CN103219419A - Method for producing copper-indium-gallium-selenium film by using copper-indium-gallium-selenium alloy sputtering target material - Google Patents
Method for producing copper-indium-gallium-selenium film by using copper-indium-gallium-selenium alloy sputtering target material Download PDFInfo
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Abstract
The invention provides a method for producing a copper-indium-gallium-selenium film by using a copper-indium-gallium-selenium alloy sputtering target material. The method comprises the following steps of sputtering a copper-indium-gallium-selenium alloy serving as a target material on a substrate to form a first copper-poor layer; sputtering the copper-indium-gallium-selenium alloy serving as the target material on the first copper-poor layer to form a copper-rich layer; and sputtering the copper-indium-gallium-selenium alloy serving as the target material on the copper-rich layer to form a second copper-poor layer to obtain the copper-indium-gallium-selenium film. According to the production method, a co-evaporation three-step process method and a non-vacuum internal absorbing layer connecting structure method are combined, so that the raw material utilization ratio can be remarkably increased, the cost is low, and depositing speed in a sputtering process is high; and meanwhile, an optimal gallium gradient structure and a nanometer domain p-n junction internal absorbing layer connecting structure IAJ are formed in a copper-indium-gallium-selenium absorbing layer, so that the produced copper-indium-gallium-selenium has the advantages of high efficiency, large area and high uniformity.
Description
Technical field
The invention belongs to field of solar utilizing equipment, particularly a kind of method of utilizing the plain Copper Indium Gallium Selenide target of single quaternary High-efficient Production CIGS thin-film.
Background technology
In the past few decades, the manufacturing industry scale of solar panel enlarges rapidly.2011, the growth rate of U.S.'s solar energy industry is up to 109%, and was leading in technical field of new energies.Copper-indium-galliun-selenium film solar cell in the development of solar panel field rapidly, it is provided with molybdenum layer (1), p-type CIGS thin-film absorbed layer (2), cadmium sulfide resilient coating (3), intrinsic zinc oxide (4), aluminium-zinc oxide Window layer (5) and surperficial contact layer (6) usually successively on the glass film plates of one deck rigidity or flexible corrosion resistant plate, see Fig. 1.According to the research report of Lux Research, CIGS thin-film solar market production capacity reached 1.2GW in 2011, and will reach 2.3GW in 2015; Other solar cell research institutions all predict copper-indium-galliun-selenium film solar cell the market share will by 2010 3% rise to 2015 6%, and will reach 33% at the year two thousand twenty.This shows that fully the copper-indium-galliun-selenium film solar cell technology will lead following solar cell market, and has huge business potential.As being classified as the most promising thin film solar cell technologies by the well-known solar cell of USDOE and other research institution, the copper-indium-galliun-selenium film solar cell technology just by feat of its widely advantage attracting increasing researcher and investor.Up to now, the efficient of copper-indium-galliun-selenium film solar cell has broken through 20.3% in the laboratory.Simultaneously, increasing company, mechanism are being devoted to realize the commercialization of this technology.
Yet the commercialization process of copper-indium-galliun-selenium film solar cell still lags behind monocrystaline silicon solar cell and other thin-film solar cells, for example Cadimium telluride thin film battery at present.Cause copper-indium-galliun-selenium film solar cell to realize that the biggest obstacle of scale of mass production is the high production cost of CIGS thin-film.To the year two thousand twenty, USDOE is 0.5 dollar/watt to system's installation cost target of solar panel, and this still is higher than monocrystaline silicon solar cell and other thin-film solar cells.
Existing, the production method of CIGS thin-film can be divided into antivacuum method and vacuum method substantially.Antivacuum method comprises electrochemical filming method, ink-jet printing process, FASST method and method of spin coating etc.; Efficient on the low side is the big problem that non-vacuum method still need solve.Vacuum method comprises that mainly common vapour deposition method and two step sputters add the selenizing method.
Vapour deposition method all is a kind of common deposition process in laboratory and commercial the application altogether.Vapour deposition method uses a plurality of evaporation sources and three step process to make Copper Indium Gallium Selenide film absorption layer altogether, can well control process parameters and adjusting film composition structure and band gap.The copper-indium-galliun-selenium film solar cell of peak efficiency is exactly to make in this way at present, this high efficiency mainly gives the credit to effective classification of gallium, produce the back field simultaneously, stoped reconfiguring of electronics and cavity, thereby effectively raised energy conversion efficiency.Yet the uniformity of vapour deposition method still faces some problems when large-scale production altogether; Simultaneously, how accurately controlling each evaporation source also is the big problem that the associating vapour deposition method need solve.
Two step sputtering methods.This method is the technology of present production Copper Indium Gallium Selenide film absorption layer forefront.It comprises technical processs such as sputter and selenizing.This method is a raw material with copper gallium or copper/gallium target and indium target, the method for using cosputtering or sputter continuously with alloy deposition to amorphous thin film; Again film is carried out selenizing in the environment of hydrogen selenide or selenium afterwards, finally form the p-type absorbed layer.At present, Ri Ben Solar Frontier company has produced the low-cost copper-indium-galliun-selenium film solar cell production line of 900MW production capacity with the method.Miasole and Nuvosun company have also produced the production line of 80MW and 50MW respectively with the method.The target as sputter method or has led the scale of mass production of copper-indium-galliun-selenium film solar cell, because this method all has significant advantage on large-area uniformity and high deposition rate.Yet the last selenizing step of this method has certain environment hidden danger, because hydrogen selenide gas has toxicity; This method needs high temperature simultaneously, and this has also increased the technology cost.
The pluses and minuses of the production method of the production method of CIGS thin-film see Table 1.
The production method contrast of the production method of table 1 CIGS thin-film
Vapour deposition method can make copper-indium-galliun-selenium film solar cell efficient reach 20.3% altogether, and this not only gives the credit to evaporation process, and the factor of structure optimization is equally also arranged; And sputter three step process method not only has important breakthrough on the hierarchy of gallium, has formed back aluminum back surface field, and the synthetic product of this method has the border structure of bulky grain degree simultaneously, and this characteristic is proved to be having raised the efficiency important function.In addition, doctor Stanbery of Heliovolt thinks that copper-indium-galliun-selenium film solar cell efficient also depends on the interior absorbed layer connecting structure between the n-type Copper Indium Gallium Selenide of the p-type Copper Indium Gallium Selenide of rich copper and poor copper.Absorbed layer links model and will can be good at explaining at present about a lot of difficult problems of copper-indium-galliun-selenium film solar cell in this, comprises that gallium also has the facilitation of indium to the n-type Copper Indium Gallium Selenide structure that lacks copper to the facilitation of the p-type Copper Indium Gallium Selenide structure that is rich in copper.
Copper-indium-galliun-selenium film solar cell is quickening to come into the market.Though solar energy giant Solyndra has before met with some setbacks, nova Solar Frontier is emerging and is becoming the maximum winner of copper-indium-galliun-selenium film solar cell industry; It will be the problem of time that copper-indium-galliun-selenium film solar cell leads whole solar energy industry.Yet present CuInGaSe absorbed layer deposition technique has become the biggest obstacle in its commercialization process.Therefore whole industry exigence searches out a kind of effective ways and overcomes this obstacle, the scale of mass production cost of copper-indium-galliun-selenium film solar cell plate will be dropped to below 1 dollar/watt simultaneously.
Summary of the invention
Goal of the invention: the production method that the purpose of this invention is to provide the CIGS thin-film that a kind of production cost is low, absorption efficiency is high.
Technical scheme: the invention provides a kind of method of utilizing Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film, may further comprise the steps:
(1) under 300-400 ℃, as target ground floor film in sputter in the substrate, sputtering time is 5-40min to the power of use 40W-300W, forms the first poor copper layer with the Copper Indium Gallium Selenide alloy; Because temperature and power are lower, so indium gallium selenium atom can sputter out, and copper atom can't sputter out, and therefore the main component of the first poor copper layer is gallium indium selenium and a spot of copper;
(2) under 500-600 ℃, as target second layer film in sputter on the first poor copper layer, sputtering time is 20min-3h to the power of use 60W-350W, forms rich copper layer with the Copper Indium Gallium Selenide alloy; Because temperature and power are higher, so the Copper Indium Gallium Selenide atom all can sputter out, and is Copper Indium Gallium Selenide thereby make the main component of rich copper layer;
(3) under 500-600 ℃, as target three-layer thin-film in sputter on the rich copper layer, sputtering time is 5-40min to the power of use 20W-200W, forms the second poor copper layer, promptly gets CIGS thin-film with the Copper Indium Gallium Selenide alloy; Because power is lower, so indium gallium selenium atom can sputter out, and copper atom can't sputter out, and therefore the main component of the first poor copper layer is gallium indium selenium and a spot of copper.
Wherein, in the step (1), the horizontal cross sectional geometry that is shaped as of described substrate is square cube shaped for circular round pie or horizontal cross sectional geometry.
Wherein, in the step (1), described substrate is soda-lime glass, stainless steel thin slice, aluminium foil or plastic sheet, preferred polyimide plastics of described plastic sheet or poly terephthalic acid class plastics.
Wherein, in the step (1), described substrate surface is provided with the sodium fluoride layer, and the thickness of described sodium fluoride layer is 3-20nm; Thereby sodium atom content is between 1% to 15% in the assurance CuInGaSe absorbed layer, the size of crystal grain is increased, and then improve the efficient of solar cell.
Wherein, in the step (1), the thickness of described substrate is 2-6mm.
Wherein, in the step (1), the atomicity of Copper Indium Gallium Selenide is than being (20-25) in the described Copper Indium Gallium Selenide alloy: (10-19): (6-12.5): (50-60).
Wherein, in the step (1), further comprising the steps of: adopt method of evaporating or sputtering method to plate molybdenum layer in the substrate, the thickness of described molybdenum layer is 200-1500nm, and the resistivity of described molybdenum layer is the 0.2-5 ohmcm.
Wherein, in the step (2), further comprising the steps of: adopt chemical basin sedimentation (CBD) to plate the cadmium sulfide transition zone on the second poor copper layer, the thickness of described cadmium sulfide transition zone is 40-250nm, and 1-5min then anneals under 150-250 ℃ of condition.
Beneficial effect: the production method of CIGS thin-film provided by the invention will be total to evaporation three step process method and the combination of antivacuum intrinsic absorption layer connecting structure method, not only can promote utilization rate of raw materials significantly, cost is low, and deposition rate is fast in the sputtering technology process, also will form absorbed layer connecting structure IAJ in the gallium gradient-structure optimized and the nanometer farmland p-n junction simultaneously in CuInGaSe absorbed layer, the CIGS thin-film efficient height of producing, area is big, the uniformity is high.
Particularly, the present invention has following outstanding advantage with respect to prior art:
1. efficient height
In order to obtain high efficiency product and reducing production costs, the present invention uses Copper Indium Gallium Selenide sputtering target material and three step depositing operations, obtaining to have the film of unique CIGS thin-film absorbent layer structure, thereby has improved battery efficiency.The most important innovative point of the present invention is unique CIGS thin-film absorbent layer structure: absorbed layer connecting structure in the p-n on the hierarchy of gallium, large-sized granular boundary and nanometer farmland.The present invention will realize the deposition of high efficiency battery core layer by changing size of current, base reservoir temperature and sputtering power, thereby obtain the interior absorbed layer connecting structure of p-n on hierarchy, large-sized granular boundary and the nanometer farmland of gallium.Whole CIGS thin-film absorbed layer is made up of nanometer p-n junction structure, so the probability that electronics and hole recombination form photon diminishes, and battery efficiency will be improved.The gallium hierarchy can produce the back field, reduces electronics and hole recombination probability, is the key factor that common vapour deposition method can obtain the high efficiency copper-indium-galliun-selenium film solar cell; The connecting structure (IAJ) of absorbed layer in can also forming simultaneously, thereby the probability that makes electronics and hole recombination form photon diminishes, CIGS thin-film efficient is got a promotion, and the unique texture of product makes copper-indium-galliun-selenium film solar cell all have commercial competitiveness on efficient and cost.
Because adopt Copper Indium Gallium Selenide quaternary element alloy target, the content of selenium is abundant in the target, in whole steps, the film that is plated is in the atmosphere of selenizing from the beginning to the end.The CIGS thin-film that makes does not need to pass through the selenizing step again, has avoided the pollution of hydrogen selenide and other toxic gases.Simultaneously, shorten the production time greatly, saved heating cost, thereby reduced the manufacturing cost of final products.
2. cost is low
The best method that reduces the manufacture of solar cells cost of CIGS thin-film mainly will rely on three aspects: improve raw-material utilization rate 1.; 2. thereby optimize production process and technology and improve speed of production and productive rate; 3. optimize product structure and improve the efficient of solar panel.Production method of the present invention will significantly improve production efficiency, simplify production technology, improve solar battery efficiency, can not form pressure to environmental protection simultaneously, thereby finally reduce the production cost of the solar cell of CIGS thin-film.
3. the CIGS thin-film uniformity height that makes
The present invention uses quaternary element alloy sputtering target material to replace traditional copper gallium/copper/gallium and indium target, quaternary element alloy sputtering target material can be controlled the CuInGaSe absorbed layer structure accurately, thereby has guaranteed because the CIGS thin-film of sputter system method preparation has better uniformity when having large tracts of land, high deposition rate.
4. be widely used
The present invention will reduce the production cost of copper-indium-galliun-selenium film solar cell, thereby enlarge the application of solar cell, as space exploration, rural electrification and building field.Preparation method's technology of the present invention will have business potential, and be that whole industry and environmental protection bring lifting and Gospel.
Description of drawings
Fig. 1 is the structural representation of copper indium gallium selenium solar cell.
Fig. 2 prepares the flow chart of CIGS thin-film for the present invention.
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, process conditions and result thereof only are used to illustrate the present invention, and should also can not limit the present invention described in detail in claims.
Utilize the method for Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film, in the described Copper Indium Gallium Selenide alloy diameter of Copper Indium Gallium Selenide be 3 inches, thickness be 1/4 inch, atomicity than being 25:17.5:7.5:50, may further comprise the steps:
(1) plate the sodium fluoride layer with method of evaporating at the soda-lime glass substrate surface, evaporation conditions is that initial depression is 10
-6Torr, voltage 7KV, electric current 20mA, the thickness of described sodium fluoride layer are 3nm;
(2) adopt sputtering method will be coated with in the soda-lime glass substrate of sodium fluoride layer and plate molybdenum layer, evaporation conditions is that initial depression is 10
-6The argon gas of Torr, feeding 20SCCM makes vacuum pressure reach 6mTorr, sputtering power 150W, sputtering time 45min, and the thickness of described molybdenum layer is 200nm, and the resistivity of described molybdenum layer is 5 ohmcms;
(3) under 300 ℃, the power that uses 40W with the Copper Indium Gallium Selenide alloy as target thickness as the soda-lime glass substrate that is coated with sodium fluoride layer and molybdenum layer of 2mm on ground floor film in the sputter, sputtering time is 5min, forms the first poor copper layer; Described substrate be shaped as round pie, its horizontal cross sectional geometry is circular;
(4) under 500 ℃, as target second layer film in sputter on the first poor copper layer, sputtering time is 3h to the power of use 60W, forms rich copper layer with the Copper Indium Gallium Selenide alloy;
(5) under 500 ℃, as target three-layer thin-film in sputter on the rich copper layer, sputtering time is 40min to the power of use 20W, forms the second poor copper layer with the Copper Indium Gallium Selenide alloy;
(6) adopt chemical basin sedimentation to plate the cadmium sulfide transition zone on the second poor copper layer, promptly get the CIGS thin-film of overall poor copper, the thickness of described cadmium sulfide transition zone is 40nm, concrete operations are: with the distilled water of 240ml with after the 28-30% ammoniacal liquor of 37.5ml mixes, add the cadmium sulfate of 0.015mol33ml, the sulphur urine mixing of 1.5mol16.5ml more successively, add the material that step (5) obtains, keep water temperature at 55-80 ℃, and constantly stir 5min to 1h, clean for several times with distilled water then, dry up with nitrogen; 1min then anneals under 250 ℃ of conditions.
Utilize the method for Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film, in the described Copper Indium Gallium Selenide alloy diameter of Copper Indium Gallium Selenide be 3 inches, thickness be 1/4 inch, atomicity than being 25:17.5:7.5:55, may further comprise the steps:
(1) plate the sodium fluoride layer with method of evaporating at stainless steel thin slice substrate surface, evaporation conditions is that initial depression is 10-6Torr, voltage 7KV, electric current 20mA, and the thickness of described sodium fluoride layer is 8nm;
(2) adopt sputtering method will be coated with in the soda-lime glass substrate of sodium fluoride layer and plate molybdenum layer, evaporation conditions is that initial depression is that 10-6Torr, the argon gas that feeds 20SCCM make vacuum pressure reach 6mTorr, sputtering power 150W, sputtering time 45min, the thickness of described molybdenum layer is 600nm, and the resistivity of described molybdenum layer is 3.2 ohmcms;
(3) under 350 ℃, the power that uses 60W with the Copper Indium Gallium Selenide alloy as target thickness as the soda-lime glass substrate that is coated with sodium fluoride layer and molybdenum layer of 4mm on ground floor film in the sputter, sputtering time is 15min, forms the first poor copper layer; Being shaped as of described substrate is cube shaped, and its horizontal cross sectional geometry is square;
(4) under 550 ℃, as target second layer film in sputter on the first poor copper layer, sputtering time is 2h to the power of use 200W, forms rich copper layer with the Copper Indium Gallium Selenide alloy;
(5) under 550 ℃, as target three-layer thin-film in sputter on the rich copper layer, sputtering time is 30min to the power of use 60W, forms the second poor copper layer with the Copper Indium Gallium Selenide alloy;
(6) adopt chemical basin sedimentation to plate the cadmium sulfide transition zone on the second poor copper layer, the thickness of described cadmium sulfide transition zone is 150nm, promptly gets the CIGS thin-film of overall poor copper; Concrete operations are: with the distilled water of 240ml with after the 28-30% ammoniacal liquor of 37.5ml mixes, add the cadmium sulfate of 0.015mol33ml, the sulphur urine mixing of 1.5mol16.5ml more successively, keep water temperature at 55-80 ℃, the Copper Indium Gallium Selenide sample that step (5) prepares is put into this solution, and constantly stir 5min to 1h, and the sample that plates cadmium sulfide is taken out, clean for several times with distilled water then, dry up with nitrogen, 5min then anneals under 150 ℃ of conditions.
Utilize the method for Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film, in the described Copper Indium Gallium Selenide alloy diameter of Copper Indium Gallium Selenide be 3 inches, thickness be 1/4 inch, atomicity than being 20:10:12.5:50, may further comprise the steps:
(1) plate the sodium fluoride layer with method of evaporating at the aluminium foil substrate surface, evaporation conditions is that initial vacuum degree is 10-6Torr, voltage 7KV, electric current 20mA, and the thickness of described sodium fluoride layer is 14nm;
(2) adopt sputtering method will be coated with in the soda-lime glass substrate of sodium fluoride layer and plate molybdenum layer, evaporation conditions is that initial vacuum degree is that 10-6Torr, the argon gas that feeds 20SCCM make vacuum pressure reach 6mTorr, sputtering power 150W, sputtering time 45min, the thickness of described molybdenum layer is 1000nm, and the resistivity of described molybdenum layer is 1.0 ohmcms;
(3) under 400 ℃, the power that uses 300W with the Copper Indium Gallium Selenide alloy as target thickness as the soda-lime glass substrate that is coated with sodium fluoride layer and molybdenum layer of 5mm on ground floor film in the sputter, sputtering time is 30min, forms the first poor copper layer; Described substrate be shaped as round pie, its horizontal cross sectional geometry is circular;
(4) under 500 ℃, as target second layer film in sputter on the first poor copper layer, sputtering time is 45min to the power of use 350W, forms rich copper layer with the Copper Indium Gallium Selenide alloy;
(5) under 550 ℃, as target three-layer thin-film in sputter on the rich copper layer, sputtering time is 20min to the power of use 150W, forms the second poor copper layer with the Copper Indium Gallium Selenide alloy;
(6) adopt chemical basin sedimentation to plate the cadmium sulfide transition zone on the second poor copper layer, the thickness of described cadmium sulfide transition zone is 150nm, promptly gets the CIGS thin-film of overall poor copper; Concrete operations are: with the distilled water of 240ml with after the 28-30% ammoniacal liquor of 37.5ml mixes, add the cadmium sulfate of 0.015mol33ml, the sulphur urine mixing of 1.5mol16.5ml more successively, keep water temperature at 55-80 ℃, the Copper Indium Gallium Selenide sample that step (5) prepares is put into this solution, and constantly stir 5min to 1h, and the sample that plates cadmium sulfide is taken out, clean for several times with distilled water then, dry up with nitrogen, 5min then anneals under 150 ℃ of conditions.
Utilize the method for Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film, in the described Copper Indium Gallium Selenide alloy diameter of Copper Indium Gallium Selenide be 3 inches, thickness be 1/4 inch, atomicity than being 22.5:19:6:60, may further comprise the steps:
(1) plate the sodium fluoride layer with method of evaporating at the plastic base basal surface, evaporation conditions is that initial vacuum degree is 10-6Torr, voltage 7KV, electric current 20mA, and the thickness of described sodium fluoride layer is 20nm; Described plastic sheet can be polyimide plastics or poly terephthalic acid class plastics;
(2) adopt sputtering method will be coated with in the soda-lime glass substrate of sodium fluoride layer and plate molybdenum layer, evaporation conditions is that initial vacuum degree is that 10-6Torr, the argon gas that feeds 20SCCM make vacuum pressure reach 6mTorr, sputtering power 150W, sputtering time 45min, the thickness of described molybdenum layer is 1500nm, and the resistivity of described molybdenum layer is 0.2 ohmcm;
(3) under 350 ℃, the power that uses 150W with the Copper Indium Gallium Selenide alloy as target thickness as the soda-lime glass substrate that is coated with sodium fluoride layer and molybdenum layer of 6mm on ground floor film in the sputter, sputtering time is 40min, forms the first poor copper layer; Being shaped as of described substrate is cube shaped, and its horizontal cross sectional geometry is square;
(4) under 600 ℃, as target second layer film in sputter on the first poor copper layer, sputtering time is 20min to the power of use 250W, forms rich copper layer with the Copper Indium Gallium Selenide alloy;
(5) under 600 ℃, as target three-layer thin-film in sputter on the rich copper layer, sputtering time is 5min to the power of use 200W, forms the second poor copper layer with the Copper Indium Gallium Selenide alloy;
(6) adopt chemical basin sedimentation to plate the cadmium sulfide transition zone on the second poor copper layer, the thickness of described cadmium sulfide transition zone is 150nm, promptly gets the CIGS thin-film of overall poor copper; Concrete operations are: the distilled water of 240ml with after the 28-30% ammoniacal liquor of 37.5ml mixes, is added cadmium sulfate, the 1.5mol16.5ml of 0.015mol33ml more successively
Sulphur urine mix, keep water temperature at 55-80 ℃, the Copper Indium Gallium Selenide sample that step (5) prepares is put into this solution, and constantly stir 5min to 1h, and the sample that plates cadmium sulfide is taken out, clean for several times with distilled water then, dry up with nitrogen, 5min then anneals under 150 ℃ of conditions.
Utilize the method for Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film, in the described Copper Indium Gallium Selenide alloy diameter of Copper Indium Gallium Selenide be 3 inches, thickness be 1/4 inch, atomicity than being 25:17.5:7.5:50, may further comprise the steps:
(1) under 450 ℃, the power that uses 50W with the Copper Indium Gallium Selenide alloy as target thickness as the soda-lime glass substrate of 2mm on ground floor film in the sputter, sputtering time is 15min, forms the first poor copper layer;
(2) under 550 ℃, as target second layer film in sputter on the first poor copper layer, sputtering time is 45min to the power of use 250W, forms rich copper layer with the Copper Indium Gallium Selenide alloy;
(3) under 600 ℃, as target three-layer thin-film in sputter on the rich copper layer, sputtering time is 20min to the power of use 50W, forms the second poor copper layer, promptly gets the CIGS thin-film of overall poor copper with the Copper Indium Gallium Selenide alloy.
The CIGS thin-film of utilizing embodiment 1 to 5 to make is used for copper-indium-galliun-selenium film solar cell, and measures solar battery efficiency.The current-voltage data of solar cell are measured on Oriel solar simulator and Keithley2400 current source instrument, can directly obtain the efficient of solar cell from the Labview I-V operating software, survey 3 times, the results are shown in Table 1 for every group.
The CIGS thin-film that table 1 utilizes embodiment 1 to 5 to make is used for the efficient of copper-indium-galliun-selenium film solar cell
Claims (8)
1. method of utilizing Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film is characterized in that: may further comprise the steps:
(1) under 300-400 ℃, as target ground floor film in sputter in the substrate, sputtering time is 5-40min to the power of use 40W-300W, forms the first poor copper layer with the Copper Indium Gallium Selenide alloy;
(2) under 500-600 ℃, as target second layer film in sputter on the first poor copper layer, sputtering time is 20min-3h to the power of use 60W-350W, forms rich copper layer with the Copper Indium Gallium Selenide alloy;
(3) under 500-600 ℃, as target three-layer thin-film in sputter on the rich copper layer, sputtering time is 5-40min to the power of use 20W-200W, forms the second poor copper layer, promptly gets CIGS thin-film with the Copper Indium Gallium Selenide alloy.
2. a kind of method of utilizing Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film according to claim 1, it is characterized in that: in the step (1), the horizontal cross sectional geometry that is shaped as of described substrate is square cube shaped for circular round pie or horizontal cross sectional geometry.
3. a kind of method of utilizing Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film according to claim 1 is characterized in that: in the step (1), described substrate is soda-lime glass, stainless steel thin slice, aluminium foil or plastic sheet.
4. a kind of method of utilizing Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film according to claim 1, it is characterized in that: in the step (1), described substrate surface is provided with the sodium fluoride layer, and the thickness of described sodium fluoride layer is 3-20nm.
5. a kind of method of utilizing Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film according to claim 1 is characterized in that: in the step (1), the thickness of described substrate is 2-6mm.
6. a kind of method of utilizing Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film according to claim 1, it is characterized in that: in the step (1), the atomicity of Copper Indium Gallium Selenide is than being (20-25) in the described Copper Indium Gallium Selenide alloy: (10-19): (6-12.5): (50-60).
7. a kind of method of utilizing Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film according to claim 3, it is characterized in that: in the step (1), further comprising the steps of: as to adopt method of evaporating or sputtering method to plate molybdenum layer in the substrate, the thickness of described molybdenum layer is 200-1500nm, and the resistivity of described molybdenum layer is the 0.2-5 ohmcm.
8. a kind of method of utilizing Copper Indium Gallium Selenide alloy sputtering target production CIGS thin-film according to claim 1, it is characterized in that: in the step (2), further comprising the steps of: as to adopt chemical basin sedimentation to plate the cadmium sulfide transition zone on the second poor copper layer, the thickness of described cadmium sulfide transition zone is 40-250nm, and 1-5min then anneals under 150-250 ℃ of condition.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112002780A (en) * | 2020-07-21 | 2020-11-27 | 重庆神华薄膜太阳能科技有限公司 | Thin film solar cell and method for manufacturing same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768729A (en) * | 2010-03-05 | 2010-07-07 | 中国科学院上海硅酸盐研究所 | Method for preparing light absorption layer of CIGS (copper indium gallium selenide) thin film solar cell by magnetron sputtering method |
| CN102290339A (en) * | 2011-10-07 | 2011-12-21 | 南昌航空大学 | Novel process for preparing CIGS (Cu (In, Ga) Se2) solar cell absorption layer through sputtering CIGS (Cu (In, Ga) Se2) target material continuously |
| JP2012092438A (en) * | 2010-09-27 | 2012-05-17 | Hitachi Metals Ltd | Mo-based sputtering target and method of manufacturing the same, and cigs-based thin-film solar cell using the same |
-
2013
- 2013-03-26 CN CN201310099414.XA patent/CN103219419B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768729A (en) * | 2010-03-05 | 2010-07-07 | 中国科学院上海硅酸盐研究所 | Method for preparing light absorption layer of CIGS (copper indium gallium selenide) thin film solar cell by magnetron sputtering method |
| JP2012092438A (en) * | 2010-09-27 | 2012-05-17 | Hitachi Metals Ltd | Mo-based sputtering target and method of manufacturing the same, and cigs-based thin-film solar cell using the same |
| CN102290339A (en) * | 2011-10-07 | 2011-12-21 | 南昌航空大学 | Novel process for preparing CIGS (Cu (In, Ga) Se2) solar cell absorption layer through sputtering CIGS (Cu (In, Ga) Se2) target material continuously |
Non-Patent Citations (2)
| Title |
|---|
| ZHAO-HUI LI, ET AL.: "Properties of the Cu(In,Ga)Se2 absorbers deposited by electron-beam evaporation method for solar cells", 《CURRENT APPLIED PHYSICS》, no. 11, 31 December 2011 (2011-12-31), pages 28 - 33, XP027332205 * |
| 谈晓辉: "铜铟镓硒薄膜太阳电池吸收层的研究", 《中国博士学位论文全文数据库 工程科技II辑》, no. 7, 15 July 2012 (2012-07-15), pages 22 - 36 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112002780A (en) * | 2020-07-21 | 2020-11-27 | 重庆神华薄膜太阳能科技有限公司 | Thin film solar cell and method for manufacturing same |
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