A kind of method preparing precursor alloy and absorption layer film
Technical field
The present invention relates to a kind of method preparing novel precursor alloy and absorption layer film, belong to solar cell photovoltaic field.
Background technology
Global energy requirements is climbed to a higher point year by year, and under energy-conservation and environmental consciousness come back, the development renewable energy resources are global common target; With the renewable energy resources, no matter waterpower, wind-force, geothermal power generation, all need obtain efficiency of conversion with kinetic energy conversion regime, solar electrical energy generation is then the power generation system utilizing sunlight to convert electric energy to, without moving part in solar power system, rotary machine must be used unlike in the power generation systems such as wind-force, waterpower, underground heat, therefore not have the puzzlement such as High Temperature High Pressure and noise, in power generation process, do not cause environmental pressure, be a cleanly green energy resource.In addition, the characteristic that solar source is inexhaustible, makes solar power system can have the large advantage of one of continuous utilization; Although the photoelectric transformation efficiency of solar electrical energy generation is still not high now, it is its advantage that solar power system does not need to expend extra energy cost, and in other words, these are not had fraction as power source by the energy that people utilize originally now.The sun is irradiated to the energy on earth's surface every day, and exceed the energy required for the universe 30 years, solar cell has become the main flow of following substitute energy.
The huge number of solar cell, and CIGS (copper-indium-galliun-selenium) thin-film solar cells has high conversion efficiency and development potentiality and is attracted attention, the most high conversion efficiency of current CIGS (copper-indium-galliun-selenium) thin-film solar cells created by U.S.'s Renewable Energy Laboratory (NREL), and its efficiency reaches 20%.CIGS is developed so far efficiency of conversion from nineteen ninety-five and has improved and have 7% more than fully, within the same time CdTe 4%, silicon single crystal and polysilicon be respectively 1% of 3% and non-crystalline silicon, be enough to find out the development potentiality of CIGS in efficiency of conversion.CIGS belongs to polycrystalline yellow copper structure (Chalcopyrite) compound of I-III-VI race, be a kind of by II-VI compounds of group zincblende lattce structure (Zinc-Blend Structure) the semiconductor material that derives, formed by the unit cell storehouse of two zink sulphide, the crystallographic site belonging to II race's element originally is replaced by I race and III race and is formed, crystallographic site residing for the inner In of chalcopyrite then can be the Ga element that adds replace.CIGS (copper-indium-galliun-selenium) has the P-type characteristic of semiconductor of direct gap (Direct band-gap) character, and has quite high photoabsorption coefficient α (α=10
4~ 10
5cm
-1), be 100 times of silicon single crystal, most solar spectrum can be contained, compared with other solar cell, therefore only need the thickness of 1 ~ 3 μm, be i.e. the incident sunlight of Absorbable rod more than 99%.The most high conversion efficiency of current CIGS thin film solar cell created by U.S.'s Renewable Energy Laboratory (NREL), and its efficiency reaches 20%.And NREL shows in assessment report in 2011, CIGS (copper-indium-galliun-selenium) up can grow up with annual 0.3% in efficiency of conversion.
CIGS (copper-indium-galliun-selenium) thin-film solar cells be developed so far its unit construction roughly part be made up of top electrode (AL/Ni), anti-reflecting layer (MgF2), optical window layer (AZO/ITO), buffer layer (CdS), absorption layer (CIGS), back electrode (Mo) and substrate (SS/GLASS/PET), in single rete, the parameter allotment of each material composition ratio, film crystal structure, processing procedure mode and various factorss such as optimizing processing procedure are the challenge on it is prepared, in addition, also need to consider that each rete is stacked into the matching of assembly, the many factors such as to influence each other between each Film preparation mode and processing procedure, especially CIGS (copper-indium-galliun-selenium) is shown for extremely responsive for component influences various process parameter from pertinent literature, more increase the difficulty of CIGS (copper-indium-galliun-selenium) thin-film solar cells in preparation, also make technology door relatively improve simultaneously, a kind of solar cell that technical difficulty is larger is thought at international photovoltaic circle.
Target has the mother metal of solid shape for sputter coating.If target can be divided into metal and pottery two large classes simply according to materials classification, if melting processing procedure and the large class of powder metallurgy processing procedure two usually generally can be divided into according to processing procedure classification.Most metals target adopts melting processing procedure, and minority target just adopts powder metallurgy processing procedure in view of the factors such as grain size controls, alloy ingredient fusing point gap is too large during use.Generally adopt vacuum induction melting to allocate composition for metal or alloy target material, and obtain required target through machining mode such as the forging of back segment and thermal treatments.As touch screen, unicircuit, liquid crystal display, building glass, blooming and thin-film solar cells etc. in current photoelectricity and semiconductor industry, be obtain large-area uniformity and production, associated film uses vacuum magnetic control sputter process all in a large number.
Multi-element compounds solar cell is at present by belonging to one of object material, be that the solar battery obsorbing layer formed with I race of race of race-III-IV can the regulation and control of its composition carry out being change and reaching best photoelectric conversion efficiency, wherein, I race is copper (Cu), silver (Ag), gold (Au), III race is aluminium (Al), gallium (Ga), indium (In), IV race is sulphur (S), selenium (Se), antimony (Te), the highest with copper indium gallium selenium solar cell photoelectric transformation efficiency at present.
In CIGS rete, absorption layer is the important rete affecting battery efficiency and the mode of production, and absorption layer generally uses vacuum evaporation and vacuum magnetic control sputter to add the heat treated two kinds of main processing procedures of rear selenizing, has the characteristic of big area film forming and the better homogeneity of acquisition.Typical case's CIGS solar cell is Mo (molybdenum dorsum electrode layer)/CIGS (CuInGaSe absorbed layer)/CdS (Cadmium Sulfide buffer layer)/ZnO+AZO (zinc oxide with mix aluminum zinc oxide optical window layer)/Al (aluminium upper electrode layer) according to base material from lower to upper, general dorsum electrode layer, optical window layer adopt vacuum splashing and plating mode, buffer layer adopts chemical waters mode, compared in each rete of unit construction, absorption layer preparation method is divided into two large classes: 1. vacuum process, comprises common evaporation and sputter precursors and selenizing processing procedure; 2. antivacuum processing procedure, comprises plating and coating etc.; Wherein use that to prepare buffer layer major cause absorption layer surface made by the current stage in chemical bath mode very thick, need reach complete batch of buffer layer by immersion method is overlying on absorption layer, but, in whole production CIGS solar cell process, immersion method processing procedure mode is used to have several restriction: 1. do not add for continuous production; 2. large-area uniformity is wayward; 3. need in immersion method making processes to consume large water gaging; 4. immersion method uses chemical solvents subsequent treatment cost high.If the flattening surface of absorption layer just can not be able to be adopted waters method to do buffer layer, avoid the discontinuity of producing to enhance productivity and yield, and reduce production cost.
Absorption layer film is prepared for a large amount of and big area, current processing procedure mode system adopts sputter precursors and rear selenizing processing procedure, wherein, early stage precursors metallic film is designed to single-element or double base alloyed metal adopts multiple gun sputter, processing procedure passage is many, time is grown and has the factors such as low melting point alloy processing procedure unstable, the present invention's ternary precursor Composition Design is in the past Cu/ (In+Ga) ≒ 0.6-0.95, Ga/ (In+Ga) ≒ 0.2-0.42, this alloy designs to cause in selenidation process phase change in advance cause reaction not exclusively and roughness of film large, be unfavorable for the preparation of follow-up buffer layer and optical window layer, and required formation absorption layer phase change temperature reduces, cause follow-up selenizing cannot continue to diffuse in precursors film and react, make selenizing not exclusively and efficiency of conversion cannot effectively promote, improve manufacturing cost because of above-mentioned reason and reduce process rate and productive rate.
Summary of the invention
The object of this invention is to provide a kind of polynary precursors alloy designs and prepare absorption layer method, absorption layer precursor is made with having the above precursors alloy ingredient of adjustable change ternary, control the Composition Design of precursor, ternary precursor is not yet reached at selenization temperature, and the temperature of fusion (200 DEG C-250 DEG C) of selenium is front can not produce phase change, guarantee that selenidation process complete reaction can complete (500-650 DEG C) in certain temperature range, and make the Flatness that the film surface after selenizing reaches best, be conducive to the making of follow-up buffer layer and optical window layer, the efficiency of CIGS thin film solar cell can be promoted.
Prepare a method for new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1-1.56, Ga/ (In+Ga)=0.29-0.52; First the material of part by weight is put into vacuum induction melting furnace and carry out melting, vacuum tightness 5 × 10
-2torr, melting temperature (Tm) is 650 DEG C/15mins, then casts in the mould of the soft steel of three cun, treats that cooling 12 as a child demoulding taking-up target idiosome is for subsequent use through being machined to three cun of sputter targets; Then be substrate with non-alkali glass, then plate glass baseplate and sputter target puts into sputter cavity required, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.7 × 10
-5-0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through throttling valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, plating rate 40nm/min, first with the Mo film that DC power supply sputter the first layer 500nm is thick, then use operating pressure 2.5 × 10
-3torr, plating rate 12nm/min carrys out the thick CIG absorption layer precursors film of sputter second layer 1000nm, then coated film is placed in selenizing stove and carries out rear selenizing, selenizing temperature 500-650 DEG C, time 10-30min, it is thick that selenizing rear film thickness is about 2000nm, then takes out the measurement that surface roughness is carried out in test piece.
A kind of method preparing new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1-1.56, Ga/ (In+Ga)=0.29-0.52, and add the 4th element Al/ (In+Ga)=0.1-0.5, Ag/ (In+Ga)=0.1-0.5 or Au/ (In+Ga)=0.1-0.5; First the material of part by weight is put into vacuum induction melting furnace and carry out melting, vacuum tightness 5 × 10
-2torr, melting temperature (Tm), at 650 DEG C/15mins, then casts in the mould of the soft steel of three cun, treats that cooling 12 as a child demoulding taking-up target idiosome is for subsequent use through being machined to three cun of sputter targets; Then be substrate with non-alkali glass, then plate glass baseplate and sputter target puts into sputter cavity required, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.7 × 10
-5-0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through throttling valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, plating rate 40nm/min, first with the Mo film that DC power supply sputter the first layer 500nm is thick, then use operating pressure 2.5 × 10
-3torr, plating rate 12nm/min carrys out the thick CIG absorption layer precursors film of sputter second layer 1000nm, then coated film is placed in selenizing stove and carries out rear selenizing, selenizing temperature 500-650 DEG C, time 10-30min, it is thick that selenizing rear film thickness is about 2000nm, then takes out the measurement that surface roughness is carried out in test piece.
Feature of the present invention is the method in a kind of new multicomponent precursors alloying constituent of preparation and absorption layer film thereof, vacuum melting is used to make alloy ingredient fully mix to improve the density of target and homogeneity to extend target work-ing life, and by composition redesign and add quad alloy element the surface roughness of the absorption layer film after selenizing reduced, obtain large-area homogeneity, the procedure for producing of CIGS battery can be carried out completely in a vacuum, and all over exempting to use the CdS of waters method to avoid the problem of Cd pollution, make the volume production of CIGS thin film solar cell more feasible, and obtain preferably PN characteristic, the CIGS battery of high conversion efficiency can be obtained, reduce production cost and the requirement meeting volume production.
embodiment:
Embodiment 1:
Prepare a method for new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1, Ga/ (In+Ga)=0.29; First the material of part by weight is put into vacuum induction melting furnace and carry out melting, vacuum tightness 5 × 10
-2torr, melting temperature (Tm) is 650 DEG C/15mins, then casts in the mould of the soft steel of three cun, treats that cooling 12 as a child demoulding taking-up target idiosome is for subsequent use through being machined to three cun of sputter targets; Then be substrate with non-alkali glass, then plate glass baseplate and sputter target puts into sputter cavity required, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.7 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through throttling valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, plating rate 40nm/min, first with the Mo film that DC power supply sputter the first layer 500nm is thick, then use operating pressure 2.5 × 10
-3torr, plating rate 12nm/min carry out the thick CIG absorption layer precursors film of sputter second layer 1000nm, are then placed in selenizing stove by coated film and carry out rear selenizing, selenizing temperature 500 DEG C, time 10min, it is thick that selenizing rear film thickness is about 2000nm, then takes out the measurement that surface roughness is carried out in test piece.
Embodiment 2:
Prepare a method for new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1.28, Ga/ (In+Ga)=0.40; First the material of part by weight is put into vacuum induction melting furnace and carry out melting, vacuum tightness 5 × 10
-2torr, melting temperature (Tm) is 650 DEG C/15mins, then casts in the mould of the soft steel of three cun, treats that cooling 12 as a child demoulding taking-up target idiosome is for subsequent use through being machined to three cun of sputter targets; Then be substrate with non-alkali glass, then plate glass baseplate and sputter target puts into sputter cavity required, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through throttling valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, plating rate 40nm/min, first with the Mo film that DC power supply sputter the first layer 500nm is thick, then use operating pressure 2.5 × 10
-3torr, plating rate 12nm/min carry out the thick CIG absorption layer precursors film of sputter second layer 1000nm, are then placed in selenizing stove by coated film and carry out rear selenizing, selenizing temperature 580 DEG C, time 20min, it is thick that selenizing rear film thickness is about 2000nm, then takes out the measurement that surface roughness is carried out in test piece.
Embodiment 3:
Prepare a method for new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1.56, Ga/ (In+Ga)=0.52; First the material of part by weight is put into vacuum induction melting furnace and carry out melting, vacuum tightness 5 × 10
-2torr, melting temperature (Tm) is 650 DEG C/15mins, then casts in the mould of the soft steel of three cun, treats that cooling 12 as a child demoulding taking-up target idiosome is for subsequent use through being machined to three cun of sputter targets; Then be substrate with non-alkali glass, then plate glass baseplate and sputter target puts into sputter cavity required, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.9 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through throttling valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, plating rate 40nm/min, first with the Mo film that DC power supply sputter the first layer 500nm is thick, then use operating pressure 2.5 × 10
-3torr, plating rate 12nm/min carrys out the thick CIG absorption layer precursors film of sputter second layer 1000nm, then coated film is placed in selenizing stove and carries out rear selenizing, selenizing temperature 650 DEG C, time 10-30min, it is thick that selenizing rear film thickness is about 2000nm, then takes out the measurement that surface roughness is carried out in test piece.
Embodiment 4:
A kind of method preparing new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1, Ga/ (In+Ga)=0.29, and add the 4th element Al/ (In+Ga)=0.1; All the other are with embodiment 1.
Embodiment 5:
A kind of method preparing new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1.28, Ga/ (In+Ga)=0.40, and add the 4th element Al/ (In+Ga)=0.3; All the other are with embodiment 2.
Embodiment 6:
A kind of method preparing new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1.56, Ga/ (In+Ga)=0.52, and add the 4th element Al/ (In+Ga)=0.5; All the other are with embodiment 3.
Embodiment 7:
A kind of method preparing new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1, Ga/ (In+Ga)=0.29, and add the 4th element Ag/ (In+Ga)=0.1; All the other are with embodiment 1.
Embodiment 8:
A kind of method preparing new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1.28, Ga/ (In+Ga)=0.40, and add the 4th element Ag/ (In+Ga)=0.3; All the other are with embodiment 2.
Embodiment 9:
A kind of method preparing new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1.56, Ga/ (In+Ga)=0.52, and add the 4th element Ag/ (In+Ga)=0.5; All the other are with embodiment 3.
Embodiment 10:
A kind of method preparing new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1, Ga/ (In+Ga)=0.29, and add the 4th element Au/ (In+Ga)=0.1; All the other are with embodiment 1.
Embodiment 11:
A kind of method preparing new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1.28, Ga/ (In+Ga)=0.40, and add the 4th element Au/ (In+Ga)=0.3; All the other are with embodiment 2.
Embodiment 12:
A kind of method preparing new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=1.56, Ga/ (In+Ga)=0.52, and add the 4th element Au/ (In+Ga)=0.5; All the other are with embodiment 3.
Comparative example 1:
Prepare a method for new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=0.69, Ga/ (In+Ga)=0.23; First the material of part by weight is put into vacuum induction melting furnace and carry out melting, vacuum tightness 5 × 10
-2torr, melting temperature (Tm) is 650 DEG C/15mins, then casts in the mould of the soft steel of three cun, treats that cooling 12 as a child demoulding taking-up target idiosome is for subsequent use through being machined to three cun of sputter targets; Then be substrate with non-alkali glass, then plate glass baseplate and sputter target puts into sputter cavity required, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.7 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through throttling valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, plating rate 40nm/min, first with the Mo film that DC power supply sputter the first layer 500nm is thick, then use operating pressure 2.5 × 10
-3torr, plating rate 12nm/min carry out the thick CIG absorption layer precursors film of sputter second layer 1000nm, are then placed in selenizing stove by coated film and carry out rear selenizing, selenizing temperature 520 DEG C, time 15min, it is thick that selenizing rear film thickness is about 2000nm, then takes out the measurement that surface roughness is carried out in test piece.
Comparative example 2:
A kind of method preparing new multicomponent precursors alloy and absorption layer film, ternary alloy composition part by weight span of control be: Cu/ (In+Ga)=0.85, Ga/ (In+Ga)=0.55, and add the 4th element Ag/ (In+Ga)=0.08; First the material of part by weight is put into vacuum induction melting furnace and carry out melting, vacuum tightness 5 × 10
-2torr, melting temperature (Tm), at 650 DEG C/15mins, then casts in the mould of the soft steel of three cun, treats that cooling 12 as a child demoulding taking-up target idiosome is for subsequent use through being machined to three cun of sputter targets; Then be substrate with non-alkali glass, then plate glass baseplate and sputter target puts into sputter cavity required, with vacuum-pumping system, sputter cavity background pressure is evacuated to 0.8 × 10
-5after torr, utilizing argon gas to be used as working gas, is 2 × 10 through throttling valve by the operating pressure passing into argon gas and control sputter cavity
-3torr, plating rate 40nm/min, first with the Mo film that DC power supply sputter the first layer 500nm is thick, then use operating pressure 2.5 × 10
-3torr, plating rate 12nm/min carry out the thick CIG absorption layer precursors film of sputter second layer 1000nm, are then placed in selenizing stove by coated film and carry out rear selenizing, selenizing temperature 600 DEG C, time 25min, it is thick that selenizing rear film thickness is about 2000nm, then takes out the measurement that surface roughness is carried out in test piece.
The measurement of the absorption layer film surface rugosity that each embodiment and comparative example obtain is as shown in the table:
As can be seen from upper table result, the CIGS thin film that the alloy target material of the specific composition that the present invention adopts and specified weight ratio is made effectively significantly can reduce surface roughness, simplify the plated film of follow-up buffer layer and optical window layer, production cost can be reduced and improve volume production efficiency, improve efficiency of conversion, obviously be better than the made CIGS thin film of other part by weight alloy target materials (comparative example 1 and comparative example 2), wherein more excellent with the effect of embodiment 2, embodiment 5, embodiment 8, embodiment 11, meet the needs of production.