CN103626495A - Preparation method for CIGS target material through pressureless sintering - Google Patents
Preparation method for CIGS target material through pressureless sintering Download PDFInfo
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Abstract
The invention relates to a preparation method for a CIGS target material through pressureless sintering. The preparation method comprises the following steps: preparing selenium-lacked CIGS(1-delta) powder: weighing a copper source, an indium source, a gallium source and a selenium source respectively according to stoichiometric ratio of the CIGS(1-delta), mixing, then performing vacuum packaging, performing reaction at the temperature of 900 to 1100 DEG C for 1 to 10 hours, and preparing CIGS(1-delta) powder comprising a second phase (In(1-x)Gax)Se, wherein delta is the selenium lacking ratio, and is lager than 0 and less than 1, and x is larger than or equal to 0 and less than or equal to 0.5; preparing precursor powder: fully blending the obtained CIGS(1-delta) powder and Se powder according to the respective Se element ratio of (1-delta):delta, smashing to a regulated granularity, and preparing the precursor powder; performing compression moulding: performing compression moulding on the precursor powder, and obtaining a precursor block; performing pressureless sintering: putting the precursor block in a sintering furnace under sealed protective atmosphere with negative pressure, and conducting pressureless sintering so as to obtain the CIGS target material.
Description
Technical field
The present invention relates to the technology of preparing of mineral compound ceramic target, relate generally to the preparation method of copper-indium-galliun-selenium (CIGS) thin film solar cell light absorption layer forerunner target, belong to photovoltaic material technical field of new energies.
Background technology
The energy and environment are two great strategy problems of human social, and it is more and more important and urgent that the development and utilization of clean reproducible energy seems.Sun power is a kind of clean, abundant and be not subject to the renewable energy source of regional limits, the effective exploitation of sun power and utilize tool to be of great significance.Solar cell is one of mankind's principal mode of effectively utilizing sun power.Copper-indium-galliun-selenium (Cu (In, Ga) Se
2, be called for short CIGS) thin film solar cell is the most promising solar cell of a new generation, it has, and cost is low, efficiency is high, the life-span is long, low light level performance is good, capability of resistance to radiation by force, can flexibility and many-sided advantage such as environmental friendliness.Since the nineties in 20th century, CIGS, in all thin film solar cells, is just the highest thin film solar cell of laboratory efficiency of conversion always.In April, 2008, the Repins for 19.9%(Ingrid is refreshed, Miguel A.Contreras, Brian Egaas by the high conversion efficiency in its laboratory again in U.S.'s renewable energy source laboratory (NREL), Clay DeHart, John Scharf, Craig L.Perkins, Bobby To and Rommel Noufi, Progress in Photovoltaics:Research and Applications, 16 (3), 235-239,2008); In January, 2013, Swiss Confederation's Materials science and technology experiment chamber Empa announce, the flexible substrate CIGS solar-energy photo-voltaic cell of its research and development has relied on 20.4% high conversion efficiency to refresh world record.
The preparation of CIGS light absorbing zone is the core process of CIGS thin film solar cell.The main technique that at present industrial community is prepared CIGS light absorbing zone comprises selenizing method and evaporation-sputter hydridization method etc. after method of evaporation, magnetron sputtering C u-In-Ga prefabricated membrane.But these methods all inevitably there will be volatile middle phase in the preparation process of film, make the final actual constituent of film and nominal composition difference very large; And because the factors such as the dividing potential drop of the generation of phase in the middle of volatile and evaporation rate and temperature, air pressure, volatile matter and airflow on surface state are all closely related, the fluctuation of uncontrollable factor in Temperature in Large Area field (dividing potential drop, air-flow condition etc.), can cause large area film composition to occur uncontrollable variation, thereby cause the homogeneity of film and repeatability to be all difficult to control, the production yield of battery cannot be guaranteed, and has seriously restricted the extensive expansion that industrialization is produced.
CIGS ceramic target sputtering method has started to be used to prepare CIGS light absorbing zone in recent years, can substantially solve the poor problem of film composition controllability.CIGS ceramic target mainly adopts high temperature hot pressing technique to prepare (such as referring to Chinese patent CN102199751A, CN102463349A, CN103014623A, CN101397647B etc.) at present, the method forming, density is high, but cost is higher, be not easy to the preparation of large size CIGS target simultaneously.Based on CIGS material self character, the CIGS ceramic plate density of high temperature pressure-free sintering is extremely low, cannot be as sputtering target material normal use.
Therefore, develop a kind of novel preparation process to overcome the defect of aforesaid method, the industrialization of CIGS thin-film solar cell is undoubtedly to a kind of huge promotion, tool is of great significance.
Summary of the invention
In the face of the problem that prior art exists, the object of the present invention is to provide a kind of preparation method of copper-indium-galliun-selenium (CIGS) target of can be simply, easily producing in batches.
At this, the invention provides a kind of pressureless sintering preparation method of CIGS target material, comprising:
(1) CIGS of selenium position disappearance
1-δthe preparation of powder: press CIGS
1-δstoichiometric ratio take respectively ,Jia source, ,Yin source, copper source and selenium source, mix final vacuum encapsulation, in 900～1100 ℃ of reactions, within 1～10 hour, make and comprise the second phase (In
1-xga
x) CIGS of Se
1-δpowder, wherein, δ is selenium disappearance ratio, 0< δ <1,0≤x≤0.5;
(2) preparation of precursor powder: by gained CIGS
1-δpowder and Se powder are (1-δ) in the ratio of Se element separately: the ratio of δ fully mixes and is crushed to designated size and makes precursor powder;
(3) compression moulding: described precursor powder compression moulding is made to forerunner's block; And
(4) pressureless sintering: described forerunner's block is placed on and carries out pressureless sintering in the sintering oven under the protective atmosphere of airtight and negative pressure and make CIGS target material.
The present invention prepares the CIGS that lacks selenium by design
1-δpowder, makes CIGS
1-δin powder, produce the second phase (In
1- xga
x) Se, (the In of low melting point
1-xga
x) Se can effectively reduce CIGS
1-δthe fusing point of powder, induction CIGS
1-δin the reaction sintering process with simple substance selenium, CIGS particle is in conjunction with finer and close, and the decomposition of CIGS when lower temperature of reaction has been avoided high temperature simultaneously finally obtains forming, CIGS target that density is high, and energy consumption is little, and cost is low.
Preferably, described CIGS
1-δmolecular formula can be: Cu (In
1-xga
x) Se
2-y, 0≤x≤0.5 wherein, 0.1≤y≤0.6; Cu (In
1-xga
x)
5se
8-z, 0≤x≤0.5 wherein, 0.5≤z≤2.5; Or Cu (In
1-xga
x)
3se
5-w, 0≤x≤0.5 wherein, 0.5≤w≤1.5.
Preferably, described copper source is any one or the two or more combination in elemental copper, copper selenide, selenkupfer, CuIn alloy, CuGa alloy, CuInGa alloy and copper-indium-galliun-selenium.
Preferably, described indium source is any one or the two or more combination in simple substance indium, indium selenide, indium selenide gallium, CuIn alloy, InGa alloy, CuInGa alloy and copper-indium-galliun-selenium.
Preferably, described gallium source is any one or the two or more combination in Metallic Gallium, gallium selenide, indium selenide gallium, InGa alloy, CuGa alloy, CuInGa alloy and copper-indium-galliun-selenium.
Preferably, described selenium source is any one or the two or more combination in simple substance selenium, copper selenide, selenkupfer, indium selenide, gallium selenide, indium selenide gallium and copper-indium-galliun-selenium.
Preferably, described designated size can be 100 orders.
Preferably, the method for described compacting can be cold press process, isostatic pressing method or cold pressing after the static pressure facture such as carry out again.
Preferably, described protective atmosphere is argon gas and/or nitrogen.Described negative pressure can be 1 below normal atmosphere.
Preferably, the sintering temperature of described pressureless sintering is 680～950 ℃, and sintering time is 0.5～10 hour.
Preferably, in step (4), before the heating that heats up, first the furnace chamber of described sintering oven found time and thoroughly oxygen and steam removed with rare gas element.
Preferably, when pressureless sintering, at described forerunner's block periphery, place simple substance selenium powder grain, described simple substance selenium powder grain is 0～0.2 with the mass ratio that is mixed in the simple substance selenium in described forerunner's block.
Relatively high pressure sintering or general pressureless sintering, beneficial effect of the present invention is, can obtain fine and close CIGS target, is suitable for that large size preparation, energy consumption are little, low of cost, controllability are good, be easy to large-scale production.
Accompanying drawing explanation
Fig. 1 is the CIGS of the selenium position disappearance that makes in embodiment 1
1-δpowder (Cu (In
0.7ga
0.3)
5se
6) X-ray diffractogram;
Fig. 2 is the prepared Cu (In of embodiment 1
0.7ga
0.3)
5se
8the X-ray diffractogram of target;
Fig. 3 is the prepared Cu (In of embodiment 1
0.7ga
0.3)
5se
8the SEM scanning electron microscope (SEM) photograph of target section.
Embodiment
Below in conjunction with accompanying drawing and following embodiment, further illustrate the present invention, should be understood that accompanying drawing and following embodiment are only for the present invention is described, and unrestricted the present invention.
The invention provides a kind of can be simply, the easy preparation method of copper-indium-galliun-selenium (CIGS) target of batch production.Particularly, as example, preparation method of the present invention can comprise the following steps.
(1) CIGS of selenium position disappearance
1-δthe preparation of powder: press CIGS
1-δthe stoichiometric ratio of (0< δ <1) takes respectively ,Jia source, ,Yin source, copper source and selenium source, carries out the CIGS that solid state reaction (for example reacting at 900～1050 ℃ 1～10 hour) is prepared selenium position disappearance after mixing
1-δpowder, gained powder comprises the second phase (In
1-xga
x) Se.
In one example, the molecular formula of copper-indium-galliun-selenium to be prepared (CIGS) target is Cu (In
1-xga
x) Se
2, the CIGS of designed selenium position disappearance
1-δmolecular formula be Cu (In
1-xga
x) Se
2-y, 0≤x≤0.5 wherein, 0.1≤y≤0.6.
In another example, the molecular formula of copper-indium-galliun-selenium to be prepared (CIGS) target is Cu (In
1-xga
x)
5se
8, the CIGS of designed selenium position disappearance
1-δmolecular formula be Cu (In
1-xga
x)
5se
8-z, 0≤x≤0.5 wherein, 0.5≤z≤2.5.
In another example, the molecular formula of copper-indium-galliun-selenium to be prepared (CIGS) target is Cu (In
1-xga
x)
3se
5, the CIGS of designed selenium position disappearance
1-δmolecular formula be Cu (In
1-xga
x)
3se
5-w, 0≤x≤0.5 wherein, 0.5≤w≤1.5.
The copper source adopting can be any one or the two or more combination in elemental copper, copper selenide, selenkupfer, CuIn alloy, CuGa alloy, CuInGa alloy and copper-indium-galliun-selenium.
The indium source adopting can be any one or the two or more combination in simple substance indium, indium selenide, indium selenide gallium, CuIn alloy, InGa alloy, CuInGa alloy and copper-indium-galliun-selenium.
The gallium source adopting can be any one or the two or more combination in Metallic Gallium, gallium selenide, indium selenide gallium, InGa alloy, CuGa alloy, CuInGa alloy and copper-indium-galliun-selenium.
The selenium source adopting can be any one or the two or more combination in simple substance selenium, copper selenide, selenkupfer, indium selenide, gallium selenide, indium selenide gallium and copper-indium-galliun-selenium.
Wherein, ,Jia source, ,Yin source, copper source and selenium source can be respectively from different materials, can be also two or more from same substance in ,Jia source, ,Yin source, copper source and selenium source.For example, can adopt respectively elemental copper, simple substance indium, Metallic Gallium, simple substance selenium as ,Jia source, ,Yin source, copper source, selenium source.Or can adopt elemental copper as copper source, adopt InGa alloy as He Jia source, indium source, adopt simple substance selenium as selenium source.Or can adopt selenkupfer as copper source and the first selenium source, adopt simple substance selenium as the second selenium source, adopt respectively simple substance indium and Metallic Gallium as He Jia source, indium source.Or can adopt elemental copper as copper source, adopt indium selenide gallium as ,Jia source, indium source and selenium source.Should be understood that above each combination is only as example, the ,Jia source, ,Yin source, copper source and the selenium source that in the present invention, adopt also comprise other various combinations.
(2) preparation of precursor powder: by the CIGS of the selenium position disappearance making
1-δthe simple substance selenium of powder and stoichiometric ratio (, makes CIGS
1-δin powder, the mass ratio of the quality of Se element and simple substance selenium is (1-δ): δ) fully mix and be crushed to designated size and make precursor powder.Grinding mode is such as being grinding, ball milling etc.Designated size can be for example 100 orders.
(3) compression moulding: precursor powder is transferred in mould and is pressed, obtain forerunner's block after the demoulding.The size and shape of mould can be selected as required.The method of compacting can be cold press process, isostatic pressing method or cold pressing after the static pressure facture such as carry out again.For example, cold press process can be that precursor powder is placed in steel die under the pressure of 10～30MPa to pressurize 1～5 minute.Isostatic pressing method can be that precursor powder is placed in isostatic tooling under 1500～2500 newton's pressure to pressurize 1～5 minute.
(4) pressureless sintering: forerunner's block of moulding is positioned in sintering oven; airtightly rear furnace chamber is found time and used shielding gas (for example argon gas and/or nitrogen) thoroughly oxygen vapor to be removed; by the air pressure adjustment in furnace chamber, be negative pressure (for example 1 normal atmosphere is following) subsequently; then be warming up to 680～950 ℃ of insulations and carry out sintering in 0.5～10 hour, then be down to room temperature and make copper-indium-galliun-selenium (CIGS) target.In addition, before sintering oven is airtight, can also place simple substance selenium powder grain at forerunner's block periphery, its quality can be controlled at 0～0.2 with the mass ratio that is mixed in the simple substance selenium in forerunner's block.By means of this, can evenly supplement the selenium losing because of evaporation.
< sample characterization >
Gained sample of the present invention is passed through to scanning electron microscope (JSM-6510) viewing film surface topography; By x-ray powder diffraction instrument (Bruker-AXS/D8Advance), analyze phase; Adopt GH-120C drainage Density Measuring Instrument to measure the density of gained target.
Fig. 1 illustrates the CIGS making in example of the present invention
1-δthe X-ray diffractogram of powder, as seen from the figure, at CIGS
1-δin powder, produced the second phase (In
1-xga
x) Se.(the In of low melting point
1-xga
x) Se can effectively reduce CIGS
1-δthe fusing point of powder, induction CIGS
1-δin the reaction sintering process with simple substance selenium, CIGS particle is in conjunction with finer and close, and the decomposition of CIGS when lower temperature of reaction has been avoided high temperature simultaneously finally obtains forming, CIGS target that density is high, and energy consumption is little, and cost is low.Fig. 2 illustrates the X-ray diffractogram of a prepared CIGS target of example of the present invention, as seen from the figure, in this CIGS target, there is no dephasign.Fig. 2 illustrates the SEM scanning electron microscope (SEM) photograph of the prepared CIGS target of an example section of the present invention, and as seen from the figure, this CIGS target section is fine and close.In addition, known after tested, the relative density of CIGS target of the present invention is more than 0.91.Therefore, CIGS target of the present invention can be used as sputtering target material application.
The present invention prepares the CIGS that lacks selenium by design
1-δpowder, makes CIGS
1-δin powder, produce the second phase (In
1- xga
x) Se, (the In of low melting point
1-xga
x) Se can effectively reduce CIGS
1-δthe fusing point of powder, induction CIGS
1-δat the reaction sintering with simple substance selenium, obtain in CIGS process, CIGS particle is in conjunction with finer and close, and the decomposition of CIGS when lower temperature of reaction has been avoided high temperature simultaneously finally obtains forming, CIGS target that density is high.Relatively high pressure sintering or general pressureless sintering, beneficial effect of the present invention is, can obtain fine and close CIGS target, is suitable for that large size preparation, energy consumption are little, low of cost, controllability are good, be easy to large-scale production.
Further exemplify embodiment below to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The processing parameters such as the quality that following example is concrete, temperature, pressure, time are only also examples in OK range, be that those skilled in the art can be done in suitable scope and be selected by explanation herein, and do not really want to be defined in the below concrete numerical value of example.
Embodiment 1
Press Cu (In
0.7ga
0.3)
5se
6stoichiometric ratio in formula is got simple substance Cu19.06g, In24.11g, Ga6.28g and Se142.13g, is placed in quartz reaction container and Vacuum Package.After fully shaking up, transfer to and in stove, under 930 ℃ of conditions, react 3h and obtain Cu (In
0.7ga
0.3)
5se
6, its XRD test data (referring to Fig. 1) shows the In of low melting point
0.7ga
0.3se second-phase exists.Cu (the In that negate should obtain
0.7ga
0.3)
5se
695.79g, after interpolation simple substance Se23.69g, fully grinding evenly to 100 order obtains black precursor.Precursor is transferred in the steel die that diameter is 86mm, and under 20MPa pressure pressurize 2min, the demoulding obtains the precursor disk of moulding.Shift precursor disk to stove, periphery is placed 2g simple substance selenium, then stove is carried out airtightly, adopts to vacuumize the mode that is filled with again argon gas and remove oxygen and steam, subsequently by the normal atmosphere of the air pressure adjustment to 0.1 in stove chamber.Stove is warming up to 800 ℃ and be incubated 5h, is down to room temperature and finally obtains Cu (In
0.7ga
0.3)
5se
8target, its XRD test data (referring to Fig. 2) shows does not have dephasign, SEM test (referring to Fig. 3) shows Cu (In
0.7ga
0.3)
5se
8target section is fine and close.Known after tested, the relative density of the CIGS target that the present embodiment makes is 0.95.
Embodiment 2
Press Cu (In
0.8ga
0.2) Se
1.6stoichiometric ratio in formula is got simple substance Cu31.77g, In45.93g, Ga6.97g and Se63.17g, is placed in quartz reaction container and Vacuum Package.After fully shaking up, transfer in stove and react 5h under 1030 ℃ of conditions.Cu (the In that negate should obtain
0.8ga
0.2) Se
1.688.70g, after interpolation simple substance Se9.48g, fully grinding evenly to 100 order obtains black precursor.Precursor is transferred in the steel die that diameter is 86mm, and under 20MPa pressure pressurize 2min, the demoulding obtains the precursor disk of moulding.Shift precursor disk to stove, periphery is placed 1.0g simple substance selenium, then stove is carried out airtightly, adopts to vacuumize the mode that is filled with again argon gas and remove oxygen and steam, subsequently by the normal atmosphere of the air pressure adjustment to 0.2 in stove chamber.Stove is warming up to 950 ℃ and be incubated 0.5h, is down to room temperature and finally obtains Cu (In
0.8ga
0.2) Se
2target.Known after tested, the relative density of the CIGS target that the present embodiment makes is 0.92.
Embodiment 3
Press Cu (In
0.5ga
0.5)
3se
3.5stoichiometric ratio in formula is got simple substance Cu63.55g, In172.23g, Ga104.58g and Se276.36g, is placed in quartz reaction container and Vacuum Package.After fully shaking up, transfer in stove and react 2h under 980 ℃ of conditions.Cu (the In that negate should obtain
0.5ga
0.5)
3se
3.5308.36g, after interpolation simple substance Se59.22g, fully grinding evenly to 100 order obtains black precursor.Precursor is transferred in the isostatic tooling of 250 * 125mm, and under 2000 newton's pressure pressurize 2min, the demoulding obtains rectangular of the precursor of moulding.Periphery is placed 5g simple substance Se to stove to shift rectangular of precursor, then stove is carried out airtightly, adopts to vacuumize the mode that is filled with again argon gas and remove oxygen and steam, subsequently by the normal atmosphere of the air pressure adjustment to 0.5 in stove chamber.Stove is warming up to 850 ℃ and be incubated 6h, is down to room temperature and finally obtains Cu (In
0.5ga
0.5)
3se
5target.Known after tested, the relative density of the CIGS target that the present embodiment makes is 0.93.
Embodiment 4
Press Cu (In
0.7ga
0.3)
5se
6stoichiometric ratio in formula is got simple substance Cu19.06g, In24.11g, Ga6.28g and Se142.13g, is placed in quartz reaction container and Vacuum Package.After fully shaking up, transfer in stove and react 3h under 930 ℃ of conditions.Cu (the In that negate should obtain
0.7ga
0.3)
5se
695.79g, after interpolation simple substance Se23.69g, fully grinding evenly to 100 order obtains black precursor.Precursor is transferred in the steel die that diameter is 86mm, and under 20MPa pressure pressurize 2min, the demoulding obtains the precursor disk of moulding.Shift precursor disk to stove, then stove is carried out airtightly, adopt to vacuumize the mode that is filled with again argon gas and remove oxygen and steam, subsequently by air pressure adjustment to 0.8 normal atmosphere in stove chamber.Stove is warming up to 680 ℃ and be incubated 10h, is down to room temperature and finally obtains Cu (In
0.7ga
0.3)
5se
8target.Known after tested, the relative density of the CIGS target that the present embodiment makes is 0.91.
Embodiment 5
Press Cu (In
0.8ga
0.2) Se
1.8stoichiometric ratio in formula is got simple substance Cu31.77g, In
0.8ga
0.248.39g and Se71.06g, be placed in quartz reaction container and Vacuum Package.After fully shaking up, transfer in stove and react 4h under 1050 ℃ of conditions.Cu (the In that negate should obtain
0.8ga
0.2) Se
1.890.74g, after interpolation simple substance Se4.47g, fully grinding evenly to 100 order obtains black precursor.Precursor is transferred in the steel die that diameter is 86mm, and under 20MPa pressure pressurize 2min, the demoulding obtains the precursor disk of moulding.Shift precursor disk to stove, periphery is placed 0.4g simple substance selenium, then stove is carried out airtightly, adopts to vacuumize the mode that is filled with again argon gas and remove oxygen and steam, subsequently by the normal atmosphere of the air pressure adjustment to 0.2 in stove chamber.Stove is warming up to 950 ℃ and be incubated 2h, is down to room temperature and finally obtains Cu (In
0.8ga
0.2) Se
2target.Known after tested, the relative density of the CIGS target that the present embodiment makes is 0.93.
Embodiment 6
Press Cu (In
0.7ga
0.3)
5se
7stoichiometric ratio in formula is got Cu
2se16.48g, In64.30g, Ga16.73g and Se82.12g, be placed in quartz reaction container and Vacuum Package.After fully shaking up, transfer in stove and react 8h under 980 ℃ of conditions.Cu (the In that negate should obtain
0.7ga
0.3)
5se
740g, after interpolation simple substance Se2.82g, fully grinding evenly to 100 order obtains black precursor.Precursor is transferred in the steel die that diameter is 55mm, and under 10MPa pressure pressurize 1.5min, the demoulding obtains the precursor disk of moulding.Shift precursor disk to stove, periphery is placed 0.56g simple substance selenium, then stove is carried out airtightly, adopts to vacuumize the mode that is filled with again argon gas and remove oxygen and steam, subsequently by air pressure adjustment to 0.3 normal atmosphere in stove chamber.Stove is warming up to 850 ℃ and be incubated 5h, is down to room temperature and finally obtains Cu (In
0.7ga
0.3)
5se
8target.Known after tested, the relative density of the CIGS target that the present embodiment makes is 0.93.
Embodiment 7
Press CuInSe
1.8stoichiometric ratio in formula is got simple substance Cu15.25g, Cu
2se37.29g, In
2se
3139.95g, is placed in quartz reaction container and Vacuum Package.After fully shaking up, transfer in stove and react 5h under 1050 ℃ of conditions.The CuInSe that negate should obtain
1.896.14g, after interpolation simple substance Se4.74g, fully grinding evenly to 100 order obtains black precursor.Precursor is transferred in the steel die that diameter is 86mm, and under 20MPa pressure pressurize 3min, the demoulding obtains the precursor disk of moulding.Shift precursor disk to stove, periphery is placed 0.5g simple substance Se, then stove is carried out airtightly, adopts to vacuumize the mode that is filled with again argon gas and remove oxygen and steam, subsequently by the normal atmosphere of the air pressure adjustment to 0.4 in stove chamber.Stove is warming up to 900 ℃ and be incubated 5h, is down to room temperature and finally obtains CuInSe
2target.Known after tested, the relative density of the CIGS target that the present embodiment makes is 0.94.
Embodiment 8
Press Cu (In
0.9ga
0.1)
3se
4.5stoichiometric ratio in formula is got simple substance Cu38.13g and (In
0.9ga
0.1) Se
3411.75g, is placed in quartz reaction container and Vacuum Package.After fully shaking up, transfer in stove and react 5h under 1000 ℃ of conditions.Cu (the In that negate should obtain
0.9ga
0.1)
3se
4.5330g, after interpolation simple substance Se17.38g, fully grinding evenly to 100 order obtains black precursor.Precursor is transferred in the steel die that is of a size of 150 * 150mm, and under 25MPa pressure pressurize 5min, the demoulding obtains the precursor square piece of moulding.Shift precursor square piece to stove, periphery is placed 3g simple substance selenium, then stove is carried out airtightly, adopts to vacuumize the mode that is filled with again argon gas and remove oxygen and steam, subsequently by the normal atmosphere of the air pressure adjustment to 0.05 in stove chamber.Stove is warming up to 900 ℃ and be incubated 1.5h, is down to room temperature and finally obtains Cu (In
0.9ga
0.1)
3se
5target.Known after tested, the relative density of the CIGS target that the present embodiment makes is 0.92.
Embodiment 9
Press Cu (In
0.7ga
0.3)
3se
4stoichiometric ratio in formula is got Cu (In
0.7ga
0.3) Se
280.69g (In
0.7ga
0.3) Se90.12g, be placed in quartz reaction container and Vacuum Package.After fully shaking up, transfer in stove and react 2h under 1050 ℃ of conditions.Cu (the In that negate should obtain
0.7ga
0.3)
3se
488.82g, after interpolation simple substance Se10.26g, fully grinding evenly to 100 order obtains black precursor.Precursor is transferred in the steel die that diameter is 86mm, and under 20MPa pressure pressurize 2min, the demoulding obtains the precursor disk of moulding.Shift precursor disk to stove, periphery is placed 0.5g simple substance selenium, then stove is carried out airtightly, adopts to vacuumize the mode that is filled with again argon gas and remove oxygen and steam, subsequently by air pressure adjustment to 0.9 normal atmosphere in stove chamber.Stove is warming up to 950 ℃ and be incubated 1h, is down to room temperature and finally obtains Cu (In
0.7ga
0.3)
3se
5target.Known after tested, the relative density of the CIGS target that the present embodiment makes is 0.93.
Industrial applicability: the present invention can obtain fine and close CIGS target, is suitable for that large size preparation, energy consumption are little, low of cost, controllability are good, be easy to large-scale production, can be applied to the photovoltaic material technical field of new energies such as CIGS thin-film solar cell.
Claims (9)
1. a pressureless sintering preparation method for CIGS target material, is characterized in that, comprising:
(1) CIGS of selenium position disappearance
1-
δ the preparation of powder: press CIGS
1-
δ stoichiometric ratio take respectively ,Jia source, ,Yin source, copper source and selenium source, mix final vacuum encapsulation, in 900～1100 ℃ of reactions, within 1～10 hour, make and comprise the second phase (In
1-
x ga
x ) CIGS of Se
1-
δ powder, wherein,
δfor selenium disappearance ratio, 0 <
δ<1,0≤
x≤ 0.5;
(2) preparation of precursor powder: by gained CIGS
1-
δ powder and Se powder are (1-in the ratio of Se element separately
δ):
δratio fully mix and be crushed to designated size and make precursor powder;
(3) compression moulding: described precursor powder compression moulding is made to forerunner's block; And
(4) pressureless sintering: described forerunner's block is placed on and carries out pressureless sintering in the sintering oven under the protective atmosphere of airtight and negative pressure and make CIGS target material.
2. preparation method according to claim 1, is characterized in that, described CIGS
1-
δ molecular formula be:
Cu (In
1-
x ga
x ) Se
2-
y , wherein 0≤
x≤ 0.5,0.1≤
y≤ 0.6;
Cu (In
1-
x ga
x )
5se
8-
z , wherein 0≤
x≤ 0.5,0.5≤
z≤ 2.5; Or
Cu (In
1-
x ga
x )
3se
5-
w , wherein 0≤
x≤ 0.5,0.5≤
w≤ 1.5.
3. preparation method according to claim 1 and 2, is characterized in that, described copper source is at least one in elemental copper, copper selenide, selenkupfer, CuIn alloy, CuGa alloy, CuInGa alloy and copper-indium-galliun-selenium; Described indium source is at least one in simple substance indium, indium selenide, indium selenide gallium, CuIn alloy, InGa alloy, CuInGa alloy and copper-indium-galliun-selenium; Described gallium source is at least one in Metallic Gallium, gallium selenide, indium selenide gallium, InGa alloy, CuGa alloy, CuInGa alloy and copper-indium-galliun-selenium; Described selenium source is at least one in simple substance selenium, copper selenide, selenkupfer, indium selenide, gallium selenide, indium selenide gallium and copper-indium-galliun-selenium.
4. according to the preparation method described in any one in claims 1 to 3, it is characterized in that, described designated size is 100 orders.
5. according to the preparation method described in any one in claim 1 to 4, it is characterized in that, the method for described compacting be cold press process, isostatic pressing method or cold pressing after the static pressure facture such as carry out again.
6. according to the preparation method described in any one in claim 1 to 5, it is characterized in that, described protective atmosphere is argon gas and/or nitrogen; Described negative pressure is 1 below normal atmosphere.
7. according to the preparation method described in any one in claim 1 to 6, it is characterized in that, the sintering temperature of described pressureless sintering is 680～950 ℃, and sintering time is 0.5～10 hour.
8. preparation method according to claim 7, is characterized in that, in step (4), before the heating that heats up, first the furnace chamber of described sintering oven is found time and thoroughly oxygen and steam is removed with rare gas element.
9. according to the preparation method described in any one in claim 1 to 8, it is characterized in that, when pressureless sintering, at described forerunner's block periphery, place simple substance selenium powder grain, described simple substance selenium powder grain is 0～0.2 with the mass ratio that is mixed in the simple substance selenium in described forerunner's block.
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| CN109877335A (en) * | 2019-03-12 | 2019-06-14 | 先导薄膜材料（广东）有限公司 | Copper indium gallium selenide raw powder's production technology |
| CN110373641A (en) * | 2019-07-10 | 2019-10-25 | 桂林理工大学 | A kind of fast preparation method of solar battery CIGS target |
| CN116332645A (en) * | 2023-03-29 | 2023-06-27 | 宁波江丰电子材料股份有限公司 | Molybdenum oxide tantalum target material and preparation method and application thereof |
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