ink of copper and indium aluminium sulphur；
S03. copper and indium aluminium sulphur nanometer ink is coated on plating bilayer Mo matrix, forms Cu-In-Al-Se presoma pre-
Film, wherein, the matrix of the plating bilayer Mo has pure Mo layers and the Mo layers for mixing aluminium matrix for deposition respectively；
S04. the preparation of copper indium aluminum selenium membrane：The Cu-In-Al-Se presoma prefabricated membrane is obtained by selenizing, annealing
Obtain copper indium aluminum selenium membrane.
Specifically, in above-mentioned steps S01, in order to be able to effective dissolving copper source compound, aluminum source compound, indium source compound and
Sulphur source, and stable, volatility is small in the range of synthesis temperature, the embodiment of the present invention is used as synthesis copper and indium aluminium sulphur nanometer from oleyl amine
The solvent of particle.The mode that copper source compound, aluminum source compound, indium source compound and sulphur source are mixed with oleyl amine is unrestricted,
As the presently preferred embodiments, can be added to together after mixing copper source compound, aluminum source compound, indium source compound and sulphur source
It is added in oleyl amine or respectively by copper source compound, aluminum source compound, indium source compound and sulphur source in oleyl amine, it adds
Enter order unrestricted.Wherein, in a preferred embodiment, the copper source compound is chlorate, acetate, acetylacetonate, oxygen
At least one in compound；Source of aluminium compound is at least one in chlorate, acetate, acetylacetonate, oxide；
The indium source compound is at least one in chlorate, acetate, acetylacetonate, oxide；The sulphur source is sulphur powder, sulphur
Change at least one in hydrogen, carbon disulfide, thiocarbamide.
In the copper indium aluminum selenium membrane, the ratio of each component have on the band structure of film certain influence, especially indium and
Influence of the ratio of aluminium to film wideband structural is larger, and the content of aluminium is different, and the bandwidth of thin-film material is different, certain proportion
In the range of, the bandwidth of the bigger film of aluminium content is bigger, still, when aluminium content is too big, and the performance of film also can be by shadow
Ring.Study discovery repeatedly through inventor, the indium, aluminium element percentage composition ratio are：0<Aluminium/(indium+aluminium)<When 40%, film material
The better performances of material, wherein, when aluminium/(indium+aluminium)=30%, the performance of film is best.
As the presently preferred embodiments, for the generation for completely cutting off air, avoiding other side reactions, add after raw material, in a device
Gas washing is circulated to reaction solution by the way of vacuum and nitrogen atmosphere is passed through, then reaction vessel is full of with nitrogen.Wherein,
Gas washing number of times is preferably 2 times, and each gas washing time is preferably 15min.Of course it is to be understood that other are pacifying at reaction conditions
Other gases for entirely and not occurring side reaction with product are also within the scope of the present invention.
In step S01, as particular preferred embodiment, the synthesis temperature of the sulphur nano particle of copper and indium aluminium described in S01 is excellent
Elect 180-280 DEG C as, the reaction time is 10-100min.Wherein, for homogeneous heating in synthetic reaction process, above-mentioned synthesis is anti-
Mode of heating selects magnetic agitation mode of heating in answering.
In step S01, after synthetic reaction terminates in S01, reaction solution is cooled to after room temperature, filtering reacting liquid obtains solid
Product, is cleaned after 1~5 time with organic solvent, obtains clean copper and indium aluminium sulphur nano particle.It is above-mentioned to have as specific embodiment
Machine solvent is preferably at least one in ethanol, isopropanol, hexane or chloroform.
Wherein, in above-mentioned steps S02, in order to obtain, adhesive force is good, the nanocrystalline ink of impurity less residue copper and indium aluminium sulphur,
As further preferred embodiments, the organic solvent is at least one in amine, benzene class or alkanethiol class compound.At this
In preferred embodiment, the organic solvent plays a part of dispersant simultaneously so that the copper and indium aluminium sulphur nano particle energy of reaction generation
It is dispersed, and the adhesive force of the nanocrystalline ink of copper and indium aluminium sulphur and matrix can be improved.As specific embodiment, the preferred pyrrole of amine
In at least one in pyridine, butylamine, amylamine, hexylamine, 2- ethyl butyl amines, the preferred toluene of benzene class, dimethylbenzene, benzene, ethylbenzene, propyl benzene
At least one at least one, the preferred hexyl mercaptan of alkanethiol, dimethylbenzene, benzene, ethylbenzene, propyl benzene.
In the S02 steps, the concentration of the nanocrystalline ink of copper and indium aluminium sulphur has direct influence, individual layer to the thickness of film
The thickness of film and the concentration of ink are proportional, and concentration is bigger, and the thickness of single thin film is bigger.As the presently preferred embodiments,
In order to obtain the individual layer copper and indium aluminium sulphur film that thickness is suitable, be evenly distributed, the concentration of the nanocrystalline ink of copper and indium aluminium sulphur is 10-
300mg/mL。
In above-mentioned steps S03, the Cu-In-Al-Se presoma prefabricated membrane prefabricated membrane is by using physical method by copper and indium aluminium
The nanocrystalline ink of sulphur is coated on plating bilayer Mo quartz glass substrate and is prepared from, before the Cu-In-Al-Se prepared is nanocrystalline
It is 800-3000nm to drive the prefabricated film thickness of body.Using antivacuum physical method, it is not necessary to expensive equipment, reduce and invest into
This, and it is simple to operate, it is easy to large-scale industrial production.The physical method is preferably knife coating, spin-coating method, czochralski method, drop coating
One kind in method, silk screen print method.Of course it is to be understood that to be used for the nanocrystalline presoma of Cu-In-Al-Se pre- in the art other
The physical method for being film-made film is all within the scope of the present invention.
Wherein, as particular preferred embodiment, above-mentioned plating bilayer Mo quartz glass substrate for be respectively adopted sputtering method and
Cosputtering method deposits pure Mo layers on quartz substrate and mixes the double-deck Mo quartz glass substrates of the Mo layers of aluminium.As specific preferred real
Example is applied, the preparation method of plating Mo quartz glass substrates is：From quartz glass as substrate, matrix is cut into the length of side is
1.0cm × 2.0cm matrix is standby, respectively with acetone, ethanol, deionized water excusing from death cleaning calcium soda-lime glass matrix, obtains surface
Clean matrix, then by magnetically controlled DC sputtering plating last layer 300-800nm on clean matrix metal Mo films, so
The thick metal Mo films containing aluminium of one layer of 20-500nm are deposited by cosputtering method again afterwards, the content of aluminium is 0.5-15%.Mix aluminium
Mo film layers realize the gradient distribution of aluminium by the thermal diffusion of following step S04 intermediate ions, and concrete principle is：In heat treatment
The diffusion rate of aluminium than copper, indium it is all low, easily in film congregate, cause aluminium content at the top of film too low.And use and mix
The Mo layers of aluminium, had both avoided aluminium and had largely been aoxidized, while the also aluminium of supplement film bottom, adds the concentration of aluminium in film bottom
Greatly, it can be spread in heat treatment process aluminium to top, the film of aluminium gradient distribution thus be formed, while the downward diffusion into the surface of aluminium is arrived
Mo layers form Al with the contact surface and oxygen reaction of glass2O3, promote Mo and the raising of glass attachment, so as to prepare with ladder
The copper indium aluminum selenium membrane of distribution is spent, and then improves its electricity conversion.
As particular preferred embodiment, selenization concretely comprises the following steps described in S04：Heat treatment work is used as using tube furnace
Tool, is first placed on Cu-In-Al-Se presoma prefabricated membrane and appropriate selenium source in graphite, then the graphite is placed in tube furnace
In, and full of Ar gas, then heated up with 10-30/min speed, body of heater heating is given, selenization is carried out, finally obtains copper and indium
Aluminium selenium film.Wherein, selenizing temperature be 500-600 DEG C, the selenizing time be 10-90min, wherein, selenium source be selenium powder, hydrogen selenide,
At least one in diethyl selenide.Ar gas is as protective gas in above-mentioned steps, for preventing Cu-In-Al-Se presoma prefabricated membrane
Side reaction occurs for prefabricated membrane.Of course it is to be understood that in the art other can serve as under these conditions Cu-In-Al-Se it is nanocrystalline before
The gas of body protective gas is driven, all within the scope of the present invention.In the embodiment of the present invention, the purpose of selenization is thin
Replace the position of sulphur in film, so as to form copper indium aluminum selenium membrane.The consumption of selenium influences larger to selenization, when selenium consumption is too low
When, do not reach the effect of substitution sulphur completely；When Se content is too high, waste is easily caused.As the presently preferred embodiments, when selenium powder is used
Measure as 1-30mmol, selenium amount can cause the loss of selenium in film very little, can cause to waste too much.
As the presently preferred embodiments, the copper indium aluminum selenium membrane thickness prepared is 800-3000nm.Ground repeatedly through inventor
Study carefully discovery, the thickness of copper indium aluminum selenium membrane is larger to the inhalation effects of light：When the thickness of film is too small, film will be reduced to light
Absorb and then influence film photoelectric conversion ratio, make the limited performance of product；Film thickness is thicker, and absorption of the film to light is higher,
The utilization rate of light is higher, and the performance of product is also better, but thickness is too thick will to increase film cost.When copper indium aluminum selenium membrane is thick
When spending for 800-3000nm, the performance of copper indium aluminum selenium membrane can be met, cost can be efficiently controlled again.
Rare metal gallium is replaced using relatively inexpensive aluminium in the embodiment of the present invention, experiment is not only reduced to noble metal
Dependence, also reduces the consumption of rare metal, the problem of solving rare raw material and easily oxidized metallic aluminium.Meanwhile, use
The Mo film layers of aluminium are mixed as back-contact electrode, are prepared the copper indium aluminum selenium membrane being distributed with gradient, are conducive to preparing high conversion
The copper indium aluminum selenium membrane battery of rate.In addition, the present invention is a kind of antivacuum masking technique, it not only improves the energy band point of film
Cloth, widens the light abstraction width (energy gap of Cu-In-Al-Se is in 1.0-2.7eV) of film, promotes thin absorption and profit to light
With, and then electricity conversion is improved, the manufacturing cost of solar cell is also greatly reduced, is conducive to the uniform copper and indium of large area
The preparation of aluminium selenium film.
Embodiment one
(1) preparation of copper and indium aluminium sulphur nano particle：By 2.0mmol stannous chlorides, 1.70mmol indium trichlorides, 0.30mmol
Alchlor and 6.0mmol sulphur powders are added in 100mL three-necked bottles, add 35mL oleyl amines, and are put into temperature control heating set, then
Connect, and heat with Shrek air interchanger.Reaction solution is followed by way of vacuum and argon atmosphere circulation simultaneously
Washing-round gas 2 times, each gas washing 15min.Finally reaction vessel is full of with argon gas.Under magnetic stirring, continue to heat, when temperature liter
Height keeps constant, stops reaction after 60min to 220 DEG C.Room temperature is then cooled to, filter centrifugation reaction solution obtains solid product,
And cleaned with ethanol, hexane 5 times, obtain clean solid product.
(2) the nanocrystalline ink of copper and indium aluminium sulphur is prepared：It is 20mg/ that copper and indium aluminium sulphur nano particle, which is put into toluene, and forms concentration
Colloidal solution-nanocrystalline ink of copper and indium aluminium sulphur stable mL.
(3) preparation of molybdenum glass is plated：Quartz glass substrate is cut into 1.0cm × 2.0cm sizes, respectively with acetone, second
Alcohol, deionized water excusing from death are cleaned up.Metal Mo is plated on quartz glass substrate by direct current magnetron sputtering process, thickness is
500nm；Then the metal Mo films containing Al that a layer thickness is 200mn are deposited by cosputtering method, the content of wherein aluminium is
5%.
(4) preparation of copper indium aluminum selenium membrane：The nanocrystalline ink of copper and indium aluminium sulphur is coated in by knife coating plating Mo matrix
On, the thick nanocrystalline presoma prefabricated membranes of Cu-In-Al-Se of 1500nm are formed, is subsequently put on 300 DEG C of electric hot plate and dries.Dry
The diethyl selenide of Cu-In-Al-Se presoma prefabricated membrane prefabricated membrane and slightly excessive (5mmol) after dry is placed in graphite, then
The stone mill box is placed in tube furnace, Ar gas is passed through, the air in stove is drained, and Ar is full of furnace chamber.Then with 15 DEG C/min
Programming rate, give body of heater heating, cavity temperature is risen rapidly to 530 DEG C, then Cu-In-Al-Se presoma prefabricated membrane entered
The showing tremendous enthusiasm processing of row selenizing.Stop heating after 30min, and be cooled to room temperature, finally obtain the Cu-In-Al-Se with gradient distribution thin
Film.
Embodiment two
(1) preparation of copper and indium aluminium sulphur nano particle：By 2.0mmol stannous chlorides, 1.70mmol indium trichlorides, 0.30mmol
Alchlor and 4.0mmol sulphur powders are added in 100mL three-necked bottles, add 35mL oleyl amines, and are put into temperature control heating set, then
Connect, and heat with Shrek air interchanger.Reaction solution is followed by way of vacuum and argon atmosphere circulation simultaneously
Washing-round gas 2 times, each gas washing 15min.Finally reaction vessel is full of with argon gas.Under magnetic stirring, continue to heat, when temperature liter
Height keeps constant, stops reaction after 60min to 190 DEG C.Room temperature is then cooled to, filter centrifugation reaction solution obtains solid product,
And cleaned with ethanol, hexane 5 times, obtain clean solid product.
(2) the nanocrystalline ink of copper and indium aluminium sulphur is prepared：It is 50mg/ that copper and indium aluminium sulphur nano particle, which is put into toluene, and forms concentration
Colloidal solution-nanocrystalline ink of copper and indium aluminium sulphur stable mL.
(3) preparation of molybdenum glass is plated：Quartz glass substrate is cut into 1.0cm × 2.0cm sizes, respectively with acetone, ethanol,
Deionized water excusing from death is cleaned up.Metal Mo is plated on quartz glass substrate by direct current magnetron sputtering process, thickness is 600nm；
Then the metal Mo films containing Al that a layer thickness is 500mn are deposited by cosputtering method, the wherein content of aluminium is 10%.
(4) preparation of copper indium aluminum selenium membrane：The nanocrystalline ink of copper and indium aluminium sulphur is coated in by knife coating plating Mo matrix
On, the thick nanocrystalline presoma prefabricated membranes of Cu-In-Al-Se of 1500nm are formed, is subsequently put on 300 DEG C of electric hot plate and dries.Dry
The diethyl selenide of Cu-In-Al-Se presoma prefabricated membrane prefabricated membrane and slightly excessive (5mmol) after dry is placed in graphite, then
The stone mill box is placed in tube furnace, Ar gas is passed through, the air in stove is drained, and Ar is full of furnace chamber.Then with 20 DEG C/min
Programming rate, give body of heater heating, cavity temperature is risen rapidly to 560 DEG C, then Cu-In-Al-Se presoma prefabricated membrane entered
The showing tremendous enthusiasm processing of row selenizing.Stop heating after 20min, and be cooled to room temperature, finally obtain the Cu-In-Al-Se with gradient distribution thin
Film.
Embodiment three
(1) preparation of copper and indium aluminium sulphur nano particle：By 2.0mmol stannous chlorides, 1.70mmol indium trichlorides, 0.30mmol
Alchlor and 5.0mmol sulphur powders are added in 100mL three-necked bottles, add 35mL oleyl amines, and are put into temperature control heating set, then
Connect, and heat with Shrek air interchanger.Reaction solution is followed by way of vacuum and argon atmosphere circulation simultaneously
Washing-round gas 2 times, each gas washing 15min.Finally reaction vessel is full of with argon gas.Under magnetic stirring, continue to heat, when temperature liter
Height keeps constant, stops reaction after 60min to 200 DEG C.Room temperature is then cooled to, filter centrifugation reaction solution obtains solid product,
And cleaned with ethanol, hexane 5 times, obtain clean solid product.
(2) the nanocrystalline ink of copper and indium aluminium sulphur is prepared：Copper and indium aluminium sulphur nano particle, which is put into formation concentration in toluene, is
Colloidal solution-nanocrystalline ink of copper and indium aluminium sulphur stable 100mg/mL.
(3) preparation of molybdenum glass is plated：Quartz glass substrate is cut into 1.0cm × 2.0cm sizes, respectively with acetone, ethanol,
Deionized water excusing from death is cleaned up.Metal Mo is plated on quartz glass substrate by direct current magnetron sputtering process, thickness is 500nm；
Then the metal Mo films containing Al that a layer thickness is 100mn are deposited by cosputtering method, the wherein content of aluminium is 15%.
(4) preparation of copper indium aluminum selenium membrane：The nanocrystalline ink of copper and indium aluminium sulphur is coated in by knife coating plating Mo matrix
On, the thick nanocrystalline presoma prefabricated membranes of Cu-In-Al-Se of 1500nm are formed, is subsequently put on 300 DEG C of electric hot plate and dries.Dry
The diethyl selenide of Cu-In-Al-Se presoma prefabricated membrane prefabricated membrane and slightly excessive (5mmol) after dry is placed in graphite, then
The stone mill box is placed in tube furnace, Ar gas is passed through, the air in stove is drained, and Ar is full of furnace chamber.Then with 25 DEG C/min
Programming rate, give body of heater heating, cavity temperature is risen rapidly to 550 DEG C, then Cu-In-Al-Se presoma prefabricated membrane entered
The showing tremendous enthusiasm processing of row selenizing.Stop heating after 30min, and be cooled to room temperature, finally obtain the Cu-In-Al-Se with gradient distribution thin
Film.
Example IV
(1) preparation of copper and indium aluminium sulphur nano particle：By 1mmol copper chlorides, 0.8mmol indium trichlorides, 0.2mmol tri-chlorinations
Gallium and 3mmol sulphur powders are added in 100mL three-necked bottles, add 35mL oleyl amines, and are put into temperature control heating set, then with Shrek
Air interchanger is connected, and is heated.Gas washing 2 is circulated to reaction solution by way of vacuum and argon atmosphere circulation simultaneously
It is secondary, each gas washing 15min.Finally reaction vessel is full of with argon gas.Under magnetic stirring, continue to heat, when temperature is increased to 210
DEG C, keep constant, stop reaction after 60min.Room temperature is then cooled to, filter centrifugation reaction solution obtains solid product, and uses second
Alcohol, hexane are cleaned 5 times, obtain clean solid product.
(2) the nanocrystalline ink of copper and indium aluminium sulphur is prepared：Copper and indium aluminium sulphur nano particle, which is put into formation concentration in toluene, is
Colloidal solution-nanocrystalline ink of copper and indium aluminium sulphur stable 150mg/mL.
(3) preparation of molybdenum glass is plated：Quartz glass substrate is cut into 1.0cm × 2.0cm sizes, respectively with acetone, ethanol,
Deionized water excusing from death is cleaned up.Metal Mo is plated on quartz glass substrate by direct current magnetron sputtering process, thickness is 500nm；
Then the metal Mo films containing Al that a layer thickness is 150mn are deposited by cosputtering method, the wherein content of aluminium is 1%.
(4) preparation of copper indium aluminum selenium membrane：The nanocrystalline ink of copper and indium aluminium sulphur is coated in by knife coating plating Mo matrix
On, the thick nanocrystalline presoma prefabricated membranes of Cu-In-Al-Se of 2000nm are formed, is subsequently put on 300 DEG C of electric hot plate and dries.Dry
The diethyl selenide of Cu-In-Al-Se presoma prefabricated membrane prefabricated membrane and slightly excessive (5mmol) after dry is placed in graphite, then
The stone mill box is placed in tube furnace, Ar gas is passed through, the air in stove is drained, and Ar is full of furnace chamber.Then with 12 DEG C/min
Programming rate, give body of heater heating, cavity temperature is risen rapidly to 590 DEG C, then Cu-In-Al-Se presoma prefabricated membrane entered
The showing tremendous enthusiasm processing of row selenizing.Stop heating after 40min, and be cooled to room temperature, finally obtain the Cu-In-Al-Se with gradient distribution thin
Film.
Embodiment five
(1) preparation of copper and indium aluminium sulphur nano particle：By 3.0mmol copper acetates, 2.60mmol indium acetates, 0.40mmol nitric acid
Aluminium aluminium and 9.0mmol sulphur urines are added in 100mL three-necked bottles, add 35mL oleyl amines, and are put into temperature control heating set, then with history
Rec air interchanger is connected, and is heated.Reaction solution is circulated by way of vacuum and argon atmosphere circulation simultaneously and washed
Gas 2 times, each gas washing 15min.Finally reaction vessel is full of with argon gas.Under magnetic stirring, continue to heat, when temperature is increased to
250 DEG C, keep constant, stop reaction after 60min.Room temperature is then cooled to, filter centrifugation reaction solution obtains solid product, is used in combination
Ethanol, hexane are cleaned 5 times, obtain clean solid product.
(2) the nanocrystalline ink of copper and indium aluminium sulphur is prepared：Copper and indium aluminium sulphur nano particle, which is put into formation concentration in toluene, is
Colloidal solution-nanocrystalline ink of copper and indium aluminium sulphur stable 200mg/mL.
(3) preparation of molybdenum glass is plated：Quartz glass substrate is cut into 1.0cm × 2.0cm sizes, respectively with acetone, ethanol,
Deionized water excusing from death is cleaned up.Metal Mo is plated on quartz glass substrate by direct current magnetron sputtering process, thickness is 500nm；
Then the metal Mo films containing Al that a layer thickness is 300mn are deposited by cosputtering method, the wherein content of aluminium is 10%.
(4) preparation of copper indium aluminum selenium membrane：The nanocrystalline ink of copper and indium aluminium sulphur is coated in by knife coating plating Mo matrix
On, the thick nanocrystalline presoma prefabricated membranes of Cu-In-Al-Se of 3000nm are formed, is subsequently put on 300 DEG C of electric hot plate and dries.Dry
The diethyl selenide of Cu-In-Al-Se presoma prefabricated membrane prefabricated membrane and slightly excessive (5mmol) after dry is placed in graphite, then
The stone mill box is placed in tube furnace, Ar gas is passed through, the air in stove is drained, and Ar is full of furnace chamber.Then with 15 DEG C/min
Programming rate, give body of heater heating, cavity temperature is risen rapidly to 580 DEG C, then Cu-In-Al-Se presoma prefabricated membrane entered
The showing tremendous enthusiasm processing of row selenizing.Stop heating after 80min, and be cooled to room temperature, finally obtain the Cu-In-Al-Se with gradient distribution thin
Film.
Embodiment six
(1) preparation of copper and indium aluminium sulphur nano particle：By 1.0mmol acetylacetone coppers, 0..70mmol Indium Tris acetylacetonates,
0.30mmol aluminum nitrates and 3.0mmol sulphur powders are added in 100mL three-necked bottles, add 35mL oleyl amines, and be put into temperature control heating set
In, then connected with Shrek air interchanger, and heat.Simultaneously to reaction solution by way of vacuum and argon atmosphere circulation
It is circulated gas washing 2 times, each gas washing 15min.Finally reaction vessel is full of with argon gas.Under magnetic stirring, continue to heat,
When temperature is increased to 200 DEG C, keeps constant, stop reaction after 80min.Room temperature is then cooled to, filter centrifugation reaction solution is obtained
Solid product, and cleaned 5 times with ethanol, hexane, obtain clean solid product.
(2) the nanocrystalline ink of copper and indium aluminium sulphur is prepared：Copper and indium aluminium sulphur nano particle, which is put into formation concentration in toluene, is
Colloidal solution-nanocrystalline ink of copper and indium aluminium sulphur stable 280mg/mL.
(3) preparation of molybdenum glass is plated：Quartz glass substrate is cut into 1.0cm × 2.0cm sizes, respectively with acetone, ethanol,
Deionized water excusing from death is cleaned up.Metal Mo is plated on quartz glass substrate by direct current magnetron sputtering process, thickness is 500nm；
Then the metal Mo films containing Al that a layer thickness is 250mn are deposited by cosputtering method, the wherein content of aluminium is 10%.
(4) preparation of copper indium aluminum selenium membrane：The nanocrystalline ink of copper and indium aluminium sulphur is coated in by knife coating plating Mo matrix
On, the thick nanocrystalline presoma prefabricated membranes of Cu-In-Al-Se of 1500nm are formed, is subsequently put on 300 DEG C of electric hot plate and dries.Dry
The diethyl selenide of Cu-In-Al-Se presoma prefabricated membrane prefabricated membrane and slightly excessive (5mmol) after dry is placed in graphite, then
The stone mill box is placed in tube furnace, Ar gas is passed through, the air in stove is drained, and Ar is full of furnace chamber.Then with 15 DEG C/min
Programming rate, give body of heater heating, cavity temperature is risen rapidly to 530 DEG C, then Cu-In-Al-Se presoma prefabricated membrane entered
The showing tremendous enthusiasm processing of row selenizing.Stop heating after 30min, and be cooled to room temperature, finally obtain the Cu-In-Al-Se with gradient distribution thin
Film.
Embodiment seven
(1) preparation of copper and indium aluminium sulphur nano particle：By 2.0mmol copper acetates, 1.70mmol indium acetates, 0.30mmol acetic acid
Aluminium and 5.0mmol sulphur powders are added in 100mL three-necked bottles, add 35mL oleyl amines, and are put into temperature control heating set, then with history Lay
Gram air interchanger is connected, and is heated.Gas washing 2 is circulated to reaction solution by way of vacuum and argon atmosphere circulation simultaneously
It is secondary, each gas washing 15min.Finally reaction vessel is full of with argon gas.Under magnetic stirring, continue to heat, when temperature is increased to 230
DEG C, keep constant, stop reaction after 60min.Room temperature is then cooled to, filter centrifugation reaction solution obtains solid product, and uses second
Alcohol, hexane are cleaned 5 times, obtain clean solid product.
(2) the nanocrystalline ink of copper and indium aluminium sulphur is prepared：Copper and indium aluminium sulphur nano particle, which is put into formation concentration in toluene, is
Colloidal solution-nanocrystalline ink of copper and indium aluminium sulphur stable 180mg/mL.
(3) preparation of molybdenum glass is plated：Quartz glass substrate is cut into 1.0cm × 2.0cm sizes, respectively with acetone, ethanol,
Deionized water excusing from death is cleaned up.Metal Mo is plated on quartz glass substrate by direct current magnetron sputtering process, thickness is 500nm；
Then the metal Mo films containing Al that a layer thickness is 280mn are deposited by cosputtering method, the wherein content of aluminium is 8%.
(4) preparation of copper indium aluminum selenium membrane：The nanocrystalline ink of copper and indium aluminium sulphur is coated in by knife coating plating Mo matrix
On, the thick nanocrystalline presoma prefabricated membranes of Cu-In-Al-Se of 2000nm are formed, is subsequently put on 300 DEG C of electric hot plate and dries.Dry
The diethyl selenide of Cu-In-Al-Se presoma prefabricated membrane prefabricated membrane and slightly excessive (5mmol) after dry is placed in graphite, then
The stone mill box is placed in tube furnace, Ar gas is passed through, the air in stove is drained, and Ar is full of furnace chamber.Then with 15 DEG C/min
Programming rate, give body of heater heating, cavity temperature is risen rapidly to 530 DEG C, then Cu-In-Al-Se presoma prefabricated membrane entered
The showing tremendous enthusiasm processing of row selenizing.Stop heating after 30min, and be cooled to room temperature, finally obtain the Cu-In-Al-Se with gradient distribution thin
Film.
Embodiment eight
(1) preparation of copper and indium aluminium sulphur nano particle：By 2.0mmol copper nitrates, 1.70mmol indium nitrates, 0.30mmol nitric acid
Aluminium and 6.0mmol sulphur powders are added in 100mL three-necked bottles, add 35mL oleyl amines, and are put into temperature control heating set, then with history Lay
Gram air interchanger is connected, and is heated.Gas washing 2 is circulated to reaction solution by way of vacuum and argon atmosphere circulation simultaneously
It is secondary, each gas washing 15min.Finally reaction vessel is full of with argon gas.Under magnetic stirring, continue to heat, when temperature is increased to 235
DEG C, keep constant, stop reaction after 100min.Room temperature is then cooled to, filter centrifugation reaction solution obtains solid product, and uses second
Alcohol, hexane are cleaned 5 times, obtain clean solid product.
(2) the nanocrystalline ink of copper and indium aluminium sulphur is prepared：It is 80mg/ that copper and indium aluminium sulphur nano particle, which is put into toluene, and forms concentration
Colloidal solution-nanocrystalline ink of copper and indium aluminium sulphur stable mL.
(3) preparation of molybdenum glass is plated：Quartz glass substrate is cut into 1.0cm × 2.0cm sizes, respectively with acetone, ethanol,
Deionized water excusing from death is cleaned up.Metal Mo is plated on quartz glass substrate by direct current magnetron sputtering process, thickness is 800nm；
Then the metal Mo films containing Al that a layer thickness is 500mn are deposited by cosputtering method, the wherein content of aluminium is 12%.
(4) preparation of copper indium aluminum selenium membrane：The nanocrystalline ink of copper and indium aluminium sulphur is coated in by knife coating plating Mo matrix
On, the thick nanocrystalline presoma prefabricated membranes of Cu-In-Al-Se of 1500nm are formed, is subsequently put on 300 DEG C of electric hot plate and dries.Dry
The diethyl selenide of Cu-In-Al-Se presoma prefabricated membrane prefabricated membrane and slightly excessive (5mmol) after dry is placed in graphite, then
The stone mill box is placed in tube furnace, Ar gas is passed through, the air in stove is drained, and Ar is full of furnace chamber.Then with 18 DEG C/min
Programming rate, give body of heater heating, cavity temperature is risen rapidly to 520 DEG C, then Cu-In-Al-Se presoma prefabricated membrane entered
The showing tremendous enthusiasm processing of row selenizing.Stop heating after 30min, and be cooled to room temperature, finally obtain the Cu-In-Al-Se with gradient distribution thin
Film.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, all essences in the present invention
Any modification, equivalent and improvement made within refreshing and principle etc., should be included within the scope of the present invention.
Claims (8)
1. a kind of preparation method with the copper indium aluminum selenium membrane that can be distributed with gradient, comprises the following steps：
Copper source compound, aluminum source compound, indium source compound, sulphur source and oleyl amine are mixed, copper and indium aluminium sulphur nano particle is synthesized, its
In, aluminium, phosphide element molar content ratio are：0<Aluminium/(indium+aluminium)<40%, the synthesis temperature of the copper and indium aluminium sulphur nano particle
For 180-280 DEG C；
The copper and indium aluminium sulphur nano particle is scattered in organic solvent, it is configured to the nanocrystalline ink of copper and indium aluminium sulphur；
On the matrix that the nanocrystalline ink of copper and indium aluminium sulphur is coated in plating bilayer Mo, Cu-In-Al-Se presoma prefabricated membrane is formed,
Wherein, the matrix of the plating bilayer Mo is the matrix for the Mo layers for being sequentially depositing pure Mo layers and mixing aluminium；
The Cu-In-Al-Se presoma prefabricated membrane is obtained into copper indium aluminum selenium membrane by selenizing, annealing.
2. the preparation method according to claim 1 with the copper indium aluminum selenium membrane that can be distributed with gradient, it is characterised in that：
In the preparation process of Cu-In-Al-Se presoma prefabricated membrane, in the matrix of the plating bilayer Mo, the Mole percent of aluminium in Mo layers of aluminium is mixed
Content is 0.5-15%.
3. the preparation method according to claim 1 or 2 with the copper indium aluminum selenium membrane that can be distributed with gradient, its feature exists
In：In the preparation process of Cu-In-Al-Se presoma prefabricated membrane, in the matrix of the plating bilayer Mo, aluminium Mo thickness degree is mixed for 20-
500nm。
4. the preparation method as claimed in claim 1 with the copper indium aluminum selenium membrane that can be distributed with gradient, it is characterised in that：Institute
State synthesis copper and indium aluminium sulphur nano particle the step of in, copper source compound, aluminum source compound, indium source compound be respectively containing
At least one in copper, aluminium, the chlorate of indium, acetate, acetylacetonate, oxide；The sulphur source be sulphur powder, hydrogen sulfide,
At least one in carbon disulfide, thiocarbamide.
5. the preparation method according to claim 1 with the copper indium aluminum selenium membrane that can be distributed with gradient, it is characterised in that：
It is described the step of be configured to copper and indium aluminium sulphur nanocrystalline ink in, the nanocrystalline body of copper and indium aluminium sulphur is 10-300mg/mL.
6. the preparation method according to claim 1 with the copper indium aluminum selenium membrane that can be distributed with gradient, it is characterised in that：
It is described the step of be configured to copper and indium aluminium sulphur nanocrystalline ink in, the organic solvent is amine, benzene class or alkanethiol class compound
In at least one.
7. the preparation method according to claim 1 with the copper indium aluminum selenium membrane that can be distributed with gradient, it is characterised in that：
During the selenizing, selenizing temperature is 500-600 DEG C, and the selenizing time is 10-90min.
8. the preparation method with the copper indium aluminum selenium membrane that can be distributed with gradient according to claim 1 or 7, its feature exists
In：The selenium source used during the selenizing is at least one in selenium powder, hydrogen selenide, diethyl selenide.
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