CN102709393A - Method for preparing thin-film solar cells from copper-zinc-tin sulfur compound single target materials - Google Patents
Method for preparing thin-film solar cells from copper-zinc-tin sulfur compound single target materials Download PDFInfo
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Abstract
The invention relates to the field of solar energy, in particular to a method for preparing thin-film solar cells from copper-zinc-tin sulfur compound single target materials. The method comprises the following steps that A, I-III-VI2 copper-zinc-tin sulfur compound single target materials with chalcopyrite structures are sputtered on a soda-lime glass molybdenum (Mo) substrate or a stainless steel sheet molybdenum (Mo) substrate by adopting a vacuum magnetron sputtering method, and a solar cell absorbing layer is formed; B, the solar cell absorbing layer is subjected to annealing treatment through fast heating in vacuum; C, an In2Se3 or In2S3 buffer layer is deposited on the solar cell absorbing layer treated in the step B by adopting the vacuum magnetron sputtering method; D, the deposition of an intrinsic zinc oxide (i-ZnO) high impedance layer is carried out on the deposited In2Se3 or In2S3 buffer layer by adopting a radio frequency vacuum magnetron sputtering method; and E, the deposition of an aluminum-doped zinc oxide (ZnO:Al) low impedance layer is carried out on the deposited intrinsic zinc oxide (i-ZnO) high impedance layer by adopting the radio frequency vacuum magnetron sputtering method. The method can be used for preparing the thin-film solar cells from I-III-VI2 with the chalcopyrite structures under the pollution-free condition.
Description
Technical field
The present invention relates to field of solar energy, be specifically related to a kind of method for preparing thin-film solar cells with the single target of copper zincium tin sulfur compound.
Background technology
The available energy is deficient day by day on the earth, and fossil energy in use can emission of carbon, sulfur oxide causes the greenhouse effect of the air pollution and the aggravation earth, makes the ecological deterioration unusual weather conditions of the earth, has been undisputable fact.Therefore developing non-pollution of renewable energy is one of primary scientific research project of our times various countries.And the utilization of solar energy is optimal selection pollution-free, regenerative resource, and the scope of application of solar energy almost is all passable everywhere on earth, and solar energy is at present unique by generally acknowledged inexhaustible non-pollution of renewable energy.What development and use solar energy head was heavy is the material that exploitation can produce the high efficiency conversion solar.
The compound semiconductor that I-III-VI2 has yellow copper structure is the direct band gap material, the bigger sunlight of ability absorbing wavelength scope, and can form to reach p type, n N-type semiconductor N by modulation self; Be to generally acknowledge one of optimal material as solar cell master absorbed layer; Cu (Zn, Sn) S2, copper zinc-tin two sulphur for example; Be called for short CZTS, for having the semiconductor of high light absorpting ability at present.Because the high absorptivity advantage of CZTS; Make the thickness of CZTS absorbed layer get final product at 1～2 micron; With general rough estimation, when volume production was made, the semi-conducting material expense was lower than 0.05 dollar/watt; Therefore have competitive advantage, and be expected to make the solar power generation can be identical even lower with traditional fossil fuel cost of electricity-generating.Therefore the I-III-VI2 that how to prepare low-cost high-efficiency has the compound semiconductor of yellow copper structure, be at present the problem of worth developmental research it
The CZTS thin-film solar cells is different from other kinds solar cell except the use of material; Still have two big characteristics; Its opto-electronic conversion layer thickness of the first can be as thin as several microns, removes in view of the above and can reduce material cost, also can save the energy that is dropped into when making simultaneously.In case photoelectric conversion layer attenuation, the light absorpting ability of CZTS material can become quite high.
Another feature then is that the generating efficiency of its theoretical property can be up to 10～15%, and is more high than monocrystalline silicon.The CZTS semiconductor has the character that aspect thickness, changes its composition and can control its absorbing wavelength scope, if suitably allotment on this constituent lets the absorbing wavelength scope become extensively, just can improve the generating efficiency of solar cell.The CZTS thin-film solar cells also has a big characteristic, that be exactly it under light or radiation exposure, have the advantage that more is difficult to deterioration than polysilicon solar cell, have that stable performance is not failed, capability of resistance to radiation is strong, under rainy weather, send characteristics such as electric weight height.Its stability of existing in addition evidence is good not to fail, capability of resistance to radiation is strong, and life of product is longer.The CZTS solar cell belongs to Direct Transfer ability stage structure; Has good optical absorption characteristics; Its absorption coefficient of light is superior to other solar cell; Being that the CZTS solar cell has characteristics such as soft, light in addition first of the various thin-film solar cells, is one of the most promising solar cell of new generation.Now ripe thin-film solar cells is cadmium telluride (CdTe), but the energy shortage of tellurium material, and copper, zinc, tin, sulphur energy abundance, and do not have toxicity.
The CZTS thin-film solar cells is the multi-layer film structure assembly; Its primary structure has: substrate (the normally stainless steel or the polymer of glass, flexibility), back electrode (normally Mo), absorbed layer (p-CZTS), resilient coating (normally n-In2S3), transparency conducting layer (normally intrinsic Zn0 and Al doping of Zn 0 double-decker), top electrode (being generally Ni/Al), antireflection layer (normally MgF2 not necessarily will have).The structure of each tunic and characteristic all will influence the performance of CZTS battery.Present popular research work mainly concentrates on the research and development of absorbed layer preparation technology exploitation, alternative buffer layers.
Having put down in writing the method for preparing the CZTS film in the document mainly contains: (l) sulfuration method, (2) lay-up method, (3) multi-source (two or three sources) evaporation, (4) sputtering method, (5) sedimentation, (6) spraying process, (7) spin-coating method, (8) heating in vacuum synthetic method etc.And this (1) sulfuration method; (2) lay-up method; (3) multi-source (two or three sources) evaporation; (4) sputtering method all need carry out vulcanizing treatment to the CZTS film in certain technological process, can make the S atom react generation CuZnSnS compound through diffusion and Cu-Zn-Sn through vulcanizing treatment, and this process is called sulfuration.
The method that sulfuration preparation I-III-VI2 has the thin-film solar cells of yellow copper structure exists following several shortcoming:
Production cycle long, production efficiency is low;
2.S boiling point be 444.6 ℃, the temperature of Sization is higher than 444.6 ℃;
3. it is many to consume S: have only part S steam to contact with the Cu-Zn-Sn layer;
4.S steam severe toxicity is arranged, cause security incident easily: the S of gaseous state meets water (comprising airborne water) and promptly forms gaseous state H2S (being a kind of poison gas); In addition, gaseous state S has very strong corrosivity to other metals, leaks out S steam easily;
5. in the CuZnxSnx-1S2 compound film of sulfuration method preparation, there is gradient in the skewness of S: low near molybdenum (Mo) the layer S of place content.
The CZTS thin-film solar cells uses cadmium sulfide CdS as resilient coating usually, and cadmium has the potential hazard that causes cadmium poisoning.Cadmium poisoning is contact a kind of intoxicating phenomenon that cadmium or its compound caused.Acute cadmium poisoning is mainly damaged respiratory system, mainly because of sucking due to the flue dust that contains cadmium compound in a large number.Chronic cadium poisoning then can cause the renal tubule pathology, makes renal failure then, also can cause skeleton softening (osteoporosis), and testis dwindles, anosmia, and the infringement of other organ.The plant that is planted on the soil of cadmium pollution also can have cadmium, and is edible and suck (such as hemp) and can cause cadmium poisoning.The water source of cadmium pollution also can cause poisoning in addition.Because cadmium is widely used on the manufacturing industry, so the occupational cadmium poisoning is modal cadmium poisoning.High risk industries comprises the smelting that relates to cadmium and welding, nickel-cadmium cell manufacturing, pigment manufacturing, metal surface cadmium plating or the like.
Summary of the invention
The present invention provides a kind of and prepares the method for thin-film solar cells with the single target of copper zincium tin sulfur compound, can under free of contamination situation, prepare I-III-VI2 and have the thin-film solar cells of yellow copper structure.
The invention provides and a kind ofly prepare the method for thin-film solar cells with the single target of copper zincium tin sulfur compound, this method comprises:
A. utilize the vacuum magnetic-control sputtering method, sputter has the I-III-single target of VI 2 copper zincium tin sulfur compounds of yellow copper structure on soda-lime glass molybdenum (Mo) substrate or stainless steel substrates molybdenum (Mo) substrate, forms solar battery obsorbing layer;
B. under vacuum environment, the solar battery obsorbing layer that the A step is prepared carries out annealing in process;
C. utilize the vacuum magnetic-control sputtering method, on the said solar battery obsorbing layer after the B step process, deposit In
2Se
3Or In
2S
3Resilient coating;
D. utilize radio frequency vacuum magnetic-control sputtering method, at the In of step C deposition
2Se
3Or In
2S
3Carry out the deposition of intrinsic zinc oxide i-ZnO high impedance layer on the resilient coating;
E. utilize radio frequency vacuum magnetic-control sputtering method, on the said intrinsic zinc oxide i-ZnO of step D deposition, join the deposition of aluminum zinc oxide ZnO:Al low impedance layers.
In said steps A, said I-III-single target of VI 2 copper zincium tin sulfur compounds is preferably CuZn
xSn
1-xS
2Single target.
In said steps A, be preferably and carry out twice sputter, the first time is with the CuZn of rich copper
xSn
1-xS
2Single target as sputter forms rich copper absorbing layer of thin film solar cell; The second time is with the CuZn of poor copper
xSn
1-xS
2Single target as sputter forms poor copper absorbing layer of thin film solar cell.
The ratio of copper atom is preferably 24.5% ~ 27% in the single target of the copper zincium tin sulfur compound of said rich copper, and the mass ratio of sulphur atom is preferably 46% ~ 49%;
And/or,
The mass ratio of copper atom is preferably 20% ~ 24% in the single target of the copper zincium tin sulfur compound of said poor copper, and the mass ratio of sulphur atom is preferably 50% ~ 53%.
In the said steps A, the vacuum degree of said vacuum magnetic-control sputtering method is preferably 1 * 10
-3~ 5 * 10
-3Holder is preferably and feeds that to contain volume ratio be 5%O
2Argon Ar gas, said soda-lime glass molybdenum (Mo) substrate or stainless steel substrates molybdenum (Mo) substrate temperature are preferably 350 ℃ ~ 450 ℃, said rich copper film, said poor copper depositing of thin film thickness are preferably 1 micron ~ 2 microns respectively.
Annealing temperature is preferably 450 ℃ ~ 580 ℃, and the duration is preferably 2 ~ 3 hours.
In step C, the parametric optimization of said vacuum magnetic-control sputtering method is 1 * 10
-3~ 5 * 10
-3Holder, and be preferably feeding argon Ar gas, substrate temperature preferably keeps 10 ℃ ~ 30 ℃, said In
2Se
3Or In
2S
3The thickness of resilient coating is preferably 5 nanometers.
In step D, the target that said radio frequency vacuum magnetic-control sputtering method is used is preferably zinc oxide (ZnO), and the parametric optimization of vacuum sputtering is 1 * 10
-3~ 5 * 10
-3Holder, frequency is preferably 400kHz ~ 2MHz, and preferably feeds argon Ar gas, and substrate temperature preferably keeps 10 ℃ ~ 30 ℃, and the thickness of said intrinsic zinc oxide (i-ZnO) high impedance layer is preferably 5 ~ 20 nanometers.
In step e, the target that said radio frequency vacuum magnetic-control sputtering method is used is preferably zinc oxide ZnO: aluminium Al, the parametric optimization of vacuum sputtering are 1 * 10
-3~ 5 * 10
-3Holder, and preferred the feeding contained 5%O
2Argon gas (Ar) gas, substrate temperature preferably keeps 10 ℃ ~ 30 ℃, the film thickness of said zinc oxide is preferably 0.3 ~ 0.6 micron.
Provide the single target of a kind of copper zincium tin sulfur compound to prepare the method for thin-film solar cells through the present invention, can reach following beneficial effect:
1. all technology of the present invention is all the dry process flow process, and technical process is not used chemical solvent and solution.A step sputtering method is adopted in the film preparation of solar absorbing layer; The CZTS material (target) that will prepare exactly can make the CZTS film of uniform ingredients through a sputter; Adopt the sputter of a step can obtain the compound of stable crystalline, the industrial procedure that no longer need vulcanize film has shortened the production cycle greatly; Reduce production equipment, also avoided environmental pollution and potential danger in the production process.Processing step is simplified, and energy resource consumption is little, has therefore reduced production cost.
2. the present invention has also improved the tradition of the resilient coating of use cadmium sulfide (CdS), uses In
2Se
3Or In
2S
3, the neither cadmium that contains of these two kinds of compounds.Manifested the value of environmental protection.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; Below will do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art; Obviously, the accompanying drawing in below describing only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other embodiment and accompanying drawing thereof according to these accompanying drawing illustrated embodiments.
Fig. 1 is the schematic flow sheet of a specific embodiment of the present invention;
A certain solar battery obsorbing layer Cu (Zn, Sn) S that Fig. 2 produces for the present invention
2The architectural characteristic figure of x ray film.
Embodiment
Below will combine accompanying drawing that the technical scheme of various embodiments of the present invention is carried out clear, complete description, obviously, described embodiment only is a part of embodiment of the present invention, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are resulting all other embodiment under the prerequisite of not making creative work, the scope that all belongs to the present invention and protected.
The present invention provides a kind of and prepares the method for thin-film solar cells with the single target of copper zincium tin sulfur compound, and this method comprises:
A. utilize the vacuum magnetic-control sputtering method, sputter has the I-III-single target of VI 2 copper zincium tin sulfur compounds of yellow copper structure on soda-lime glass molybdenum (Mo) substrate or stainless steel substrates molybdenum (Mo) substrate, forms solar battery obsorbing layer;
B. under vacuum environment, the solar battery obsorbing layer that the A step is prepared carries out annealing in process;
C. utilize the vacuum magnetic-control sputtering method, on the said solar battery obsorbing layer after the B step process, deposit In
2Se
3Or In
2S
3Resilient coating;
D. utilize radio frequency vacuum magnetic-control sputtering method, at the In of step C deposition
2Se
3Or In
2S
3Carry out the deposition of intrinsic zinc oxide (i-ZnO) high impedance layer on the resilient coating;
E. utilize radio frequency vacuum magnetic-control sputtering method, on the said intrinsic zinc oxide (i-ZnO) of step D deposition, join the deposition of aluminum zinc oxide ZnO:Al low impedance layers.
The all technology of the present invention is all the dry process flow process, and technical process is not used chemical solvent and solution.A step sputtering method is adopted in the film preparation of solar absorbing layer; The CZTS material (target) that will prepare exactly can make the CZTS film of uniform ingredients through a sputter; Adopt the sputter of a step can obtain the compound of stable crystalline, the industrial procedure that no longer need vulcanize film has shortened the production cycle greatly; Reduce production equipment, also avoided environmental pollution and potential danger in the production process.Processing step is simplified, and energy resource consumption is little, has therefore reduced production cost.
The present invention has also improved the tradition of the resilient coating of use cadmium sulfide (CdS), uses In
2Se
3Or In
2S
3, the neither cadmium that contains of these two kinds of compounds has manifested the value of environmental protection.
In said steps A, said I-III-single target of VI 2 copper zincium tin sulfur compounds is preferably CuZn
xSn
1-xS
2Single target.
In said steps A, be preferably and carry out twice sputter, the first time is with the CuZn of rich copper
xSn
1-xS
2Single target as sputter forms rich copper absorbing layer of thin film solar cell; The second time is with the CuZn of poor copper
xSn
1-xS
2Single target as sputter forms poor copper absorbing layer of thin film solar cell.
The ratio of copper atom is preferably 24.5% ~ 27% in the single target of the copper zincium tin sulfur compound of said rich copper, and the mass ratio of sulphur atom is preferably 46% ~ 49%;
And/or,
The mass ratio of copper atom is preferably 20% ~ 24% in the single target of the copper zincium tin sulfur compound of said poor copper, and the mass ratio of sulphur atom is preferably 50% ~ 53%.
In the said steps A, the vacuum degree of said vacuum magnetic-control sputtering method is preferably 1 * 10
-3~ 5 * 10
-3Holder is preferably and feeds that to contain volume ratio be 5%O
2Argon gas (Ar) gas, said soda-lime glass molybdenum (Mo) substrate or stainless steel substrates molybdenum (Mo) substrate temperature are preferably 350 ℃ ~ 450 ℃, said rich copper film, said poor copper depositing of thin film thickness are preferably 1 micron ~ 2 microns respectively.
Annealing temperature is preferably 450 ℃ ~ 580 ℃, and the duration is preferably 2 ~ 3 hours.
In step C, the parametric optimization of said vacuum magnetic-control sputtering method is 1 * 10
-3~ 5 * 10
-3Holder, and be preferably feeding argon gas (Ar) gas, substrate temperature preferably keeps 10 ℃ ~ 30 ℃, said In
2Se
3Or In
2S
3The thickness of resilient coating is preferably 5 nanometers.
In step D, the target that said radio frequency vacuum magnetic-control sputtering method is used is preferably zinc oxide (ZnO), and the parametric optimization of vacuum sputtering is 1 * 10
-3~ 5 * 10
-3Holder, frequency is preferably 400kHz ~ 2MHz, and (Ar) gas that preferably feeds argon gas, and substrate temperature preferably keeps 10 ℃ ~ 30 ℃, and the thickness of said intrinsic zinc oxide (i-ZnO) high impedance layer is preferably 5 ~ 20 nanometers.
In step e, the target that said radio frequency vacuum magnetic-control sputtering method is used is preferably zinc oxide (ZnO): aluminium (Al), the parametric optimization of vacuum sputtering are 1 * 10
-3~ 5 * 10
-3Holder, and preferred the feeding contained 5%O
2Argon gas (Ar) gas, substrate temperature preferably keeps 10 ℃ ~ 30 ℃, the film thickness of said zinc oxide is preferably 0.3 ~ 0.6 micron.
Below, the present invention will be described in detail the method that the single target of copper zincium tin sulfur compound prepares thin-film solar cells through a specific embodiment, like Fig. 1, shown in:
Step 101, preparation stainless steel substrates molybdenum (Mo) substrate;
On 304 stainless steel substrates of 0.3 millimeter thickness, adopt molybdenum (Mo) metal of magnetron sputtering deposition 0.8 micron thick.
Need to prove that the model of stainless steel substrates, thickness can also possess other values and limit, such as 304 stainless steel substrates of 0.35 millimeters thick, molybdenum (Mo) metal layer thickness also can possess a scope, such as 0.75 millimeter, 0.85 millimeter molybdenum layer.
Step 102 adopts the vacuum magnetic-control sputtering method, forms rich copper thin film solar absorbed layer;
Adopt the CuZn of rich copper
xSn
1-xS
2Single target (being the I-III-single target of VI 2 copper zincium tin sulfur compounds of rich copper) is done target, adopts the vacuum magnetic-control sputtering method, and wherein vacuum parameters is 1 * 10
-3~ 5 * 10
-3Holder (Torr) feeds and contains volume ratio 5%O
2Argon gas (Ar) gas; Stainless steel substrates molybdenum (Mo) substrate temperature remains on 350 ℃ ~ 450 ℃; Such as: 350 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃ or any two the value between scope; Carry out sputter, the rich copper depositing of thin film thickness of formation is 1 micron ~ 2 microns, such as: 1 micron, 1.5 microns, 1.6 microns, 1.7 microns, 1.8 microns, 1.9 microns, 2.0 microns or any two the value between scope.
Need to prove, wherein the CuZn of rich copper
xSn
1-xS
2The mass ratio of the copper atom in the single target is 24.5% ~ 27%; Such as, 24.5%, 25%, 25.5%, 26%, 26.5%, 27% or any two the value between scope, the mass ratio of sulphur atom is 46% ~ 49%; Such as, 46%, 47%, 48%, 49% or any two the value between scope.
Step 103 adopts the vacuum magnetic-control sputtering method, forms poor copper thin film solar absorbed layer;
Adopt the CuZn of poor copper
xSn
1-xS
2Single target (being the I-III-single target of VI 2 copper zincium tin sulfur compounds of poor copper) is done target, adopts the vacuum magnetic-control sputtering method, and wherein vacuum parameters is 1 * 10
-3~ 5 * 10
-3Holder (Torr) feeds and contains volume ratio 5%O
2Argon gas (Ar) gas; Stainless steel substrates molybdenum (Mo) substrate temperature remains on 350 ℃ ~ 450 ℃; Such as: 350 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃ or any two the value between scope; On rich copper film, carry out sputter, the poor copper depositing of thin film thickness of formation is 1 micron ~ 2 microns, such as: 1 micron, 1.5 microns, 1.6 microns, 1.7 microns, 1.8 microns, 1.9 microns, 2.0 microns or any two the value between scope.
Need to prove, wherein the CuZn of poor copper
xSn
1-xS
2The mass ratio of the copper atom in the single target is 20% ~ 24%; Such as; 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24% or any two the value between scope; The mass ratio of sulphur atom is 50% ~ 53%, such as, 50%, 50.5%, 51%, 51.5%, 52%, 52.5%, 53% or any two the value between scope.
Step 104, under vacuum environment, the solar battery obsorbing layer that the A step is prepared carries out annealing in process;
Mode with Fast Heating is carried out annealing in process, makes rich copper solar absorbing layer, the crystal growth of poor copper solar absorbing layer that step 102, step 103 form to improve crystalline state, consolidates the photovoltaic efficiency of solar cell master absorbed layer.
Annealing temperature is 450 ℃ ~ 580 ℃, and the duration is 2 ~ 3 hours.
Step 105 is utilized the vacuum magnetic-control sputtering method, deposits In on the solar battery obsorbing layer after step 104 is handled
2S
3Resilient coating;
In this step, the vacuum degree in the vacuum magnetic-control sputtering method is 1 * 10
-3~ 5 * 10
-3Holder (Torr) feeds argon gas ((Ar) gas), and substrate temperature remains on room temperature, is generally 10 ℃ ~ 30 ℃, In
2S
3The thickness of resilient coating is 5 nanometers, and substrate also is soda-lime glass (Mo) substrate or stainless steel substrates (Mo) substrate.
Need to prove In
2S
3Resilient coating also can use other resilient coating to replace, such as: In
2Se
3Resilient coating, its thickness also are 5 nanometers.
The present invention does not re-use the resilient coating of traditional cadmium sulfide CdS, adopts In
2S
3Resilient coating or In
2Se
3Resilient coating, the neither cadmium that contains of these two kinds of compounds is a kind of environment-friendly materials.
Step 106 is utilized radio frequency vacuum magnetic-control sputtering method, at the In of step 105 deposition
2Se
3Carry out the deposition of intrinsic zinc oxide (i-ZnO) high impedance layer on the resilient coating;
The target that said radio frequency vacuum magnetic-control sputtering method is used is zinc oxide (ZnO), and the vacuum degree of vacuum sputtering is 1 * 10
-3~ 5 * 10
-3Holder (Torr), frequency is 400kHz ~ 2MHz, and feeds argon gas (Ar) gas; Substrate temperature keeps room temperature; Be generally 10 ℃ ~ 30 ℃, the thickness of said intrinsic zinc oxide (i-ZnO) high impedance layer is 5 ~ 20 nanometers, such as; Scope between 5 nanometers, 8 nanometers, 10 nanometers, 13 nanometers, 15 nanometers, 18 nanometers, 20 nanometers or wherein any two values, substrate also is soda-lime glass (Mo) substrate or stainless steel substrates (Mo) substrate.
Step 107 is utilized radio frequency vacuum magnetic-control sputtering method, on intrinsic zinc oxide (i-ZnO) high impedance layer of step 106 deposition, joins the deposition of aluminum zinc oxide ZnO:Al low impedance layers.
In this step, the target that said radio frequency vacuum magnetic-control sputtering method is used is zinc oxide (ZnO): aluminium (Al), the parameter of vacuum sputtering are 1 * 10
-3~ 5 * 10
-3Holder, and feed that to contain volume ratio be 5%O
2Argon gas (Ar) gas; Substrate temperature keeps room temperature; Be generally 10 ℃ ~ 30 ℃, substrate also is soda-lime glass (Mo) substrate or stainless steel substrates (Mo) substrate, and the film thickness of said zinc oxide is 0.3 ~ 0.6 micron; Such as, 0.3 micron, 0.35 micron, 0.4 micron, 0.45 micron, 0.5 micron, 0.55 micron, 0.6 micron or wherein any two the value between scope.With Al target as sputter Al electrode, finally obtain Cu (Zn, Sn) S again
2The thin-film solar cells of the single target preparation of compound.
The open circuit voltage of this solar cell is 465mV, and short circuit current is 24.3mA/cm
2, fill factor, curve factor is 58%, photoelectric conversion efficiency is 6.3%.
This solar cell is carried out its membrane structure performance plot of X-ray diffraction, see Fig. 2, shown in, (112) (220) and in-plane (312) have characteristic peaks on the plane, show that its crystal habit quality is good.
Provide the single target of a kind of copper zincium tin sulfur compound to prepare the method for thin-film solar cells through the present invention, can reach following beneficial effect:
1. all technology of the present invention is all the dry process flow process, and technical process is not used chemical solvent and solution.A step sputtering method is adopted in the film preparation of solar absorbing layer; The CZTS material (target) that will prepare exactly can make the CZTS film of uniform ingredients through a sputter; Adopt the sputter of a step can obtain the compound of stable crystalline, the industrial procedure that no longer need vulcanize film has shortened the production cycle greatly; Reduce production equipment, also avoided environmental pollution and potential danger in the production process.Processing step is simplified, and energy resource consumption is little, has therefore reduced production cost.
2. the present invention has also improved the tradition of the resilient coating of use cadmium sulfide (CdS), uses In
2Se
3Or In
2S
3, the neither cadmium that contains of these two kinds of compounds.Manifested the value of environmental protection.
Various embodiment provided by the invention can make up with any-mode as required each other, the technical scheme that obtains through this combination, also within the scope of the invention.
Obviously, those skilled in the art can carry out various changes and modification to the present invention and not break away from the spirit and scope of the present invention.Like this, belong within the scope of claim of the present invention and equivalent technologies thereof if of the present invention these are revised with modification, then the present invention also comprises these changes and modification interior.
Claims (9)
1. one kind prepares the method for thin-film solar cells with the single target of copper zincium tin sulfur compound, it is characterized in that this method comprises:
A. utilize the vacuum magnetic-control sputtering method, sputter has the I-III-single target of VI 2 copper zincium tin sulfur compounds of yellow copper structure on soda-lime glass molybdenum Mo substrate or stainless steel substrates molybdenum Mo substrate, forms solar battery obsorbing layer;
B. under vacuum environment, the solar battery obsorbing layer that the A step is prepared carries out annealing in process;
C. utilize the vacuum magnetic-control sputtering method, on the said solar battery obsorbing layer after the B step process, deposit In
2Se
3Or In
2S
3Resilient coating;
D. utilize radio frequency vacuum magnetic-control sputtering method, at the In of step C deposition
2Se
3Or In
2S
3Carry out the deposition of intrinsic zinc oxide i-ZnO high impedance layer on the resilient coating;
E. utilize radio frequency vacuum magnetic-control sputtering method, on the said intrinsic zinc oxide i-ZnO of step D deposition, join the deposition of aluminum zinc oxide ZnO:Al low impedance layers.
2. the method for claim 1 is characterized in that, in said steps A, said I-III-single target of VI 2 copper zincium tin sulfur compounds is CuZn
xSn
1-xS
2Single target.
3. method as claimed in claim 2 is characterized in that, in said steps A, carries out twice sputter, and the first time is with the CuZn of rich copper
xSn
1-xS
2Single target as sputter forms rich copper absorbing layer of thin film solar cell; The second time is with the CuZn of poor copper
xSn
1-xS
2Single target as sputter forms poor copper absorbing layer of thin film solar cell.
4. method as claimed in claim 3 is characterized in that,
The atomic ratio of copper is 24.5% ~ 27% in the single target of the copper zincium tin sulfur compound of said rich copper, and the atomic ratio of sulphur is 46% ~ 49%;
And/or,
The atomic ratio of copper is 20% ~ 24% in the single target of the copper zincium tin sulfur compound of said poor copper, the atomic ratio 50% ~ 53% of sulphur.
5. method as claimed in claim 3 is characterized in that,
In the said steps A, the vacuum degree of said vacuum magnetic-control sputtering method is 1 * 10
-3~ 5 * 10
-3Holder, it is 5%O that feeding contains volume ratio
2Argon Ar gas, said soda-lime glass molybdenum Mo substrate or stainless steel substrates molybdenum Mo substrate temperature are 350 ℃ ~ 450 ℃, said rich copper film, said poor copper depositing of thin film thickness are respectively 1 micron ~ 2 microns.
6. like each described method of claim 1-5, it is characterized in that,
Annealing temperature is 450 ℃ ~ 580 ℃, and the duration is 2 ~ 3 hours.
7. like each described method of claim 1-5, it is characterized in that,
In step C, the parameter of said vacuum magnetic-control sputtering method is 1 * 10
-3~ 5 * 10
-3Holder, and feed argon Ar gas, substrate temperature keeps 10 ℃ ~ 30 ℃, said In
2Se
3Or In
2S
3The thickness of resilient coating is 5 nanometers.
8. like each described method of claim 1-5, it is characterized in that,
In step D, the target that said radio frequency vacuum magnetic-control sputtering method is used is zinc oxide ZnO, and the parameter of vacuum sputtering is 1 * 10
-3~ 5 * 10
-3Holder, frequency is 400kHz ~ 2MHz, and feeds argon Ar gas, and substrate temperature keeps 10 ℃ ~ 30 ℃ of room temperatures, and the thickness of said intrinsic zinc oxide i-ZnO high impedance layer is 5 ~ 20 nanometers.
9. like each described method of claim 1-5, it is characterized in that,
In step e, the target that said radio frequency vacuum magnetic-control sputtering method is used is zinc oxide ZnO: aluminium Al, the parameter of vacuum sputtering is 1 * 10
-3~ 5 * 10
-3Holder, and feeding contains 5%O
2Argon Ar gas, substrate temperature keeps room temperature (10 ℃ ~ 30 ℃), the film thickness of said zinc oxide is 0.3 ~ 0.6 micron.
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| CN103515482A (en) * | 2013-09-10 | 2014-01-15 | 华中科技大学 | Copper-indium-gallium-selenium thin film solar cell absorption layer and preparation method and application thereof |
| CN103219420B (en) * | 2013-03-26 | 2016-01-27 | 无锡舒玛天科新能源技术有限公司 | A kind of method of use four mischmetal preparation of target materials copper-zinc-tin-sulfur film |
| CN109904256A (en) * | 2019-01-09 | 2019-06-18 | 云南师范大学 | A kind of copper-zinc-tin-sulfur film preparation method |
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