CN103367479A - Conducting substrate of flexible solar cell texture and preparation method thereof - Google Patents
Conducting substrate of flexible solar cell texture and preparation method thereof Download PDFInfo
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- CN103367479A CN103367479A CN2013102770800A CN201310277080A CN103367479A CN 103367479 A CN103367479 A CN 103367479A CN 2013102770800 A CN2013102770800 A CN 2013102770800A CN 201310277080 A CN201310277080 A CN 201310277080A CN 103367479 A CN103367479 A CN 103367479A
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Abstract
The invention discloses a conducting substrate of a flexible solar cell texture and a preparation method thereof. The conducting substrate of the flexible solar cell texture comprises a flexible substrate, and a metal conducting film and an oxide conducting film, which are plated on the flexible substrate in sequence, wherein the surface of the oxide conducting film is a texture provided with a U-shaped nanometer feature, the metal conducting film is 5-120 nm thick, and the oxide conducting film is 20-60 nm thick. According to the invention, through an excellent light trapping structure, more light can be scattered to a cell absorption layer again, so that the thickness of the cell absorption layer is further reduced, and the production cost of a cell/component is reduced.
Description
Technical field
The present invention relates to the photovoltaic application field, be specifically related to a kind of flexible solar battery matte conductive substrates and preparation method thereof.
Background technology
Flexible thin-film solar cell receives the concern of each research structure, enterprise and government thereof for many years as a kind in the solar cell always, has in the world a lot of enterprises all falling over each other developmental research.Compare with flat crystalline silicon, glass substrate hull cell, its maximum characteristics of flexible thin-film solar cell be lightweight, collapsible, be difficult for broken, have a high mass-power ratio, transport, carry, all very convenient in the keeping.Flexible thin-film solar cell not only can be competent at all roles that existing hard substrates solar cell is used fully, but also can be applied in many other fields that the hard battery is difficult to be competent at and promote, comprise the special surface occasions such as solar telephone, aircraft, dirigible, building, even can as map, hang on the wall, the time spent does not roll and gets final product.
Take U.S. Uni-Solar company adopt stainless steel as substrate as example, stainless thickness is 127um only, and has fabulous flexibility, can be arbitrarily curling, cutting, stickup, both made to curve very little radius, and done hundreds of time curlingly, battery performance can not change yet.And the amorphous silicon solar cell for preparing take the high molecular polymer polyimides as flexible substrate, the device gross thickness approximately (contains encapsulated layer) about 100um, power-weight ratio can reach more than the 500W/Kg, exceeds nearly ten times than amorphous silicon battery at the bottom of the stainless steel lining, is the lightest in the world solar cell.
Flexible substrate has the function of conductive electrode and substrate concurrently as a requisite part in the flexible thin-film solar cell.The quality of its performance is directly connected to the performance of battery and the preparation cost of battery, therefore is one of crucial raw material of the thin-film solar cells such as preparation flexible amorphous silicon, flexible amorphous silicon/microcrystal silicon, flexible cadmium telluride.How low-cost, large-area prepare high-quality compliant conductive substrate, be one of key factor of preparing low cost, high-efficiency flexible thin-film solar cells, is to realize that flexible solar battery obtains wideling popularize the prerequisite condition of application.
At present, on the production scale, existing technique for the production of flexible substrate directly plates one deck silver exactly as back reflection layer (as shown in Figure 1) on stainless steel or polyimide plastic substrate.This back reflection layer structure is single, can't realize falling into luminous effect, and what cause that the absorbed layer of battery will do is thicker, increases battery/assembly cost.
For strengthening the light absorption of battery, improve the interfacial characteristics of argentum reflecting layer and battery layers, need to increase on the original structure basis one deck oxide conductive film, and form the suede degree of Nano/micron level on the surface of oxide conductive film, so that see through when the light of battery obsorbing layer incides this matte surface diffuse scattering occurs, thereby more luminous energy is scattered back absorbed layer again.Utilize this structure, can with the reduced thickness of battery obsorbing layer on maintenance even raising battery/assembly property basis, reduce the production cost of battery/assembly.
On the experimental size, scientific research institution, the most frequently used compliant conductive substrat structure of colleges and universities substantially all are at present: stainless steel substrates/plastic (PEN, PET, PI)+silver (Ag)+zinc oxide (ZnO).In this structure, Ag and ZnO all can't make the matte pattern, but directly make the matte pattern of nano-micro structure on stainless steel substrates or the surface of plastic with nano imprint lithography, then plate successively in the above Ag and ZnO.Wherein be used to two kinds of maximum matte patterns:
The surface topography of nano-pillar (as shown in Figure 3);
The dome-type surface topography of convex nanometer (as shown in Figure 4).
There is following technological deficiency for above-mentioned flexible substrate structure and surface topography thereof:
1) because the preparation process of flexible battery is each tunic growth that superposes in order on the basis of this substrat structure, and this substrat structure is as the direct substrate of battery obsorbing layer, its pattern directly affects growth pattern and the quality of absorbed layer.As shown in Figure 3, can form between the pillar of this matte pattern and the pillar and be similar to V-structure, battery obsorbing layer slight crack can occur at this place, has a strong impact on the performance of solar cell.And as shown in Figure 4, the surface of back reflection layer silver is very coarse, can adsorb photo-generated carrier, causes the open circuit voltage of battery performance and fill factor, curve factor to descend.
2) because the matte morphogenesis process of this substrat structure is the pattern that at first forms first certain specification with nano imprint lithography on stainless steel or plastic according to certain template, then plate in the back Ag and ZnO, and battery obsorbing layer deposits to the ZnO surface, this just means that also the coating process of different Ag and ZnO can have influence on the matte pattern of original anticipation, can be interpreted as controllability to it poor.
3) from the whole technique preparation flow of nano imprint lithography, we can find: 1. need to prepare a template with Nano grade feature with electron beam lithography, because electron beam lithography is very expensive, the cost of so corresponding template will be very high; 2. need to use macromolecule glue in the preparation process, the Young's modulus of requirement macromolecule glue is less than the hardness of template in moulding process, also require glue that less viscosity is arranged, possess certain flowability, these technological requirements have all proposed very high requirement to macromolecule glue; 3. after waiting cooling, template is taken off, will have so following two kinds of possibilities in the process that takes off: a kind of is the complete disengaging of template, obtained the imprinted pattern that needs, another is exactly that template and glue still stick together, template is got up the whole band of glue at detach procedure, and coining pattern is unsuccessful not to be said, also can cause molecular glue to adhere to the phenomenon of polluting template on the template; 4. need accurately to control imprint temperature and impression pressure, equipment has been proposed very high requirement; 5. in moulding process, owing to needing the temperature heating, template and substrate thermal coefficient of expansion can appear different and the phenomenon of aliasing occurs; 6. impression figure out also will finally be transferred on the needed substrate, also the unsuccessful phenomenons such as figure fragmentation, distortion can occur in transfer process.From the angle of cost and performance thereof, the flexible matte substrate that nano imprint lithography all can't be prepared large tracts of land, industrialization specification is applied to thin-film solar cells.
Summary of the invention
Technical problem to be solved by this invention is the irrational problem of pattern of flexible solar battery matte conductive substrates.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention provides a kind of flexible solar battery matte conductive substrates, comprise flexible substrate and the metal conductive film and the oxide conductive film that are coated with successively on it, it is characterized in that, the surface of described oxide conductive film is the matte with the U-shaped pattern of nanoscale, the thickness of described metal conductive film is 5～120nm, and the thickness of described oxide conductive film is 20～60nm.
In above-mentioned a kind of flexible solar battery matte conductive substrates, described flexible solar battery is silicon-based film solar cells, cadmium telluride diaphragm solar battery, organic flexible solar battery or dye sensitized flexible solar battery.
In above-mentioned a kind of flexible solar battery matte conductive substrates, described flexible substrate is polyimide film (PI), polyethylene naphthalate (PEN), PETG (PET) or stainless steel.
In above-mentioned a kind of flexible solar battery matte conductive substrates, described metal conductive film is silver, gold or aluminium.
In above-mentioned a kind of flexible solar battery matte conductive substrates, described oxide conductive film is Al-Doped ZnO (ZnO:Al) or mixes indium tin oxide (ITO).
The present invention also provides a kind of preparation method of flexible solar battery matte conductive substrates, it is characterized in that, may further comprise the steps: S10, employing magnetron sputtering mode plate the very thin metal conductive film of one deck at flexible substrate, obtain conductive substrates A, the deposit thickness of described metal conductive film is 5～120nm; S20, employing magnetron sputtering mode plate the very thin oxide conductive film of one deck at conductive substrates A, obtain conductive substrates B, and the deposit thickness of described oxide conductive film is 20～60nm; S30, get the Nano/micron ball solution that concentration is 0.5～1wt.%, mix in the ratio of 1:1～30 with deionized water, the material of described Nano/micron ball is polystyrene (PS) or silicon dioxide (SiO
2), particle diameter is 100nm～3um, and the pH value of this mixed solution is transferred to 2～7, and conductive substrates B is put in this solution, places 0.5min.～2min., takes out, water is rinsed well, obtains conductive substrates C; S40, utilize the magnetron sputtering mode to plate one deck oxide conductive film at conductive substrates C, obtain conductive substrates D; The Nano/micron ball of conductive substrates D upper surface is removed in S50, cleaning, obtains the U-shaped matte conductive substrates of flexible solar battery.
In the preparation method of above-mentioned a kind of flexible solar battery matte conductive substrates, in step S10, the magnetron sputtering technique condition is as follows: the base vacuum degree is better than 3.0x10
-6Torr, operating air pressure 1～4mTorr, working gas are Ar, and shielding power supply is (DC), and power 50～1000W, underlayer temperature are RT～500 ℃, and deposition rate is 30～100nm/min..
In the preparation method of above-mentioned a kind of flexible solar battery matte conductive substrates, in step S20, the magnetron sputtering technique condition is as follows: the base vacuum degree is better than 1.0x10
-5Torr, operating air pressure 1～10mTorr, working gas Ar+O
2, shielding power supply is radio frequency (13.56MHz), and power 50～1000W, underlayer temperature are (RT)～500 ℃, and deposition rate is 10～100nm/min..
In the preparation method of above-mentioned a kind of flexible solar battery matte conductive substrates, in step S40, the magnetron sputtering technique condition is as follows: the base vacuum degree is better than 1.0x10
-5Torr, operating air pressure 1～10mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, and power 50～1000W, underlayer temperature are (RT)～500 ℃, and deposition rate is 10～100nm/min..
The present invention has excellent U-shaped light trapping structure, so that more light can be scattered telegram in reply pond absorbed layer again, thereby further reduces the thickness of battery obsorbing layer, reduces the production cost of battery/assembly.
Description of drawings
Fig. 1 is the back-reflections structure chart of traditional flexible thin-film solar cell;
Fig. 2 is the U-shaped matte conductive substrates of the flexible solar battery schematic diagram that the present invention obtains;
Fig. 3 is the structural representation of the most frequently used flexible substrate structure that arrives of present scientific research institution-nano-pillar surface topography;
Fig. 4 is the structural representation of the most frequently used flexible substrate structure that arrives of present scientific research institution-convex nanometer dome-shaped surface pattern;
Fig. 5 is that nanosphere is at the distribution map on oxide conductive film surface;
Fig. 6 is that micron ball is at the distribution map on oxide conductive film surface;
Fig. 7 is the schematic diagram that magnetron sputtering sull out can enter into microballoon and microballoon gap;
Fig. 8 is the optical characteristics figure of the U-shaped matte conductive substrates of flexible solar battery prepared.
Embodiment
For the state of the art of flexible matte substrate, primary and foremost purpose of the present invention provides a kind of with low cost, novel matte substrate with large area flexible solar cell special use of evenly controlled U-shaped nano matte; Next is to provide the preparation method of the novel matte substrate of above-mentioned flexible solar battery special use; Last purpose is elaborating so that above-mentioned novel matte substrate can obtain wideling popularize application by this preparation method.
A kind of flexible solar battery matte conductive substrates provided by the invention comprises flexible substrate and the metal conductive film and the oxide conductive film that are coated with successively on it, the surface of oxide conductive film is the matte with the U-shaped pattern of nanoscale, the thickness of metal conductive film is 5～120nm, and the thickness of oxide conductive film is 20～60nm.
Flexible solar battery is silicon-based film solar cells, cadmium telluride diaphragm solar battery, organic flexible solar battery or dye sensitized flexible solar battery among the present invention.Flexible substrate is polyimide film (PI), polyethylene naphthalate (PEN), PETG (PET) or stainless steel, wherein stainless steel and PI material can be as being the flexible substrates for preparing under the high temperature, other the materials such as PET are not fine aspect thermal endurance, can be used for preparing under the low temperature.Metal conductive film is silver, gold or aluminium.Oxide conductive film is Al-Doped ZnO (ZnO:Al) or mixes indium tin oxide (ITO).
The present invention also provides a kind of preparation method of flexible solar battery matte conductive substrates, it is characterized in that, may further comprise the steps:
S10, employing magnetron sputtering mode plate the very thin metal conductive film of one deck at flexible substrate, obtain conductive substrates A, and the deposit thickness of described metal conductive film is 5～120nm.In step S10, the magnetron sputtering technique condition is as follows: the base vacuum degree is better than 3.0x10
-6Torr, operating air pressure 1～4mTorr, working gas are Ar, and shielding power supply is direct current, and power 50～1000W, underlayer temperature are room temperature (RT)～500 ℃, and deposition rate is 30～100nm/min.;
S20, employing magnetron sputtering mode plate the very thin oxide conductive film of one deck at conductive substrates A, obtain conductive substrates B, and the deposit thickness of described oxide conductive film is 20～60nm.In step S20, the magnetron sputtering technique condition is as follows: the base vacuum degree is better than 1.0x10
-5Torr, operating air pressure 1～10mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, and power 50～1000W, underlayer temperature are room temperature (RT)～500 ℃, and deposition rate is 10～100nm/min.;
S30, get the Nano/micron ball solution that concentration is 0.5～1wt.%, mix in the ratio of 1:1～30 with deionized water, the material of described Nano/micron ball is polystyrene (PS) or silicon dioxide (SiO
2), particle diameter is 100nm～3um, and the pH value of this mixed solution is transferred to 2～7, and conductive substrates B is put in this solution, places 0.5min.～2min., takes out, water is rinsed well, obtains conductive substrates C.
Because the isoelectric point (Isoelectric Point) of the conductive oxide films such as AZO, ITO is larger, probably about 6～10, and polystyrene microsphere (PS) or silicon dioxide microsphere (SiO
2) isoelectric point smaller, generally be about 2～4.Therefore be in about 2～6 faintly acid polystyrene or the solution of silica nanometer/micron ball the time when electro-conductive glass being put into PH, negative electricity can be with in the surface of conductive oxide film, and polystyrene or the surface of silica nanometer/micron ball will become positively charged causes the mutual electrostatic attraction of this bi-material.Through behind 0.5min.～2min., (such as Fig. 5, shown in Figure 6) almost will be adsorbed by one deck Nano/micron ball in the surface of sull.The Nano/micron ball can change along with the time of microspheres solution concentration, pH value, dipping plated film in the lip-deep coverage rate of sull.
S40, utilize the magnetron sputtering mode to plate one deck oxide conductive film at conductive substrates C, obtain conductive substrates D.In step S40, the magnetron sputtering technique condition is as follows: the base vacuum degree is better than 1.0x10
-5Torr, operating air pressure 1～10mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, and power 50～1000W, underlayer temperature are room temperature (RT)～500 ℃, and deposition rate is 10～100nm/min..Magnetron sputtering sull out can enter into the gap between microballoon and the microballoon, and forming does not have U-shaped matte corner angle, surface uniform (as shown in Figure 7).
The Nano/micron ball of conductive substrates D upper surface is removed in S50, cleaning, obtain the U-shaped matte conductive substrates of flexible solar battery (as shown in Figure 2), this novel matte conductive substrates possesses good electrology characteristic (surface resistance is less than 0.2ohm) and excellent sunken light characteristic, namely has high light scattering characteristic, at the 700nm place, DR (diffuse scattering part in the reflection)/TR (total reflection) reaches 90%, at the 1100nm place, DR (diffuse scattering part in the reflection)/TR (total reflection) reaches 60%, as shown in Figure 8.
The below provides eight specific embodiments of the present invention.
Embodiment 1
A kind of preparation method who is specifically designed to the novel matte conductive substrates of flexible solar battery may further comprise the steps:
Adopt magnetron sputtering apparatus to plate the very thin metal conductive film of one deck at flexible substrate, obtain conductive substrates A.The coating process of magnetron sputtering is: the base vacuum degree is 3.0x10
-6Torr, operating air pressure 4mTorr, working gas Ar, shielding power supply are direct current, and power 200W, underlayer temperature are room temperature (RT), and deposit thickness is 100nm;
Adopt the magnetron sputtering mode to plate the very thin oxide conductive film of one deck at conductive substrates A, obtain conductive substrates B.Magnetron sputtering technique is: base vacuum is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, and power 200W, underlayer temperature are room temperature (RT), and deposit thickness is 20nm;
Get Nano/micron ball solution, mix according to a certain percentage with deionized water, the pH value of this mixed solution is transferred to 4, conductive substrates B is put in the solution, place 2min., take out, water is rinsed well, obtains conductive substrates C;
Utilize the magnetron sputtering mode to plate one deck oxide conductive film at conductive substrates C, obtain conductive substrates D.Magnetron sputtering technique is: the base vacuum degree is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, power 200W, underlayer temperature are room temperature (RT);
Clean the Nano/micron ball of removing conductive substrates D upper surface, obtain the novel matte conductive substrates of flexible solar battery special use, the surface resistance of this novel matte conductive substrates is less than 0.1ohm.
Embodiment 2
A kind of preparation method who is specifically designed to the novel matte conductive substrates of flexible solar battery may further comprise the steps:
Adopt magnetron sputtering apparatus to plate the very thin metal conductive film of one deck at flexible substrate, obtain conductive substrates A.The coating process of magnetron sputtering is: the base vacuum degree is 3.0x10
-6Torr, operating air pressure 4mTorr, working gas Ar, shielding power supply are direct current, and power 200W, underlayer temperature are 200 ℃, and deposit thickness is 100nm;
Adopt the magnetron sputtering mode to plate the very thin oxide conductive film of one deck at conductive substrates A, obtain conductive substrates B.Magnetron sputtering technique is: base vacuum is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, and power 200W, underlayer temperature are 200 ℃, and deposit thickness is 20nm;
Get Nano/micron ball solution, mix according to a certain percentage with deionized water, the pH value of this mixed solution is transferred to 4, conductive substrates B is put in the solution, place 2min., take out, water is rinsed well, obtains conductive substrates C;
Utilize the magnetron sputtering mode to plate one deck oxide conductive film at conductive substrates C, obtain conductive substrates D.Magnetron sputtering technique is: the base vacuum degree is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, power 200W, underlayer temperature are room temperature (RT);
Clean the Nano/micron ball of removing conductive substrates D upper surface, obtain the novel matte conductive substrates of flexible solar battery special use, the surface resistance of this novel matte conductive substrates is less than 0.1ohm.
Embodiment 3
A kind of preparation method who is specifically designed to the novel matte conductive substrates of flexible solar battery may further comprise the steps:
Adopt magnetron sputtering apparatus to plate the very thin metal conductive film of one deck at flexible substrate, obtain conductive substrates A.The coating process of magnetron sputtering is: the base vacuum degree is 3.0x10
-6Torr, operating air pressure 4mTorr, working gas Ar, shielding power supply are direct current, and power 200W, underlayer temperature are room temperature (RT), and deposit thickness is 60nm;
Adopt the magnetron sputtering mode to plate the very thin oxide conductive film of one deck at conductive substrates A, obtain conductive substrates B.Magnetron sputtering technique is: base vacuum is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, and power 200W, underlayer temperature are room temperature (RT), and deposit thickness is 40nm;
Get Nano/micron ball solution, mix according to a certain percentage with deionized water, the pH value of this mixed solution is transferred to 5, conductive substrates B is put in the solution, place 2min., take out, water is rinsed well, obtains conductive substrates C;
Utilize the magnetron sputtering mode to plate one deck oxide conductive film at conductive substrates C, obtain conductive substrates D.Magnetron sputtering technique is: the base vacuum degree is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, power 200W, underlayer temperature are room temperature (RT);
Clean the Nano/micron ball of removing conductive substrates D upper surface, obtain the novel matte conductive substrates of flexible solar battery special use, the surface resistance of this novel matte conductive substrates is less than 0.2ohm.
Embodiment 4
A kind of preparation method who is specifically designed to the novel matte conductive substrates of flexible solar battery may further comprise the steps:
Adopt magnetron sputtering apparatus to plate the very thin metal conductive film of one deck at flexible substrate, obtain conductive substrates A.The coating process of magnetron sputtering is: the base vacuum degree is 3.0x10
-6Torr, operating air pressure 4mTorr, working gas Ar, shielding power supply are direct current, and power 200W, underlayer temperature are room temperature (RT), and deposit thickness is 20nm;
Adopt the magnetron sputtering mode to plate the very thin oxide conductive film of one deck at conductive substrates A, obtain conductive substrates B.Magnetron sputtering technique is: base vacuum is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, and power 200W, underlayer temperature are room temperature (RT), and deposit thickness is 60nm;
Get Nano/micron ball solution, mix according to a certain percentage with deionized water, the pH value of this mixed solution is transferred to 6, conductive substrates B is put in the solution, place 2min., take out, water is rinsed well, obtains conductive substrates C;
Utilize the magnetron sputtering mode to plate one deck oxide conductive film at conductive substrates C, obtain conductive substrates D.Magnetron sputtering technique is: the base vacuum degree is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, power 200W, underlayer temperature are room temperature (RT);
Clean the Nano/micron ball of removing conductive substrates D upper surface, obtain the novel matte conductive substrates of flexible solar battery special use, the surface resistance of this novel matte conductive substrates is less than 0.2ohm.
Embodiment 5
A kind of preparation method who is specifically designed to the novel matte conductive substrates of flexible solar battery may further comprise the steps:
Adopt magnetron sputtering apparatus to plate the very thin metal conductive film of one deck at flexible substrate, obtain conductive substrates A.The coating process of magnetron sputtering is: the base vacuum degree is 3.0x10
-6Torr, operating air pressure 4mTorr, working gas Ar, shielding power supply are direct current, and power 200W, underlayer temperature are 200 ℃, and deposit thickness is 60nm;
Adopt the magnetron sputtering mode to plate the very thin oxide conductive film of one deck at conductive substrates A, obtain conductive substrates B.Magnetron sputtering technique is: base vacuum is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, and power 200W, underlayer temperature are 200 ℃, and deposit thickness is 40nm;
Get Nano/micron ball solution, mix according to a certain percentage with deionized water, the pH value of this mixed solution is transferred to 4, conductive substrates B is put in the solution, place 1min., take out, water is rinsed well, obtains conductive substrates C;
Utilize the magnetron sputtering mode to plate one deck oxide conductive film at conductive substrates C, obtain conductive substrates D.Magnetron sputtering technique is: the base vacuum degree is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, power 200W, underlayer temperature are room temperature (RT);
Clean the Nano/micron ball of removing conductive substrates D upper surface, obtain the novel matte conductive substrates of flexible solar battery special use, the surface resistance of this novel matte conductive substrates is less than 0.2ohm.
Embodiment 6
A kind of preparation method who is specifically designed to the novel matte conductive substrates of flexible solar battery may further comprise the steps:
Adopt magnetron sputtering apparatus to plate the very thin metal conductive film of one deck at flexible substrate, obtain conductive substrates A.The coating process of magnetron sputtering is: the base vacuum degree is 3.0x10
-6Torr, operating air pressure 4mTorr, working gas Ar, shielding power supply are direct current, and power 200W, underlayer temperature are 200 ℃, and deposit thickness is 20nm;
Adopt the magnetron sputtering mode to plate the very thin oxide conductive film of one deck at conductive substrates A, obtain conductive substrates B.Magnetron sputtering technique is: base vacuum is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, and power 200W, underlayer temperature are 200 ℃, and deposit thickness is 60nm;
Get Nano/micron ball solution, mix according to a certain percentage with deionized water, the pH value of this mixed solution is transferred to 4, conductive substrates B is put in the solution, place 1min., take out, water is rinsed well, obtains conductive substrates C;
Utilize the magnetron sputtering mode to plate one deck oxide conductive film at conductive substrates C, obtain conductive substrates D.Magnetron sputtering technique is: the base vacuum degree is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, power 200W, underlayer temperature are room temperature (RT);
Clean the Nano/micron ball of removing conductive substrates D upper surface, obtain the novel matte conductive substrates of flexible solar battery special use, the surface resistance of this novel matte conductive substrates is less than 0.2ohm.
Embodiment 7
A kind of preparation method who is specifically designed to the novel matte conductive substrates of flexible solar battery may further comprise the steps:
Adopt magnetron sputtering apparatus to plate the very thin metal conductive film of one deck at flexible substrate, obtain conductive substrates A.The coating process of magnetron sputtering is: the base vacuum degree is 3.0x10
-6Torr, operating air pressure 4mTorr, working gas Ar, shielding power supply are direct current, and power 200W, underlayer temperature are 200 ℃, and deposit thickness is 5nm;
Adopt the magnetron sputtering mode to plate the very thin oxide conductive film of one deck at conductive substrates A, obtain conductive substrates B.Magnetron sputtering technique is: base vacuum is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, and power 200W, underlayer temperature are 200 ℃, and deposit thickness is 20nm;
Get Nano/micron ball solution, mix according to a certain percentage with deionized water, the pH value of this mixed solution is transferred to 4, conductive substrates B is put in the solution, place 2min., take out, water is rinsed well, obtains conductive substrates C;
Utilize the magnetron sputtering mode to plate one deck oxide conductive film at conductive substrates C, obtain conductive substrates D.Magnetron sputtering technique is: the base vacuum degree is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, power 200W, underlayer temperature are room temperature (RT);
Clean the Nano/micron ball of removing conductive substrates D upper surface, obtain the novel matte conductive substrates of flexible solar battery special use, the surface resistance of this novel matte conductive substrates is less than 0.2ohm.
Embodiment 8
A kind of preparation method who is specifically designed to the novel matte conductive substrates of flexible solar battery may further comprise the steps:
Adopt magnetron sputtering apparatus to plate the very thin metal conductive film of one deck at flexible substrate, obtain conductive substrates A.The coating process of magnetron sputtering is: the base vacuum degree is 3.0x10
-6Torr, operating air pressure 4mTorr, working gas Ar, shielding power supply are direct current, and power 200W, underlayer temperature are room temperature (RT), and deposit thickness is 5nm;
Adopt the magnetron sputtering mode to plate the very thin oxide conductive film of one deck at conductive substrates A, obtain conductive substrates B.Magnetron sputtering technique is: base vacuum is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, and power 200W, underlayer temperature are room temperature (RT), and deposit thickness is 20nm;
Get Nano/micron ball solution, mix according to a certain percentage with deionized water, the pH value of this mixed solution is transferred to 4, conductive substrates B is put in the solution, place 2min., take out, water is rinsed well, obtains conductive substrates C;
Utilize the magnetron sputtering mode to plate one deck oxide conductive film at conductive substrates C, obtain conductive substrates D.Magnetron sputtering technique is: the base vacuum degree is 1.0x10
-5Torr, operating air pressure 4mTorr, working gas Ar+O
2, shielding power supply is radio frequency 13.56MHz, power 200W, underlayer temperature are room temperature (RT);
Clean the Nano/micron ball of removing conductive substrates D upper surface, obtain the novel matte conductive substrates of flexible solar battery special use, the surface resistance of this novel matte conductive substrates is less than 0.2ohm.
The present invention has following advantage:
1), low cost.The thickness of metal conductive film and oxide conductive film thereof is all very thin in the structure, and the Nano/micron ball that adopts is with low cost;
2) but low temperature preparation.Whole technique all can be finished at low temperatures, can greatly reduce energy consumption;
3), than the single back reflection structure of Traditional Industrialization, the present invention has excellent light trapping structure, so that more light can be scattered telegram in reply pond absorbed layer again, thereby further reduces the thickness of battery obsorbing layer, reduces the production cost of battery/assembly;
4) but large tracts of land preparation.Whole technique only relates to magnetron sputtering apparatus, and the magnetron sputtering apparatus technology is very ripe at present, can accomplish uniformly 2.2m x2.6m in the industrialization;
5) but suitability for industrialized production.The techniques such as the used magnetron sputtering of the present invention, dipping plated film, cleaning all are complementary with industrial standard technique, can obtain fast conversion production.
6), technique can be promoted.Whole invented technology also can well be generalized in volume to volume (the Roll to roll) technology.
The present invention is not limited to above-mentioned preferred forms, and anyone should learn the structural change of making under enlightenment of the present invention, and every have identical or close technical scheme with the present invention, all falls within protection scope of the present invention.
Claims (9)
1. flexible solar battery matte conductive substrates, comprise flexible substrate and the metal conductive film and the oxide conductive film that are coated with successively on it, it is characterized in that, the surface of described oxide conductive film is the matte with the U-shaped pattern of nanoscale, the thickness of described metal conductive film is 5～120nm, and the thickness of described oxide conductive film is 20～60nm.
2. a kind of flexible solar battery matte conductive substrates as claimed in claim 1, it is characterized in that, described flexible solar battery is silicon-based film solar cells, cadmium telluride diaphragm solar battery, organic flexible solar battery or dye sensitized flexible solar battery.
3. a kind of flexible solar battery matte conductive substrates as claimed in claim 1, it is characterized in that, described flexible substrate is polyimide film (PI), polyethylene naphthalate (PEN), PETG (PET) or stainless steel.
4. a kind of flexible solar battery matte conductive substrates as claimed in claim 1 is characterized in that, described metal conductive film is silver, gold or aluminium.
5. a kind of flexible solar battery matte conductive substrates as claimed in claim 1 is characterized in that, described oxide conductive film is Al-Doped ZnO (ZnO:Al) or mixes indium tin oxide (ITO).
6. the preparation method of a flexible solar battery matte conductive substrates is characterized in that, may further comprise the steps:
S10, employing magnetron sputtering mode plate the very thin metal conductive film of one deck at flexible substrate, obtain conductive substrates A, and the deposit thickness of described metal conductive film is 5～120nm;
S20, employing magnetron sputtering mode plate the very thin oxide conductive film of one deck at conductive substrates A, obtain conductive substrates B, and the deposit thickness of described oxide conductive film is 20～60nm;
S30, get the Nano/micron ball solution that concentration is 0.5～1wt.%, mix in the ratio of 1:1～30 with deionized water, the material of described Nano/micron ball is polystyrene (PS) or silicon dioxide (SiO
2), particle diameter is 100nm～3um, and the pH value of this mixed solution is transferred to 2～7, and conductive substrates B is put in this solution, places 0.5min.～2min., takes out, water is rinsed well, obtains conductive substrates C;
S40, utilize the magnetron sputtering mode to plate one deck oxide conductive film at conductive substrates C, obtain conductive substrates D;
The Nano/micron ball of conductive substrates D upper surface is removed in S50, cleaning, obtains the U-shaped matte conductive substrates of flexible solar battery.
7. the preparation method of a kind of flexible solar battery matte conductive substrates as claimed in claim 6 is characterized in that, in step S10, the magnetron sputtering technique condition is as follows: the base vacuum degree is better than 3.0x10
-6Torr, operating air pressure 1～4mTorr, working gas are Ar, and shielding power supply is direct current (DC), and power 50～1000W, underlayer temperature are room temperature (RT)～500 ℃, and deposition rate is 30～100nm/min..
8. the preparation method of a kind of flexible solar battery matte conductive substrates as claimed in claim 6 is characterized in that, in step S20, the magnetron sputtering technique condition is as follows: the base vacuum degree is better than 1.0x10
-5Torr, operating air pressure 1～10mTorr, working gas Ar+O
2, shielding power supply is radio frequency (13.56MHz), and power 50～1000W, underlayer temperature are room temperature (RT)～500 ℃, and deposition rate is 10～100nm/min..
9. the preparation method of a kind of flexible solar battery matte conductive substrates as claimed in claim 6 is characterized in that, in step S40, the magnetron sputtering technique condition is as follows: the base vacuum degree is better than 1.0x10
-5Torr, operating air pressure 1～10mTorr, working gas Ar+O
2, shielding power supply is radio frequency (13.56MHz), and power 50～1000W, underlayer temperature are room temperature (RT)～500 ℃, and deposition rate is 10～100nm/min..
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