CN102683435B - Thin-film solar cells electro-conductive glass and preparation method thereof - Google Patents
Thin-film solar cells electro-conductive glass and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of novel high-performance electro-conductive glass, particularly a kind of thin-film solar cells electro-conductive glass and preparation method thereof.Electro-conductive glass of the present invention, between metal conductive oxide layer (2) and the second metal conductive oxide layer (4), be gripped with metal level (3), metal conductive oxide layer (2), metal level (3) and the second metal conductive oxide layer (4) are successively set on the side of glass baseplate (1) on the surface.Electro-conductive glass of the present invention prepares metal conductive oxide layer by LPCVD, PECVD, SPUTFER or SPRAY method on the glass substrate, prepare metal level with the method for magnetron sputtering or thermal evaporation, prepare the second metal conductive oxide layer with chemical gaseous phase depositing process.Electro-conductive glass light transmission of the present invention is good, and conductivity is strong, and nephelometric turbidity unit is high, film layer structure good stability; Cost performance is high; Prepare electro-conductive glass method preparation cost of the present invention low.
Description
Technical field
The present invention relates to a kind of novel high-performance electro-conductive glass, particularly a kind of thin-film solar cells electro-conductive glass and preparation method thereof, belongs to photoelectricity field of new, is particularly useful for solar energy materials field.
Background technology
Along with the utilization of the novel energy solar energy to environment protecting and power-saving, the development of novel solar battery more and more becomes the important topic in Application of Solar Energy field.Thin-film solar cell applications in current solar cell is very extensive, quality as the electro-conductive glass of thin-film solar cells important component part is directly connected to the quality of thin-film solar cells quality, is therefore very important to the reformed AHP of thin-film solar cells electro-conductive glass always.The nesa coating that existing thin-film solar cells electro-conductive glass generally comprises glass baseplate and arranges on the glass substrate, nesa coating is made up of metal conductive oxide layer.Adopting conventional preparation method time prepared by thin-film solar cells electro-conductive glass, preparing metal conductive oxide layer as adopted the methods such as low-pressure chemical vapor deposition (being called for short LPCVD), PCVD (being called for short PECVD), magnetron sputtering (being called for short SPUTTER) or thermal spraying (being called for short SPRAY).Existing thin-film solar cells electro-conductive glass glass baseplate wherein generally adopts common float glass process white glass or ultra-white float glass.Nesa coating wherein possesses good electric conductivity, there is very high transmitance to visible ray simultaneously, nesa coating is widely used in electronic industry as a kind of functional material, such as flat panel display, solar cell, touch-screen, instrument and the industrial circle such as instrument display, optical coating and building energy conservation glass.Especially in field of solar energy, as electrode before thin-film solar cells, vital effect is played to the conversion efficiency of thin-film solar cells.Because nesa coating has important effect, therefore according to the material difference that nesa coating adopts, electro-conductive glass is mainly divided into three kinds: the first is ito glass, for indium tin metal oxide, transmitance is high, and conductivity is excellent, but there is the expensive of raw material indium, be mainly used in the industrial circle such as liquid crystal display, touch-screen, seldom apply in field of thin film solar cells; The second is FTO glass, and be the tin ash of Fluorin doped, have advantage of lower cost, laser ablation is easier to, and optical property such as to be suitable at the feature, is mainly used in field of thin film solar cells; The third is AZO glass, be aluminium doping zinc oxide, optical property and conductance good, raw material is easy to get, cheap for manufacturing cost, nontoxic, be easy to realize doping, but when being applied to thin film solar battery module, there is the defect that can be limited by process for etching and interface problem.There is reflex on two surfaces of existing thin-film solar cells electro-conductive glass for light, the light transmittance of sunlight is made generally to be no more than 91.5%, cause this sunlight of about 8.5% to be utilized not yet, this sunlight of about 8.5% is also the very huge energy.Therefore people constantly improve the nesa coating film layer structure affecting electro-conductive glass light transmission, conductivity and nephelometric turbidity unit to improve light transmittance etc., increase the number of plies of metal conductive oxide layer, change layer of metal oxide conducting layer into multilayer, but be still physics superposition between multiple layer metal oxide conducting layer, nesa coating film layer structure is single, poor stability, these nesa coating film layer structures improved inherently do not change the performance of electro-conductive glass, and the light transmission of electro-conductive glass, conductivity and nephelometric turbidity unit do not obtain too large raising.Cause very huge solar energy still cannot to be fully used and to transform, this causes the reduction of solar conversion efficiency, and use cost increases.Therefore a kind of light transmission of electro-conductive glass, conductivity and nephelometric turbidity unit is badly in need of better, the stability of nesa coating film layer structure is better, inherently can change the novel thin film solar cell electro-conductive glass of the film layer structure of nesa coating, but this is an insurmountable technical barrier always.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provide one to have good electric conductivity, nephelometric turbidity unit and visible light transmissivity and nesa coating membranous layer stability, and high thin-film solar cells electro-conductive glass of cost performance and preparation method thereof.
The technical scheme realizing above-mentioned purpose is: a kind of thin-film solar cells electro-conductive glass, include glass baseplate and nesa coating, nesa coating includes metal conductive oxide layer and the second metal conductive oxide layer, between metal conductive oxide layer and the second metal conductive oxide layer, be gripped with metal level, metal conductive oxide layer, metal level and the second metal conductive oxide layer are successively set on the side of glass baseplate on the surface.
Further, described glass baseplate is common float glass process white glass or ultra-white float glass.
Further, described metal conductive oxide layer thickness is 100 ~ 500nm, and metal layer thickness is 10 ~ 100nm, and the second metal conductive oxide layer thickness is 100 ~ 500nm.
Further, described metal conductive oxide layer is AZO, GZO, ZnO, SnO
2or any one in ITO.
Further, described metal level is any one in Ag films, aluminium film, molybdenum film, or is the alloy firm of the two composition arbitrarily in silver-colored aluminium molybdenum.
Further, the second described metal conductive oxide layer is AZO, SnO
2: any one in F or ITO.
A kind of preparation method of thin-film solar cells electro-conductive glass, described preparation method is: prepare metal conductive oxide layer by the method for low-pressure chemical vapor deposition, PCVD, magnetron sputtering or thermal spraying on the glass substrate, prepare metal level with the physical gas-phase deposite method of magnetron sputtering or thermal evaporation, prepare the second metal conductive oxide layer with chemical gaseous phase depositing process.
Further, described prepares metal conductive oxide layer by the method for magnetron sputtering on the glass substrate, prepare metal level with the physical gas-phase deposite method of magnetron sputtering, prepare the second metal conductive oxide layer with the chemical gaseous phase depositing process of normal pressure, concrete operation step is as follows:
The first step, is installed in the sputtering chamber of magnetron sputtering production line by metal oxide target and metal targets;
Second step, vacuumizes sputtering chamber, is then filled with argon gas, the pressure of adjustment sputtering chamber;
3rd step, opens front end and heats trip temperature setting of going forward side by side; Open target direct current radio-frequency power supply, metallic conduction oxide target material sputtering power and metal targets target as sputter power are set;
4th step, cleaned glass baseplate is placed into section on magnetron sputtering production line, stream is pulled to the thermal treatment zone, front end, metal oxide target sputtering chamber and metal targets sputtering chamber successively, sputtering sedimentation is carried out on the basis that glow discharge is stable, is regulated by power adjustments and argon flow amount and reach the thickness requirement of metal conductive oxide layer and the thickness requirement of metal level;
5th step, the glass baseplate being coated with metal conductive oxide layer and metal level obtained in the previous step is placed in chemical vapour deposition (CVD) production line and is coated with the second metal conductive oxide layer, by the heating-up temperature of regulable control glass baseplate, raw material gas flow, glass baseplate translational speed and carrier gas flux, reach the thickness requirement of the second metal conductive oxide layer, prepare thin-film solar cells electro-conductive glass.
Further, in described step:
The first step, the spacing of target and glass baseplate is adjusted to 20 ~ 60mm;
Second step, is evacuated to 10 to sputtering chamber
-3pa; The pressure of adjustment sputtering chamber is 0.8 ~ 3pa;
3rd step, temperature is set to 100 ~ 200 DEG C; Metallic conduction oxide target material sputtering power is set to 200 ~ 300W, and metal targets sputtering power is set to 100 ~ 200W;
4th step, metal conductive oxide layer thickness is deposited as 100 ~ 500nm, and metal layer thickness is deposited as 10 ~ 100nm;
5th step, the heating-up temperature of regulable control glass baseplate is 300 ~ 600 DEG C, and glass baseplate translational speed controls at 1 ~ 2m/min, and carrier gas flux controls at 10 ~ 90L/min, and the second metal conductive oxide layer thickness is deposited as 100 ~ 500nm.In this step, the heating-up temperature of glass baseplate is 300 ~ 600 DEG C, and object is that the while of improving visible light transmissivity and petition of surrender surface resistance, glass baseplate deformation does not occur at this temperature.The performance parameters of parameter on electro-conductive glass of the present invention such as described gas flow and stream pulling rate degree have very important impact, and by regulating and controlling parameters, to ensure that the blended metal oxide conducting films such as the fluorine of deposition are evenly distributed, arrangement is fine and close.
Adopt technical scheme of the present invention, have the following advantages: (1) has good electric conductivity, nephelometric turbidity unit and visible light transmissivity and nesa coating membranous layer stability.Conducting film film layer structure when the present invention changes existing, the present invention is gripped with metal level between metal conductive oxide layer and the second metal conductive oxide layer, metal conductive oxide layer, metal level and the second metal conductive oxide layer deposit successively be arranged on glass baseplate side on the surface.Metal level deposition of the present invention is arranged on metal conductive oxide layer, metal level and the second metal conductive oxide layer deposit setting on the metal layer again, the increase of metal level makes to there occurs chemical reaction between metal level and the second metal conductive oxide layer and forms polymer, produces ball structure.The film layer structure of nesa coating of the present invention there occurs the change of essence, is different from the simple physical superposition of nesa coating film layer structure in prior art completely.The present invention is by the innovation to nesa coating film layer structure, achieve the optimum organization of multilayer complex films, substantially increase the performance of nesa coating, make the light transmission of thin-film solar cells electro-conductive glass better, conductivity is stronger, nephelometric turbidity unit is higher, nesa coating film layer structure dense uniform, stability is very good, and wherein sheet resistance can be controlled within the scope of 5.9 Ω/ ~ 28.5 Ω/, visible light transmissivity reaches more than 75%, and nephelometric turbidity unit can promote more than 5%; (2) cost performance is high, and use cost is low.The present invention compensate for the unification of the deficiencies in the prior art and nesa coating film layer structure, enrich nesa coating film layer structure, design very ingenious, the simple structure of the present invention solves this insoluble technical problem always, because performance of the present invention improves greatly, the photoelectric conversion efficiency that the present invention is applied in thin-film solar cells is very high, makes huge solar energy be fully used and transform, loss is little, and use cost reduces greatly; (3) the inventive method technique preparing electro-conductive glass of the present invention is simple, and easily realize, preparation cost is low.
Accompanying drawing explanation
Accompanying drawing is structural representation of the present invention.
Embodiment
Below by embodiment, the present invention is further detailed explanation.
Embodiment one
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, include glass baseplate 1 and nesa coating 5, nesa coating 5 includes metal conductive oxide layer 2 and the second metal conductive oxide layer 4, between metal conductive oxide layer 2 and the second metal conductive oxide layer 4, be gripped with metal level 3, metal conductive oxide layer 2, metal level 3 and the second metal conductive oxide layer 4 deposit successively and are arranged on the side of glass baseplate 1 on the surface.Described glass baseplate 1 is the common float glass process white glass of thickness 3.2mm.Described metal conductive oxide layer 2 thickness is 250nm, and metal level 3 thickness is 50nm, and the second metal conductive oxide layer 4 thickness is 250nm.Described metal conductive oxide layer 2 is AZO, and metal level 3 is Ag films, and the second metal conductive oxide layer 4 is SnO
2: F.
A kind of preparation method realizing above-mentioned thin-film solar cells electro-conductive glass, described preparation method is: on glass baseplate 1, prepare metal conductive oxide layer 2 by the method for magnetron sputtering, metal level 3 is prepared with the physical gas-phase deposite method of magnetron sputtering, prepare the second metal conductive oxide layer 4 with the chemical gaseous phase depositing process of normal pressure, concrete operation step is as follows:
The first step, be installed in the sputtering chamber of magnetron sputtering production line by highly purified metal oxide target and highly purified metal targets, the spacing of target and glass baseplate 1 is adjusted to 40mm;
Second step, vacuumizes sputtering chamber, first with mechanical pump, the base vacuum of sputtering chamber is evacuated to about 0pa when vacuumizing, then with lobe pump and molecular pump, the vacuum of sputtering chamber is evacuated to 3 × 10
-3pa; Then be filled with high-purity argon gas, the balanced gas pressure of adjustment sputtering chamber is 1.2pa;
3rd step, open front end and heat trip temperature setting of going forward side by side, temperature is set to 130 DEG C; Open target direct current radio-frequency power supply, arrange metallic conduction oxide target material sputtering power and metal targets target as sputter power, metallic conduction oxide target material sputtering power is set to 250W, and metal targets sputtering power is set to 120W;
4th step, the glass baseplate 1 cleaned with pure water is placed into section on magnetron sputtering production line, stream is pulled to the thermal treatment zone, front end, metal oxide target sputtering chamber and metal targets sputtering chamber successively, sputtering sedimentation is carried out on the basis that glow discharge is stable, regulated by power adjustments and argon flow amount and reach the thickness requirement of metal conductive oxide layer 2 and the thickness requirement of metal level 3, metal conductive oxide layer 2 thickness is deposited as 250nm, and metal level 3 thickness is deposited as 50nm;
5th step, the glass baseplate 1 being coated with metal conductive oxide layer 2 and metal level 3 obtained in the previous step is placed in chemical vapour deposition (CVD) production line and is coated with the second metal conductive oxide layer 4, by the heating-up temperature of regulable control glass baseplate, raw material gas flow, glass baseplate translational speed and carrier gas flux, reach the thickness requirement of the second metal conductive oxide layer, prepare thin-film solar cells electro-conductive glass.Wherein the heating-up temperature of regulable control glass baseplate 1 is 580 DEG C, stanniferous gas SnCl
4gas flow is 40L/min, fluoro-gas HF flow is 10L/min, glass baseplate 1 translational speed controls at 1m/min, carrier gas flux controls at 80L/min, second metal conductive oxide layer 4 thickness is deposited as 250nm, integral membrane layer thickness is 550nm, makes integral membrane layer thickness < 1100nm.In the present embodiment, the unstrpped gas of aumospheric pressure cvd is except adopting HF and SnCl
4outward, also TFA and MBTC can be adopted.
The thin-film solar cells electro-conductive glass performance that the present embodiment obtains is good, and its sheet resistance is 8.8 Ω/, and visible light wave range mean transmissivity reaches 76%.
Embodiment two
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, this embodiment electro-conductive glass is substantially identical with embodiment one structure, and described metal conductive oxide layer 2 is AZO, and metal level 3 is Ag films, and the second metal conductive oxide layer 4 is SnO
2: F.With embodiment one unlike: described glass baseplate 1 is the ultra-white float glass of thickness 3.2mm; Described metal conductive oxide layer 2 thickness is 150nm, and metal level 3 thickness is 30nm, and the second metal conductive oxide layer 4 thickness is 250nm.
Realize a preparation method for above-mentioned thin-film solar cells electro-conductive glass, described preparation method is substantially identical with preparation method in embodiment one.Unlike:
The first step, the spacing of target and glass baseplate 1 is adjusted to 50mm, and all the other are identical with embodiment one;
Second step, the balanced gas pressure of adjustment sputtering chamber is 0.8pa, and all the other are identical with embodiment one;
3rd step, the power setting of metallic conduction oxide AZO target as sputter is 200W, and argent target sputtering power is set to 80W, and all the other are identical with embodiment one;
4th step, is deposited as 150nm by metal conductive oxide layer 2 thickness, and metal level 3 thickness is deposited as 30nm, and all the other are identical with embodiment one;
5th step, wherein stanniferous gas SnCl
4gas flow is 30L/min, and the second metal conductive oxide layer 4 thickness is deposited as 250nm, and integral membrane layer thickness is 430nm, and all the other are identical with embodiment one.In the present embodiment, the unstrpped gas of aumospheric pressure cvd is except adopting HF and SnCl
4outward, also TFA and MBTC can be adopted.
The thin-film solar cells electro-conductive glass performance that the present embodiment obtains is good, and its sheet resistance is 12 Ω/, and visible light wave range mean transmissivity reaches 76%.
Embodiment three
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, this embodiment electro-conductive glass is substantially identical with embodiment one structure, and described metal level 3 is Ag films, and the second metal conductive oxide layer 4 is SnO
2: F.With embodiment one unlike: described metal conductive oxide layer 2 thickness is 200nm, and metal level 3 thickness is 50nm, and the second metal conductive oxide layer 4 thickness is 300nm.Described metal conductive oxide layer 2 is GZO.
Realize a preparation method for above-mentioned thin-film solar cells electro-conductive glass, described preparation method is substantially identical with preparation method in embodiment one.Unlike:
The first step, be installed in the sputtering chamber of magnetron sputtering production line by highly purified metal oxide GZO target and highly purified argent target, all the other are identical with embodiment one;
Second step is identical with embodiment one;
3rd step, the power setting of metallic conduction oxide GZO target as sputter is 250W, and argent target sputtering power is set to 120W, and all the other are identical with embodiment one;
4th step, is deposited as 200nm by metal conductive oxide layer 2 thickness, and metal level 3 thickness is deposited as 50nm, and all the other are identical with embodiment one;
5th step, wherein the second metal conductive oxide layer 4 thickness is deposited as 300nm, integral membrane layer thickness is 550nm, and make integral membrane layer thickness < 1100nm, all the other are identical with embodiment one.In the present embodiment, the unstrpped gas of aumospheric pressure cvd is except adopting HF and SnCl
4outward, also TFA and MBTC can be adopted.
The thin-film solar cells electro-conductive glass performance that the present embodiment obtains is good, and its sheet resistance is 9.4 Ω/, and visible light wave range mean transmissivity reaches 76%.
Embodiment four
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, this embodiment electro-conductive glass is substantially identical with embodiment one structure, and the second described metal conductive oxide layer 4 is SnO
2: F.With embodiment one unlike: described metal conductive oxide layer 2 thickness is 150nm, and metal level 3 thickness is 50nm, and the second metal conductive oxide layer 4 thickness is 280nm.Described metal conductive oxide layer 2 is GZO, and metal level 3 is aluminium film.
Realize a preparation method for above-mentioned thin-film solar cells electro-conductive glass, described preparation method is substantially identical with preparation method in embodiment one.Unlike:
The first step, highly purified metal oxide GZO target and highly purified metallic aluminium target are installed on magnetic control and penetrate in the sputtering chamber of production line, all the other are identical with embodiment one;
Second step is identical with embodiment one;
3rd step, the power setting of metallic conduction oxide GZO target as sputter is 250W, and the power setting of metallic aluminium target as sputter is 130W, and all the other are identical with embodiment one;
4th step, is deposited as 150nm by metal conductive oxide layer 2 thickness, and metal level 3 thickness is deposited as 50nm, and all the other are identical with embodiment one;
5th step, wherein the second metal conductive oxide layer 4 thickness is deposited as 280nm, integral membrane layer thickness is 480nm, and make integral membrane layer thickness < 1100nm, all the other are identical with embodiment one.In the present embodiment, the unstrpped gas of aumospheric pressure cvd is except adopting HF and SnCl
4outward, also TFA and MBTC can be adopted.
The thin-film solar cells electro-conductive glass performance that the present embodiment obtains is good, and its sheet resistance is 11 Ω/, and visible light wave range mean transmissivity reaches 76%.
Embodiment five
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, this embodiment electro-conductive glass is substantially identical with embodiment one structure.With embodiment one unlike: described glass baseplate 1 is the ultra-white float glass of thickness 3.2mm; Described metal conductive oxide layer 2 thickness is 100nm, and metal level 3 thickness is 10nm, and the second metal conductive oxide layer 4 thickness is 230nm.Described metal conductive oxide layer 2 is ZnO, and metal level 3 is molybdenum film, and the second metal conductive oxide layer 4 is AZO.
Realize a preparation method for above-mentioned thin-film solar cells electro-conductive glass, described preparation method is substantially identical with preparation method in embodiment one.Unlike:
The first step, be installed in the sputtering chamber of magnetron sputtering production line by highly purified metal oxide ZnO target and highly purified metal molybdenum target, the spacing of target and glass baseplate 1 is adjusted to 20mm;
Second step, vacuumizes sputtering chamber, is first evacuated near 0pa by the base vacuum of mechanical pump by sputtering chamber, then with lobe pump and molecular pump, the vacuum of sputtering chamber is evacuated to 5 × 10 when vacuumizing
-3pa; Then be filled with high-purity argon gas, the balanced gas pressure of adjustment sputtering chamber is 2.5pa;
3rd step, open front end and heat trip temperature setting of going forward side by side, temperature is set to 150 DEG C; Open target direct current radio-frequency power supply, arrange metallic conduction oxide ZnO target as sputter power and metal molybdenum target target as sputter power, the power setting of metallic conduction oxide ZnO target as sputter is 300W, and the power setting of metal molybdenum target as sputter is 200W;
4th step, is deposited as 100nm by metal conductive oxide layer 2 thickness, and metal level 3 thickness is deposited as 10nm, and all the other are identical with embodiment one;
5th step, wherein the heating-up temperature of regulable control glass baseplate 1 is 400 DEG C, adopting containing zinc gas diethyl zinc gas flow is 5L/min, be 1.2L/min containing aluminium gas trimethyl aluminium flow, glass baseplate 1 translational speed controls at 1.5m/min, and carrier gas flux controls at 60L/min, second metal conductive oxide layer 4 thickness is deposited as 230nm, integral membrane layer thickness is 340nm, and make integral membrane layer thickness < 1100nm, all the other are identical with embodiment one.
Embodiment six
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, this embodiment electro-conductive glass is substantially identical with embodiment one structure.With embodiment one unlike: described metal conductive oxide layer 2 thickness is 400nm, and metal level 3 thickness is 80nm, and the second metal conductive oxide layer 4 thickness is 500nm.Described metal conductive oxide layer 2 is SnO
2, metal level 3 is aerdentalloy film, and the second metal conductive oxide layer 4 is AZO.
Realize a preparation method for above-mentioned thin-film solar cells electro-conductive glass, described preparation method is substantially identical with preparation method in embodiment one.Unlike:
The first step, by highly purified metal oxide SnO
2target and highly purified argent aluminium alloy target are installed in the sputtering chamber of magnetron sputtering production line, and the spacing of target and glass baseplate 1 is adjusted to 60mm;
Second step, vacuumizes sputtering chamber, is first evacuated near 0pa by the base vacuum of mechanical pump by sputtering chamber, then with lobe pump and molecular pump, the vacuum of sputtering chamber is evacuated to 4 × 10 when vacuumizing
-3pa; Then be filled with high-purity argon gas, the balanced gas pressure of adjustment sputtering chamber is 2.5pa;
3rd step, open front end and heat trip temperature setting of going forward side by side, temperature is set to 200 DEG C; Open target direct current radio-frequency power supply, metallic conduction oxide S nO is set
2target as sputter power and argent aluminium alloy target target as sputter power, metallic conduction oxide S nO
2target as sputter power setting is 280W, and the power setting of argent aluminium alloy target as sputter is 150W;
4th step, is deposited as 400nm by metal conductive oxide layer 2 thickness, and metal level 3 thickness is deposited as 80nm, and all the other are identical with embodiment one;
5th step, wherein the heating-up temperature of regulable control glass baseplate 1 is 300 DEG C, adopting containing zinc gas diethyl zinc gas flow is 5L/min, be 1.2L/min containing aluminium gas trimethyl aluminium flow, glass baseplate 1 translational speed controls at 2m/min, and carrier gas flux controls at 90L/min, second metal conductive oxide layer 4 thickness is deposited as 500nm, integral membrane layer thickness is 980nm, and make integral membrane layer thickness < 1100nm, all the other are identical with embodiment one.
Embodiment seven
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, this embodiment electro-conductive glass is substantially identical with embodiment one structure.With embodiment one unlike: described metal conductive oxide layer 2 thickness is 500nm, and metal level 3 thickness is 100nm, and the second metal conductive oxide layer 4 thickness is 450nm.Described metal conductive oxide layer 2 is ITO, and metal level 3 is silver-molybdenbum film, and the second metal conductive oxide layer 4 is ITO.
Realize a preparation method for above-mentioned thin-film solar cells electro-conductive glass, described preparation method is substantially identical with preparation method in embodiment one.Unlike:
The first step, be installed in the sputtering chamber of magnetron sputtering production line by highly purified metal oxide ITO target and highly purified argent molybdenum alloy target, the spacing of target and glass baseplate 1 is adjusted to 60mm;
Second step, vacuumizes sputtering chamber, is first evacuated near 0pa by the base vacuum of mechanical pump by sputtering chamber, then with lobe pump and molecular pump, the vacuum of sputtering chamber is evacuated to 5 × 10 when vacuumizing
-3pa; Then be filled with high-purity argon gas, the balanced gas pressure of adjustment sputtering chamber is 2.5pa;
3rd step, open front end and heat trip temperature setting of going forward side by side, temperature is set to 180 DEG C; Open target direct current radio-frequency power supply, metallic conduction oxide ITO target sputtering power and argent molybdenum alloy target target as sputter power are set, metallic conduction oxide ITO target sputtering power is set to 250W, and argent molybdenum alloy target sputtering power is set to 200W;
4th step, is deposited as 500nm by metal conductive oxide layer 2 thickness, and metal level 3 thickness is deposited as 100nm, and all the other are identical with embodiment one;
5th step, wherein the heating-up temperature of regulable control glass baseplate 1 is 400 DEG C, adopting containing indium gas Indium Tris acetylacetonate gas flow is 15L/min, stanniferous gas tetramethyl tin gas flow is 10L/min, and glass baseplate 1 translational speed controls at 1m/min, and carrier gas flux controls at 85L/min, second metal conductive oxide layer 4 thickness is deposited as 450nm, integral membrane layer thickness is 1050nm, and make integral membrane layer thickness < 1100nm, all the other are identical with embodiment one.
Embodiment eight
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, this embodiment electro-conductive glass is substantially identical with embodiment one structure.With embodiment one unlike: be the ultra-white float glass of thickness 3.2mm unlike described glass baseplate 1 with embodiment one; Described metal conductive oxide layer 2 thickness is 120nm, and metal level 3 thickness is 20nm, and the second metal conductive oxide layer 4 thickness is 200nm.Described metal conductive oxide layer 2 is ITO, and metal level 3 is aluminium molybdenum alloys film, and the second metal conductive oxide layer 4 is SnO
2: F.
Realize a preparation method for above-mentioned thin-film solar cells electro-conductive glass, described preparation method is substantially identical with preparation method in embodiment one.Unlike:
The first step, be installed in the sputtering chamber of magnetron sputtering production line by highly purified metal oxide ITO target and highly purified metallic aluminium molybdenum alloy target, the spacing of target and glass baseplate 1 is adjusted to 30mm;
Second step, vacuumizes sputtering chamber, is first evacuated near 0pa by the base vacuum of mechanical pump by sputtering chamber, then with lobe pump and molecular pump, the vacuum of sputtering chamber is evacuated to 3 × 10 when vacuumizing
-3pa; Then be filled with high-purity argon gas, the balanced gas pressure of adjustment sputtering chamber is 1.0pa;
3rd step, open front end and heat trip temperature setting of going forward side by side, temperature is set to 120 DEG C; Open target direct current radio-frequency power supply, metallic conduction oxide ITO target sputtering power and metallic aluminium molybdenum alloy target target as sputter power are set, metallic conduction oxide ITO target sputtering power is set to 220W, and metallic aluminium molybdenum alloy target sputtering power is set to 120W;
4th step, is deposited as 120nm by metal conductive oxide layer 2 thickness, and metal level 3 thickness is deposited as 20nm, and all the other are identical with embodiment one;
5th step, wherein the heating-up temperature of regulable control glass baseplate 1 is 400 DEG C, stanniferous gas SnCl
4gas flow is 10L/min, fluoro-gas HF flow is 5L/min, glass baseplate 1 translational speed controls at 1m/min, carrier gas flux controls at 10L/min, second metal conductive oxide layer 4 thickness is deposited as 200nm, integral membrane layer thickness is 340nm, makes integral membrane layer thickness < 1100nm.All the other are identical with embodiment one.
Embodiment nine
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, this embodiment electro-conductive glass is substantially identical with embodiment one structure, and identical with embodiment one is described metal conductive oxide layer 2 is AZO, and metal level 3 is Ag films.With embodiment one unlike: described metal conductive oxide layer 2 thickness is 300nm, and metal level 3 thickness is 60nm, and the second metal conductive oxide layer 4 thickness is 100nm.The second described metal conductive oxide layer 4 is AZO.
Realize a preparation method for above-mentioned thin-film solar cells electro-conductive glass, described preparation method is substantially identical with preparation method in embodiment one.Unlike:
The first step is identical with embodiment one;
Second step is identical with embodiment one;
3rd step is identical with embodiment one;
4th step, is deposited as 300nm by metal conductive oxide layer 2 thickness, and metal level 3 thickness is deposited as 60nm, and all the other are identical with embodiment one;
5th step, wherein the heating-up temperature of regulable control glass baseplate 1 is 400 DEG C, adopting containing zinc gas diethyl zinc gas flow is 5L/min, be 1.2L/min containing aluminium gas trimethyl aluminium flow, glass baseplate 1 translational speed controls at 1.5m/min, and carrier gas flux controls at 60L/min, and the second metal conductive oxide layer 4 thickness is deposited as 100nm, integral membrane layer thickness is 460nm, and all the other are identical with embodiment one.
Embodiment ten
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, this embodiment electro-conductive glass is substantially identical with embodiment one structure.With embodiment one unlike: described metal conductive oxide layer 2 thickness is 480nm, and metal level 3 thickness is 90nm, and the second metal conductive oxide layer 4 thickness is 480nm.Described metal conductive oxide layer 2 is AZO, and metal level 3 is aluminium film, and the second metal conductive oxide layer 4 is ITO.
Realize a preparation method for above-mentioned thin-film solar cells electro-conductive glass, described preparation method is substantially identical with preparation method in embodiment one.Unlike:
The first step, be installed in the sputtering chamber of magnetron sputtering production line by highly purified metal oxide AZO target and highly purified metallic aluminium target, the spacing of target and glass baseplate 1 is adjusted to 50mm;
Second step, vacuumizes sputtering chamber, is first evacuated near 0pa by the base vacuum of mechanical pump by sputtering chamber, then with lobe pump and molecular pump, the vacuum of sputtering chamber is evacuated to 6 × 10 when vacuumizing
-3pa; Then be filled with high-purity argon gas, the balanced gas pressure of adjustment sputtering chamber is 2.8pa;
3rd step, open front end and heat trip temperature setting of going forward side by side, temperature is set to 180 DEG C; Open target direct current radio-frequency power supply, arrange metallic conduction oxide AZO target as sputter power and metallic aluminium target target as sputter power, the power setting of metallic conduction oxide AZO target as sputter is 220W, and the power setting of metallic aluminium target as sputter is 200W;
4th step, is deposited as 480nm by metal conductive oxide layer 2 thickness, and metal level 3 thickness is deposited as 90nm, and all the other are identical with embodiment one;
5th step, wherein the heating-up temperature of regulable control glass baseplate 1 is 400 DEG C, adopting containing indium gas Indium Tris acetylacetonate gas flow is 15L/min, stanniferous gas tetramethyl tin gas flow is 10L/min, and glass baseplate 1 translational speed controls at 1m/min, and carrier gas flux controls at 70L/min, second metal conductive oxide layer 4 thickness is deposited as 480nm, integral membrane layer thickness is 1050nm, and make integral membrane layer thickness < 1100nm, all the other are identical with embodiment one.
Embodiment 11
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, this embodiment electro-conductive glass structure is identical with embodiment one.
Realize a preparation method for above-mentioned thin-film solar cells electro-conductive glass, described preparation method is substantially identical with embodiment one preparation method.Unlike: on glass baseplate 1, prepare metal conductive oxide layer 2 by the method for low-pressure chemical vapor deposition, prepare metal level 3 with the physical gas-phase deposite method of thermal evaporation.
Embodiment 12
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, this embodiment electro-conductive glass structure is identical with embodiment one.
Realize a preparation method for above-mentioned thin-film solar cells electro-conductive glass, described preparation method is substantially identical with embodiment one preparation method.Unlike: on glass baseplate 1, prepare metal conductive oxide layer 2 by plasma chemical vapor deposition process, prepare metal level 3 with the physical gas-phase deposite method of thermal evaporation.
Embodiment 13
As shown in drawings, a kind of thin-film solar cells electro-conductive glass, this embodiment electro-conductive glass structure is identical with embodiment one.
Realize a preparation method for above-mentioned thin-film solar cells electro-conductive glass, described preparation method is substantially identical with embodiment one preparation method.Unlike: on glass baseplate 1, prepare metal conductive oxide layer 2 by the method for thermal spraying.
In addition to the implementation, parameters can adjust according to specific requirement in the present invention, chooses in each regulation parameter area.Embodiments of the invention two to embodiment ten is prepared metal conductive oxide layer 2 except by the method for magnetron sputtering except selecting on glass baseplate 1, and any one method in LPCVD, PECVD or SPRAY can also be adopted to prepare metal conductive oxide layer 2.Carrier gas described in various embodiments of the present invention is nitrogen and compressed-air actuated mist.
Embodiments of the invention are a lot, cannot be exhaustive, and the technical scheme that all employings are equal to replacement or equivalence replacement formation all belongs to the claimed scope of invention.
Claims (9)
1. a thin-film solar cells electro-conductive glass, include glass baseplate (1) and nesa coating (5), nesa coating (5) includes metal conductive oxide layer (2) and the second metal conductive oxide layer (4), it is characterized in that: between metal conductive oxide layer (2) and the second metal conductive oxide layer (4), be gripped with metal level (3), metal conductive oxide layer (2), metal level (3) and the second metal conductive oxide layer (4) are successively set on the side of glass baseplate (1) on the surface, wherein prepare the second metal conductive oxide layer (4) with chemical gaseous phase depositing process, the heating-up temperature of regulable control glass baseplate (1) is 300 ~ 600 DEG C, glass baseplate (1) translational speed controls at 1 ~ 2m/min, carrier gas flux controls at 10 ~ 90L/min, second metal conductive oxide layer (4) thickness is deposited as 100 ~ 500nm.
2. thin-film solar cells electro-conductive glass according to claim 1, is characterized in that: described glass baseplate (1) is common float glass process white glass or ultra-white float glass.
3. thin-film solar cells electro-conductive glass according to claim 1, it is characterized in that: described metal conductive oxide layer (2) thickness is 100 ~ 500nm, metal level (3) thickness is 10 ~ 100nm, and the second metal conductive oxide layer (4) thickness is 100 ~ 500nm.
4. thin-film solar cells electro-conductive glass according to claim 1, is characterized in that: described metal conductive oxide layer (2) is AZO, GZO, ZnO, SnO
2or any one in ITO.
5. thin-film solar cells electro-conductive glass according to claim 1, is characterized in that: described metal level (3) is Ag films, any one in aluminium film, molybdenum film, or is alloy firm of the two composition arbitrarily in silver-colored aluminium molybdenum.
6. thin-film solar cells electro-conductive glass according to claim 1, is characterized in that: the second described metal conductive oxide layer (4) is AZO, SnO
2: any one in F or ITO.
7. the preparation method of a thin-film solar cells electro-conductive glass, it is characterized in that described preparation method is: pass through low-pressure chemical vapor deposition on the glass substrate, PCVD, the method of magnetron sputtering or thermal spraying prepares metal conductive oxide layer, metal level is prepared with the physical gas-phase deposite method of magnetron sputtering or thermal evaporation, the second metal conductive oxide layer is prepared with chemical gaseous phase depositing process, when wherein preparing the second metal conductive oxide layer with chemical gaseous phase depositing process, the heating-up temperature of regulable control glass baseplate is 300 ~ 600 DEG C, glass baseplate translational speed controls at 1 ~ 2m/min, carrier gas flux controls at 10 ~ 90L/min, second metal conductive oxide layer thickness is deposited as 100 ~ 500nm.
8. the preparation method of thin-film solar cells electro-conductive glass according to claim 7, it is characterized in that: described prepares metal conductive oxide layer by the method for magnetron sputtering on the glass substrate, metal level is prepared with the physical gas-phase deposite method of magnetron sputtering, prepare the second metal conductive oxide layer with the chemical gaseous phase depositing process of normal pressure, concrete operation step is as follows:
The first step, is installed in the sputtering chamber of magnetron sputtering production line by metal oxide target and metal targets;
Second step, vacuumizes sputtering chamber, is then filled with argon gas, the pressure of adjustment sputtering chamber;
3rd step, opens front end and heats trip temperature setting of going forward side by side; Open target direct current radio-frequency power supply, metallic conduction oxide target material sputtering power and metal targets target as sputter power are set;
4th step, cleaned glass baseplate is placed into section on magnetron sputtering production line, stream is pulled to the thermal treatment zone, front end, metal oxide target sputtering chamber and metal targets sputtering chamber successively, sputtering sedimentation is carried out on the basis that glow discharge is stable, is regulated by power adjustments and argon flow amount and reach the thickness requirement of metal conductive oxide layer and the thickness requirement of metal level;
5th step, the glass baseplate being coated with metal conductive oxide layer and metal level obtained in the previous step is placed in chemical vapour deposition (CVD) production line and is coated with the second metal conductive oxide layer, by the heating-up temperature of regulable control glass baseplate, raw material gas flow, glass baseplate translational speed and carrier gas flux, reach the thickness requirement of the second metal conductive oxide layer, prepare thin-film solar cells electro-conductive glass.
9. the preparation method of thin-film solar cells electro-conductive glass according to claim 8, is characterized in that: in described step:
The first step, the spacing of target and glass baseplate is adjusted to 20 ~ 60mm;
Second step, is evacuated to 10 to sputtering chamber
-3pa; The pressure of adjustment sputtering chamber is 0.8 ~ 3pa;
3rd step, temperature is set to 100 ~ 200 DEG C; Metallic conduction oxide target material sputtering power is set to 200 ~ 300W, and metal targets sputtering power is set to 100 ~ 200W;
4th step, metal conductive oxide layer thickness is deposited as 100 ~ 500nm, and metal layer thickness is deposited as 10 ~ 100nm.
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| CN107601921A (en) * | 2017-09-06 | 2018-01-19 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of thin-film solar cells photovoltaic back-panel glass |
| CN107507878A (en) * | 2017-09-06 | 2017-12-22 | 蚌埠玻璃工业设计研究院 | A kind of photovoltaic back glass of thin-film solar cells multi-layer film structure |
| CN109913810A (en) * | 2017-12-13 | 2019-06-21 | 湘潭宏大真空技术股份有限公司 | Vacuum magnetron sputtering coating film production line |
| CN112599614A (en) * | 2020-12-25 | 2021-04-02 | 中建材蚌埠玻璃工业设计研究院有限公司 | CdTe thin-film solar cell with adjustable reflection spectrum |
| CN115896726A (en) * | 2023-02-22 | 2023-04-04 | 中国科学院宁波材料技术与工程研究所 | MAX-Ag phase composite coating and preparation method and application thereof |
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| CN1938791A (en) * | 2004-09-13 | 2007-03-28 | 住友金属矿山株式会社 | Transparent conductive film, process for producing the same, transparent conductive base material and luminescent device |
| CN101913778A (en) * | 2010-08-02 | 2010-12-15 | 常州亚玛顿股份有限公司 | Transparent conducting glass substrate with antireflection coating for thin film solar cell |
| CN202127021U (en) * | 2011-03-09 | 2012-01-25 | 常州亚玛顿股份有限公司 | Conductive glass for thin film solar cell |
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| CN1257135A (en) * | 1999-12-23 | 2000-06-21 | 复旦大学 | Metal indium-stannic oxide compound transparent electricity conductive film and preparation process thereof |
| CN1938791A (en) * | 2004-09-13 | 2007-03-28 | 住友金属矿山株式会社 | Transparent conductive film, process for producing the same, transparent conductive base material and luminescent device |
| CN101913778A (en) * | 2010-08-02 | 2010-12-15 | 常州亚玛顿股份有限公司 | Transparent conducting glass substrate with antireflection coating for thin film solar cell |
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