Copper-indium-galliun-selenium or Cu-In-Al-Se solar cell absorption layer target material and preparation method thereof
Technical field
The invention belongs to the photoelectric functional material field, particularly copper-indium-galliun-selenium or Cu-In-Al-Se solar cell absorption layer target material and preparation method thereof
Background technology
Copper indium diselenide (CIS) series film solar battery has the photoelectric conversion rate height, and the decay of low, the no performance of cost, life-span be long, can adopt characteristics such as flexible substrates, is one of photovoltaic cell technology of tool development prospect, is hopeful very much to obtain in future large-scale application.Copper indium diselenide (the CuInSe of yellow copper structure
2) energy gap is 1.04eV, is not the semiconductor material that obtains optimum efficiency, Ga, Al, In belong to III family element together, mix an amount of Ga in CIS, and part replaces In, the CuIn of formation
1-xGa
xSe
2(CIGS) energy gap is adjustable continuously in 1.04~1.67eV scope; Mix an amount of Al, part replaces In, the CuIn of formation
1-xAl
xSe
2(CIAS) energy gap is adjustable continuously in 1.04~2.67eV scope.As forming many clone systems again, can greatly improve photovoltaic cell efficiency of conversion [S.Marsillac, et.al, High-efficiency solar cells based onCu.InAl.Se
2Thin films, Applied Physics letters, 2002,81 (7), p1350-1352; Miguel A.Contreras, et.al, Diode characteristics in state-of-the-art ZnOCdS Cu (In
1-xGa
x) Se
2Solar cells, Progress in Photovoltaics:Research andApplications, 2005,13, p 209-216].
The structure of copper indium diselenide (CIS) series film solar battery is generally: antireflection layer/metal gate-shaped electrode/transparent electrode layer/Window layer/buffer layer/light absorbing zone (CIGS or CIAS)/metal back electrode/substrate.Wherein light absorbing zone is the key factor of decision photovoltaic cell performance, in the light absorbing zone stoicheiometry of each element and along the composition profiles of film thickness direction to the absorbing properties important influence.
The method for preparing at present the CIGS film mainly contains vacuum method and antivacuum method.Antivacuum method mainly comprises electrodip process, chemical spray pyrolysis method, coating process, print process etc., but these technical matters stability are bad, and the absorption layer efficiency of conversion of preparation is generally not high, is difficult to prepare the even rete of big area.Vacuum method mainly comprises polynary method and the magnetron sputtering method of steaming altogether of electron beam.Polynary steaming method altogether comprises two kinds of technologies, is respectively that (1) steams Cu, In, the prefabricated membrane+selenizing of Ga alloy altogether; (2) Cu, In, Ga, Se coevaporation.The battery efficiency of steaming method altogether preparation is than higher, and the CIGS battery of the high conversion efficiency of report promptly is with the preparation of steaming method altogether at present.But steaming method altogether requires all will accurately control the vaporator rate and the deposition of every kind of element, especially when big area deposits, require film forming good uniformity, the technology favorable reproducibility, very high to the device control accuracy requirement, increased considerably the difficulty of technology and device fabrication.Therefore, when production big area (more than 30 * 30 centimetres) CIGS cell panel, magnetically controlled sputter method is because processing parameter is easy to control, and technology stability is good, and quality of forming film is even, has higher efficiency of conversion on the contrary, thereby has the better application prospect.Magnetically controlled sputter method generally adopts simultaneously or sputter CuIn and CuGa alloys target by turns, perhaps sputter CuInGa alloys target, and to form CIS alloy preformed layer, selenizing forms the processing step of CIGS absorption layer then.Selenizing has two kinds of methods, and a kind of is at the indoor feeding H of vacuum heat treatment furnace
2Se carries out chemical gas-phase reaction method, but because H
2Se is hypertoxic inflammable gas, thereby this method is difficult to promote; Another kind is at the indoor feeding solid of vacuum heat treatment furnace selenium steam, and Cu, In, the Ga atom in Se atom and the alloy preformed layer reacts and form the CIGS rete at a certain temperature.But in the selenizing process, need be rapidly heated and cross 300~450 ℃ of temperature ranges, be easy to evaporable Ga because in this temperature range, generate easily
2Se, In
2The Se alloy phase causes the loss of In and Ga element in the CIGS rete, influences film performance.And be rapidly heated and the selenizing temperature more than 550 ℃ causes the temperature difference between the substrate top and bottom easily, cause softening or warpage, also easily cause breaking for the large-area glass substrate, influence process implementing and suitability for industrialized production [Marianna Kemell, et.al, Thin Film Deposition Methods for CuInSe
2SolarCells, Critical Reviews in Solid State and Materials Sciences, 2005,30, p1-31; F.Kessler, et.al, Approaches to flexible CIGS thin-film solarcells, Thin Solid Films, 2005,480-481, p491-498].
Summary of the invention
The object of the invention is to provide a kind of copper-indium-galliun-selenium or Cu-In-Al-Se solar cell absorption layer target material and preparation method thereof.It is characterized in that the atom percentage content of Cu, In, Ga, Se or Cu, In, Al, Se is respectively 25%, 22.5%~10% in the described solar cell absorption layer target material, 2.5%~15%, 50%, composition is even, has the CuIn of homogeneous
1-xGa
xSe
2Or CuIn
1-xAl
xSe
2(0.1≤x≤0.6) phase, the relative density of target reaches more than 90%.
Described copper-indium-galliun-selenium (CIGS) or Cu-In-Al-Se (CIAS) film absorption layer use the direct magnetron sputtering of the target of said ratio to form;
A kind of copper-indium-galliun-selenium (CIGS) and Cu-In-Al-Se (CIAS) sputtering target material is characterized in that, according to the stoichiometric ratio outfit high-purity C u of CIGS that needs to form and CIAS rete
2Se, In
2Se
3, Ga
2Se
3Or Al
2Se
3Powder stock, Cu
2Se, In
2Se
3With Ga
2Se
3The mass ratio of powder is 1:2.27 (1-x): 1.83x, Cu
2Se, In
2Se
3With Al
2Se
3The mass ratio of powder is 1:2.27 (1-x): 1.41x, 0.1≤x≤0.6; Target composition after making is even, has the CuIn of homogeneous
1-xGa
xSe
2Or CuIn
1-xAl
xSe
2Phase, relative density reaches more than 90%.The invention provides the preparation method of copper-indium-galliun-selenium (CIGS) and Cu-In-Al-Se (CIAS) sputtering target material, it is characterized in that with mixed powder or its molding biscuit, sintering is made target in protective atmosphere with behind the mixed powder of the abundant ball milling of above-mentioned powder process.
The preparation method of described copper-indium-galliun-selenium or Cu-In-Al-Se solar cell absorption layer target material is characterized in that, any one in system of selection one, method two or the method three made copper-indium-galliun-selenium (CIGS) or Cu-In-Al-Se (CIAS) target, carries out as follows:
Method one:
(1) mixes powder: 1. with high-purity C u
2Se, In
2Se
3, Ga
2Se
3Powder is pressed mass ratio 1:2.27, and (1-X): 1.83X mixes, wherein 0.1≤X≤0.6; Mixed powder mixed placing nylon ball grinder with the zirconium dioxide abrading-ball, with planetary ball mill ball milling 1~12 hour, thorough mixing was even, and the powder median size reaches below the 30 μ m behind the ball milling; Perhaps, 2. with high-purity C u
2Se, In
2Se
3, Al
2Se
3Powder is pressed mass ratio 1:2.27 (1-X): 1.41X, wherein mix 0.1≤X≤0.6, mixed powder mixed placing nylon ball grinder with the zirconium dioxide abrading-ball, even with 1~12 hour thorough mixing of planetary ball mill ball milling, the powder median size reaches below the 30 μ m behind the ball milling.
(2) sintering: with the 1. powder that mixes in (1) or 2. powder place hot pressing die, in protective atmosphere, apply 15~40MPa pressure, at the uniform velocity rise to 500~900 ℃ with 5~30 ℃/minute then, be incubated 0.5~12 hour, cool to normal temperature afterwards with the furnace, take out after the release;
Method two:
(1) mixes powder: with method one.
(2) compacting: with the 1. powder that mixes in (1) or 2. powder place cold stamping die, be forced into 400~1000MPa and pressurize moulding in 2~4 minutes, make biscuit; Perhaps, with the 1. powder that mixes in (1) or 2. powder place the isostatic cool pressing mould, be forced into 100~280MPa and pressurize moulding in 2~6 minutes, make biscuit;
(3) sintering: the biscuit of making in (2) is placed sintering oven, in protective atmosphere, at the uniform velocity be warming up to 650~900 ℃ with 5~30 ℃/minute, and be incubated 0.5~12 hour, take out after cooling to normal temperature then with the furnace;
Method three:
(1) mixes powder: with method one.
(2) compacting: same method two.
(3) sintering: with the 1. biscuit made in (2) or 2. biscuit place sintering oven, in protective atmosphere, biscuit is applied 15~40MPa pressure, at the uniform velocity rise to 500~900 ℃ with 5~30 ℃/minute then, be incubated 0.5~12 hour, cool to normal temperature afterwards with the furnace, take out after the release; Perhaps, with the 1. biscuit made in (2) or 2. biscuit place sintering oven, in protective atmosphere; at the uniform velocity rise to 500~900 ℃ with 5~30 ℃/minute earlier, again biscuit is applied 15~40MPa pressure, be incubated 0.5~12 hour afterwards; cool to normal temperature then with the furnace, take out after the release.
In the aforesaid method, Cu in the step (1)
2Se, In
2Se
3, Ga
2Se
3Or Al
2Se
3Powder purity all 〉=99.99%, the powder median size reaches below the 30 μ m behind the ball milling, to guarantee the high purity and the composition uniform distribution of target.
In the aforesaid method, described protective atmosphere is vacuum or charges into protective gas, and described protective gas is hydrogen, nitrogen or argon gas class rare gas element, and the shielding gas pressure of employing is 1 normal atmosphere; Described vacuum is below the 20Pa.
The invention has the beneficial effects as follows and adopt the direct mixing match of high-purity compound powder that meets CIGS or CIAS absorption layer stoichiometric ratio, avoid the loss of element as far as possible, realize the accurate control of target composition, the target composition that provides is even, has the CuIn of homogeneous
1-xGa
xSe
2Or CuIn
1-xAl
xSe
2Phase, relative density reach more than 90%, satisfy the sputtering technology requirement.Can directly make CIGS or CIAS film absorption layer by this target of sputter, not only can inherit magnetron sputtering method technology and be easy to control, the even film forming advantage of big area can be avoided the disadvantageous effect of selenizing process to absorption layer and substrate again easily, simplify technological process, save energy consumption.On the other hand, by matching with sputtering technology, can realize the accurate control of constituent content such as Ga, Al in the absorption layer, solve the control problem of composition profiles on the absorber thickness direction simultaneously, thereby create conditions for obtaining gradient band gap semiconductor absorption layer and lamination solar cell, significance is arranged for improving CIGS and CIAS conversion efficiency of solar cell.
Embodiment
The invention provides a kind of copper-indium-galliun-selenium or Cu-In-Al-Se solar cell absorption layer target material and preparation method thereof.Introduce the present invention below in conjunction with embodiment, but the present invention only limits to embodiment absolutely not.
Embodiment 1
With Cu
2Se, In
2Se
3, Ga
2Se
3After powder (purity all 〉=99.99%) is pressed mass ratio 1:2.04:0.18 (x=0.1) mixing and ball milling 2h, the powder median size is reached below the 30 μ m.The powder that mixes is placed cold stamping die, be forced into 400~1000MPa and pressurize moulding in 2~4 minutes and make biscuit; Perhaps the powder that mixes is placed the isostatic cool pressing mould, be forced into 100~280MPa and pressurize moulding in 2~6 minutes and make biscuit.The biscuit of making is placed sintering oven, be evacuated to below the 10Pa, keep vacuum condition or charge into 1 standard atmospheric pressure hydrogen or nitrogen or argon gas class rare gas element, at the uniform velocity be warming up to 650~900 ℃ with 5~30 ℃/minute, and be incubated 0.5~12 hour, and taking out after cooling to normal temperature then with the furnace, the atom percentage content that promptly gets Cu, In, Ga, Se is about 25%, 22.5%, 2.5%, 50% respectively, composition is even, has the CuIn of homogeneous
1-xGa
xSe
2Phase, relative density is greater than 90% CIGS target.
Embodiment 2
With Cu
2Se, In
2Se
3, Ga
2Se
3After powder (purity all 〉=99.99%) is pressed mass ratio 1:1.82:0.37 (x=0.2) mixing and ball milling 6h, the powder median size is reached below the 30 μ m.Press the method for embodiment 1, the atom percentage content that promptly gets Cu, In, Ga, Se is about 25%, 22.5%, 2.5%, 50% respectively, and composition is even, has the CuIn of homogeneous
1-xGa
xSe
2Phase, relative density is greater than 90% CIGS target.
Embodiment 3
With Cu
2Se, In
2Se
3, Ga
2Se
3After powder (purity all 〉=99.99%) is pressed mass ratio 1:1.59:0.55 (x=0.3) mixing and ball milling 10h, the powder median size is reached below the 30 μ m.Evenly be filled in the powder that mixes in the hot pressing die, sintering oven is evacuated to below the 10Pa, keep vacuum condition or charge into 1 standard atmospheric pressure hydrogen or nitrogen or argon gas class rare gas element, at the uniform velocity rise to 500~900 ℃ with 5~30 ℃/minute, to the after-applied 15~40MPa pressure of temperature, be incubated 0.5~12 hour then, cool to normal temperature afterwards with the furnace, take out after the release, the atom percentage content that promptly gets Cu, In, Ga, Se is about 25%, 17.5%, 7.5%, 50% respectively, composition is even, has the CuIn of homogeneous
1-xGa
xSe
2Phase, relative density is greater than 95% CIGS target.
Embodiment 4
With Cu
2Se, In
2Se
3, Ga
2Se
3After powder (purity all 〉=99.99%) is pressed mass ratio 1:1.36:0.73 (x=0.4) mixing and ball milling 12h, the powder median size is reached below the 30 μ m.Evenly be filled in the powder that mixes in the hot pressing die, sintering oven is evacuated to below the 10Pa, keep vacuum condition or charge into 1 standard atmospheric pressure hydrogen or nitrogen or argon gas class rare gas element, apply 15~40MPa pressure, at the uniform velocity rise to 500~900 ℃ with 5~30 ℃/minute then, be incubated 0.5~12 hour, cool to normal temperature afterwards with the furnace, take out after the release, the atom percentage content that promptly gets Cu, In, Ga, Se is about 25%, 15%, 10%, 50% respectively, composition is even, has the CuIn of homogeneous
1-xGa
xSe
2Phase, relative density is greater than 95% CIGS target.
Embodiment 5
With Cu
2Se, In
2Se
3, Ga
2Se
3After powder (purity all 〉=99.99%) is pressed mass ratio 1:1.14:0.92 (x=0.5) mixing and ball milling 7h, the powder median size is reached below the 30 μ m.Drawing method by embodiment 1 is made biscuit, then the biscuit of making is placed sintering oven, carry out sintering according to the sintering method of embodiment 3, the atom percentage content that promptly gets Cu, In, Ga, Se is about 25%, 12.5%, 12.5%, 50% respectively, composition is even, has the CuIn of homogeneous
1-xGa
xSe
2Phase, relative density is greater than 95% CIGS target.
Embodiment 6
With Cu
2Se, In
2Se
3, Ga
2Se
3After powder (purity all 〉=99.99%) is pressed mass ratio 1:0.91:1.10 (x=0.6) mixing and ball milling 10h, the powder median size is reached below the 30 μ m.Drawing method by embodiment 1 is made biscuit, then the biscuit of making is placed sintering oven, carry out sintering according to the sintering method of embodiment 4, the atom percentage content that promptly gets Cu, In, Ga, Se is about 25%, 10%, 15%, 50% respectively, composition is even, has the CuIn of homogeneous
1-xGa
xSe
2Phase, relative density is greater than 95% CIGS target.
Embodiment 7
With Cu
2Se, In
2Se
3, Al
2Se
3Powder (purity all 〉=99.99%) is pressed mass ratio 1:2.04:0.14 (x=0.1) and is mixed, press the method for embodiment 1, the final atom percentage content that obtains Cu, In, Al, Se is about 25%, 22.5%, 2.5%, 50% respectively, and composition is even, has the CuIn of homogeneous
1-xAl
xSe
2Phase, relative density is greater than 90% CIAS target.
Embodiment 8
With Cu
2Se, In
2Se
3, Al
2Se
3Powder (purity all 〉=99.99%) is pressed mass ratio 1:2.04:0.28 (x=0.2) and is mixed, press the method for embodiment 2, the final atom percentage content that obtains Cu, In, Al, Se is about 25%, 20%, 5%, 50% respectively, and composition is even, has the CuIn of homogeneous
1-xAl
xSe
2Phase, relative density is greater than 90% CIAS target.
Embodiment 9
With Cu
2Se, In
2Se
3, Al
2Se
3Powder (purity all 〉=99.99%) is pressed mass ratio 1:2.04:0.42 (x=0.3) and is mixed, press the method for embodiment 3, the final atom percentage content that obtains Cu, In, Al, Se is about 25%, 17.5%, 7.5%, 50% respectively, and composition is even, has the CuIn of homogeneous
1-xAl
xSe
2Phase, relative density is greater than 95% CIAS target.
Embodiment 10
With Cu
2Se, In
2Se
3, Al
2Se
3Powder (purity all 〉=99.99%) is pressed mass ratio 1:2.04:0.56 (x=0.4) and is mixed, press the method for embodiment 4, the final atom percentage content that obtains Cu, In, Al, Se is about 25%, 15%, 10%, 50% respectively, and composition is even, has the CuIn of homogeneous
1-xAl
xSe
2Phase, relative density is greater than 95% CIAS target.
Embodiment 11
With Cu
2Se, In
2Se
3, Al
2Se
3Powder (purity all 〉=99.99%) is pressed mass ratio 1:2.04:0.71 (x=0.5) and is mixed, press the method for embodiment 5, the final atom percentage content that obtains Cu, In, Al, Se is about 25%, 12.5%, 12.5%, 50% respectively, and composition is even, has the CuIn of homogeneous
1-xAl
xSe
2Phase, relative density is greater than 95% CIAS target.
Embodiment 12
With Cu
2Se, In
2Se
3, Al
2Se
3Powder (purity all 〉=99.99%) is pressed mass ratio 1:2.04:0.85 (x=0.6) and is mixed, press the method for embodiment 6, the final atom percentage content that obtains Cu, In, Al, Se is about 25%, 10%, 15%, 50% respectively, and composition is even, has the CuIn of homogeneous
1-xAl
xSe
2Phase, relative density is greater than 95% CIAS target.