CN101887920A - Transparent conductive film glass of solar battery and production method thereof - Google Patents
Transparent conductive film glass of solar battery and production method thereof Download PDFInfo
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- CN101887920A CN101887920A CN201010209338XA CN201010209338A CN101887920A CN 101887920 A CN101887920 A CN 101887920A CN 201010209338X A CN201010209338X A CN 201010209338XA CN 201010209338 A CN201010209338 A CN 201010209338A CN 101887920 A CN101887920 A CN 101887920A
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- transparent conductive
- conductive film
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- solar battery
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to transparent conductive film glass of a solar battery and a production method thereof. The production method is characterized by comprising the following steps: 1) installing two chemical vapor phase reactors before and after the upward side of a moving hot glass plate under 400-700 DEG C; 2) using a first chemical vapor phase reactor to deposit the mixed gas of gaseous precursor of silicon oxide and inert carrier gas on the hot glass plate; and 3) using a second chemical vapor phase reactor to deposit the mixed gas of gaseous precursor of stannic oxide, inert carrier gas, gaseous precursor of fluorine and auxiliary reactant gas on the hot glass plate, wherein the auxiliary reactant gas contains the mixture of steam and lower alkanol or ethyl acetate. The production method of the invention has simple process; and the obtained FTO transparent conductive film glass is characterized by high transmittance and conductivity and textured structure and is widely used in the amorphous silicon (a-Si:H) thin-film solar battery.
Description
Technical field
The present invention relates to a kind of used for solar batteries transparent conducting film glass and production method thereof, say so more accurately and utilize the aumospheric pressure cvd method, at the hot glass surface deposition doped sno_2 fluorine transparent conductive oxide film (FTO) that moves, this nesa coating is mainly used in amorphous silicon (a-Si:H) thin film solar cell electrode.
Background technology
Along with being on the rise of energy crisis and traditional energy environmental pollution; develop renewable clear energy sources and become one of great strategic problem in the international coverage; solar energy is inexhaustible, nexhaustible clear energy sources; therefore, research and development utilize solar energy to become the energy strategy decision-making of countries in the world government sustainable development.Wherein, amorphous silicon (a-Si:H) thin-film solar cells is with advantages such as its low cost, easy large tracts of land realizations, in thin-film solar cells, occupy the top priority, and the FTO nesa coating has the advantage of high permeability, high conductivity and self suede structure, and it is used widely in the a-Si:H thin-film solar cells.
Chinese patent CN1962510 sets forth a kind of method of utilizing spray pyrolysis to prepare tin oxide transparent conductive film.This method is utilized SnCl
22H
2O and NH
4F has obtained the SnO 2 thin film of resistance 20 Ω/, but this method film forming speed is too low, needs through repeatedly spraying the nesa coating that just can be met requirement repeatedly; Chinese patent CN101140143 has set forth the method and the equipment of ultrasound nebulization method preparing large area transparent conductive film.This method is passed through supersonic spraying, on static hot glass surface, deposited doped sno_2 fluorine nesa coating, rete conductivity and transmitance are higher, but this method does not relate to the preparation of intershield layer, simultaneously, the sample rete that this method obtains is even inadequately and size is less, should not carry out suitability for industrialized production; Chinese patent CN101188149 has set forth a kind of method of utilizing radio-frequency magnetron sputter method at the AZ0 nesa coating of glass surface codeposition Ce doping, and having obtained resistivity is 7～8 * 10
-4Ω cm, mean transmissivity reaches 80～90% nesa coating in 400～800nm visible-range, but the nesa coating that this method obtains itself does not have suede structure, needs through just being applied to electrode of solar battery after the matte processing; Chinese patent CN1145882 has set forth a kind of mode by chemical vapour deposition (CVD) on 630～640 ℃ plate glass that moves or float glass matrix, utilizes butter of tin and water premixed to form single air-flow, the method for deposition tin oxide rete.The reactive material that this method relates to requires moment decomposition reaction at high temperature, and is wayward, complex process.
Summary of the invention
Purpose of the present invention is exactly the various defectives that exist for the transparent conductive film glass of solar battery that overcomes existing technology and production, and a kind of used for solar batteries transparent conductive film glass and production method thereof are provided.
To achieve these goals, the present invention has adopted following technical scheme:
A kind of transparent conductive film glass of solar battery, comprise glass substrate 1 and top layer SnO 2 thin film 3, it is characterized in that: deposition one layer thickness is that 30-150nm, main component are the intermediate layer films 2 of tin oxide, silica on glass substrate 1, deposits one deck top layer SnO 2 thin film 3 on the intermediate layer film 2 again.The preferred 50-90nm of the thickness of intermediate layer film 2.Doped with fluorine in the top layer SnO 2 thin film 3, the thickness of top layer SnO 2 thin film 3 is 360nm at least.
A kind of production method of transparent conductive film glass of solar battery is characterized in that may further comprise the steps:
A, be provided with two cover cvd reactors before and after above 400 ℃ of-700 ℃ of mobile hot glass sheets;
B, first cvd reactor are to the gaseous state predecessor of hot glass sheet cvd silicon oxide and the mist of inert carrier gas, and the chemical formula of the gaseous state predecessor of silica is R
uO
vSi
m, wherein R is straight or branched or cycloalkyl, u=3～8, v=O～4, m=1～4;
C, second cvd reactor are gaseous state predecessor, inert carrier gas, the gaseous state predecessor of fluorine and the mist of assisted reaction gas of tin oxide to the hot glass sheet deposition, and the chemical formula of the gaseous state predecessor of tin oxide is R
nSnCl
4-n, wherein R is straight or branched or cycloalkyl, n=0, and 1 or 2, assisted reaction gas comprises the mixture that steam, low-level chain triacontanol or ethyl acetate form, or a kind of or two kinds of mixtures that material forms wherein.
Mist among the step b also comprises following reactant gas, the mixed gas that forms as the organic metal alkoxide, steam, lewis acid, triethyl phosphite of gasification, or the mixed gas that forms of the combination in any in the listed material.
The gaseous state predecessor of said fluorine is a kind of in the trifluoroacetic acid, hydrofluoric acid, phosphorus trifluoride, ammonium fluoride of gaseous state among the step c.
A kind of used for solar batteries transparent conductive film glass provided by the invention and production method thereof, be to utilize the aumospheric pressure cvd method, the hot glass surface deposition doped sno_2 fluorine transparent conductive oxide film (FTO) that adopts suitable gaseous state predecessor moving.
In the present invention, the main component of nesa coating is a SnO 2 thin film, in order to improve the conductance of rete, need in rete, mix and form the semiconductor conductive film, the composition that mixes has fluorine, antimony etc., because the fluorine doped transparent conductive film has higher visible light transmissivity, therefore preferred fluorine is as doped chemical; Simultaneously, the thickness that the tin oxide among the present invention is mixed the fluorine nesa coating is 360nm at least, preferably is not less than 400nm, and the upper limit of thickness has no particular limits, and generally is no more than 1200nm.
In the present invention, deposition one intermediate layer between glass substrate and top layer SnO 2 thin film, the purpose in this intermediate layer, on the one hand, be to cause conducting film alkalosis in the nesa coating, thereby influence the conductivity and the light transmission of rete in order to prevent that alkali metal ion in the glass substrate is diffused into; On the other hand, be in order to eliminate the interference of light striped of rete.
In the present invention, the glass substrate temperature that deposits tin oxide transparent conductive film with the aumospheric pressure cvd method is 400-700 ℃, and in order to obtain higher conductivity, at least 600 ℃ of general temperature preferably are no less than 620 ℃.
In the present invention, the chemical formula of the used tin oxide gaseous state predecessor of aumospheric pressure cvd method deposition of transparent conductive film is R
nS
nCl
4-n, wherein R is straight or branched or cycloalkyl, n=0,1 or 2; Tin source R
nS
nCl
4-nCan be gaseous state, liquid state or solid-state at normal temperatures,, then need to gasify at a certain temperature if liquid or solid-state.Their common trait is to be easier to gasification (referring to liquid or solid-state), and when contacting with glass substrate, under the residing temperature conditions of glass-board surface, can carry out thermal chemical reaction rapidly.Commonly used as organotins such as inorganic tin such as butter of tin or monobutyl-tin-trichloride.
The chemical formula of the gaseous state predecessor of silica is R
uO
vSi
m, wherein R is straight or branched or cycloalkyl, u=3-8, v=0-4, m=1-4.Typical in tetraethoxysilane (TEOS), monosilane (SiH
4).
The gaseous state predecessor of fluorine comprises trifluoroacetic acid, hydrofluoric acid, phosphorus trifluoride, ammonium fluoride etc.There is the conductivity that can improve FTO nesa coating film in they as doping.
Oxygen source in the gaseous state predecessor is oxygen, water, carbonyls class (particularly ester) etc.
Need in the gaseous state predecessor mist to add stabilizer, the existence of stabilizer can prevent that mixed gas from undesirable pre-reaction taking place.Stabilizer is ester class, carboxylic acids etc., and is typical in ethyl acetate.
The present invention can control the quality of rete by changing the prescription of gaseous state predecessor mixed airflow, improves the function of rete.
Technology of the present invention is simple, adopt suitable gaseous state predecessor to deposit doped sno_2 fluorine transparent conductive oxide film (FTO) at the hot glass surface that moves, the FTO nesa coating that obtains has the characteristics of high permeability, high conductivity and self suede structure, uses extremely wide in amorphous silicon (a-Si:H) thin-film solar cells.
Description of drawings:
Fig. 1 is the film layer structure schematic diagram of FTO nesa coating;
Fig. 2 is a process flow diagram of the present invention;
Fig. 3 is the structural representation of non-crystal silicon solar cell unit.
Embodiment
Further specify the present invention below in conjunction with embodiment, the present invention simultaneously is not restricted to these embodiment.
Embodiment
As shown in Figure 1, a kind of transparent conductive film glass of solar battery provided by the invention, comprise glass substrate 1 and top layer SnO 2 thin film 3, deposition one layer thickness is that 30-150nm, main component are the intermediate layer films 2 of tin oxide, silica on glass substrate 1, deposits one deck top layer SnO 2 thin film 3 on the intermediate layer film 2 again.The preferred 50-90nm of the thickness of intermediate layer film 2.Doped with fluorine in the top layer SnO 2 thin film 3, the thickness of top layer SnO 2 thin film 3 is 360nm at least.
The production method of a kind of transparent conductive film glass of solar battery provided by the invention, the flow process of its technology be with reference to Fig. 2, and assembling two cover plated film reactors 7 in plated film section 5, reactor 7 are from the adjustable height of glass substrate 9, general 1-15mm, preferred 4-8mm.Glass plate 9 is heated to pre-set temperature in bringing-up section 4 after, be transported in the plated film section 5 by live-roller gear 8, the electrodeless frequency conversion of live-roller gear 8 transfer rates is adjustable, in reactor 7 zones, the reactant gas predecessor is at successively quick uniform deposition intermediate layer, hot glass substrate 9 surfaces and electrically conducting transparent layer film, at last, the glass that has plated film is sent in the annealing section 6 and is cooled off annealing, in order to guarantee the cultivation of fully being grown of rete nucleus, the temperature of annealing section need be set in advance in a suitable depth-graded scope.
In the present embodiment, the temperature of glass substrate is 660 ℃; Glass substrate is the 4mm ultra-clear glasses; The plated film linear velocity is 252m/hr; First reactor that utilizes is with tetraethoxysilane (TEOS), monobutyl-tin-trichloride (MBTC), tricresyl phosphite second fat (TEP), steam (H
2O), (mole percent of each composition is respectively gaseous precursor mixture such as nitrogen: TEOS 1.2%, MBTC 0.9%, TEP 0.5%, H
2O 1.9%, and all the other are nitrogen) guide on the mobile glass basis surface cvd silicon oxide, the compound middle rete of tin oxide into;
Utilize second reactor with vaporized monobutyl-tin-trichloride (MBTC), trifluoroacetic acid (TFA), water (H
2O) etc. (mole percent of each composition is respectively the gaseous precursor mixture made of premixed: MBTC1.6mol%, TFA 0.8mol%, H
2O 4.5mol%, all the other are nitrogen) do carrier with nitrogen, be passed on the glass surface of mobile heat, deposition tin oxide is mixed the fluorine nesa coating.
After measured, intermediate layer thickness is 83nm, and FTO electrically conducting transparent layer thickness is 660nm, and the square resistance of rete is 7.6 Ω/, and resistivity p is 5.016 * 10
-4Ω/cm, the carrier concentration of rete is that n is 7.8 * 10
20Cm
3, the visible light transmissivity of FTO transparent conducting film glass is 82%.Therefore as can be known, this FTO nesa coating has good optics, electric property, can be applicable to amorphous silicon (a-Si:H) thin-film solar cells fully.
The FTO nesa coating that the present invention obtains has the characteristics of high permeability, high conductivity and self suede structure, in amorphous silicon (a-Si:H) thin-film solar cells, use extremely extensively, therefore be necessary the a-Si:H film solar battery structure is done simple declaration.
Fig. 3 is a-Si:H thin-film solar cells unit (Cell) structural representation that utilizes FTO transparent conducting film glass of the present invention, and intermediate layer 11 and 12 chemical vapour deposition (CVD)s successively of FTO transparency conducting layer are on glass substrate 10; On FTO transparency conducting layer 12, be raw material then with gases such as silane, hydrogen, adopt plasma reinforced chemical vapour deposition method (PECVD) deposition of amorphous silicon (a-Si:H) photoelectricity conversion coating 13, amorphous silicon (a-Si:H) layer 13 is by p, i, three layers of composition of n form the pin structure; Hydatogenesis metal conducting layer 14 on amorphous silicon (a-Si:H) layer 13 has so just formed an a-Si:H thin-film solar cells unit at last.
Claims (6)
1. transparent conductive film glass of solar battery, comprise glass substrate (1) and top layer SnO 2 thin film (3), it is characterized in that: going up deposition one layer thickness at glass substrate (1) is that 30-150nm, main component are the intermediate layer films (2) of tin oxide, silica, deposits one deck top layer SnO 2 thin film (3) on the intermediate layer film (2) again.
2. transparent conductive film glass of solar battery according to claim 1 is characterized in that: the preferred 50-90nm of thickness of intermediate layer film (2).
3. transparent conductive film glass of solar battery according to claim 1 and 2 is characterized in that: doped with fluorine in the top layer SnO 2 thin film (3), the thickness of top layer SnO 2 thin film (3) is 360nm at least.
4. the production method of transparent conductive film glass of solar battery is characterized in that may further comprise the steps:
A, be provided with two cover cvd reactors before and after above 400 ℃ of-700 ℃ of mobile hot glass sheets;
B, first cvd reactor are to the gaseous state predecessor of hot glass sheet cvd silicon oxide and the mist of inert carrier gas, and the chemical formula of the gaseous state predecessor of silica is R
uO
vSi
m, wherein R is straight or branched or cycloalkyl, u=3～8, v=0～4, m=1～4;
C, second cvd reactor are gaseous state predecessor, inert carrier gas, the gaseous state predecessor of fluorine and the mist of assisted reaction gas of tin oxide to the hot glass sheet deposition, and the chemical formula of the gaseous state predecessor of tin oxide is R
nSnCl
4-n, wherein R is straight or branched or cycloalkyl, n=0, and 1 or 2, assisted reaction gas comprises the mixture that steam, low-level chain triacontanol or ethyl acetate form, or the mixture of a kind of or two kinds of formation wherein.
5. the production method of used for solar batteries transparent conductive film according to claim 4, it is characterized in that the mist among the step b also comprises following reactant gas, the mixed gas that forms as the organic metal alkoxide, steam, lewis acid, triethyl phosphite of gasification, or the mixed gas that forms of the combination in any in the listed material.
6. the production method of transparent conductive film glass of solar battery according to claim 4 is characterized in that, the gaseous state predecessor of said fluorine is a kind of in the trifluoroacetic acid, hydrofluoric acid, phosphorus trifluoride, ammonium fluoride of gaseous state among the step c.
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| CN201010209338XA CN101887920A (en) | 2010-06-25 | 2010-06-25 | Transparent conductive film glass of solar battery and production method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534622A (en) * | 2012-03-20 | 2012-07-04 | 常州比太科技有限公司 | Method for forming solar dry textured black silicon by plasma excitation |
| CN103058530A (en) * | 2013-01-23 | 2013-04-24 | 秦皇岛玻璃工业研究设计院 | Film plating device and method for preparing TCO (Transparent Conducting Oxide) glass online by floating method |
| CN103803808A (en) * | 2014-02-22 | 2014-05-21 | 蚌埠玻璃工业设计研究院 | Method for large-area preparation of transparent conductive film glass |
| CN104264127A (en) * | 2014-09-28 | 2015-01-07 | 中国建材国际工程集团有限公司 | Production method for transparent conductive films for photovoltaic cells |
| CN105174742A (en) * | 2015-08-31 | 2015-12-23 | 东北电力大学 | Preparation method for conductive glass |
| CN108358467A (en) * | 2018-04-02 | 2018-08-03 | 威海中玻新材料技术研发有限公司 | A kind of broken colour Low emissivity sunlight controlling coated glass and preparation method thereof |
| CN113871539A (en) * | 2021-12-02 | 2021-12-31 | 中国华能集团清洁能源技术研究院有限公司 | Preparation method of perovskite solar cell |
| CN116002988A (en) * | 2022-12-12 | 2023-04-25 | 玻璃新材料创新中心(安徽)有限公司 | Transparent conductive film glass for solar cell and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534622A (en) * | 2012-03-20 | 2012-07-04 | 常州比太科技有限公司 | Method for forming solar dry textured black silicon by plasma excitation |
| CN103058530A (en) * | 2013-01-23 | 2013-04-24 | 秦皇岛玻璃工业研究设计院 | Film plating device and method for preparing TCO (Transparent Conducting Oxide) glass online by floating method |
| CN103058530B (en) * | 2013-01-23 | 2015-05-06 | 秦皇岛玻璃工业研究设计院 | Film plating device and method for preparing TCO (Transparent Conducting Oxide) glass online by floating method |
| CN103803808A (en) * | 2014-02-22 | 2014-05-21 | 蚌埠玻璃工业设计研究院 | Method for large-area preparation of transparent conductive film glass |
| CN104264127A (en) * | 2014-09-28 | 2015-01-07 | 中国建材国际工程集团有限公司 | Production method for transparent conductive films for photovoltaic cells |
| CN105174742A (en) * | 2015-08-31 | 2015-12-23 | 东北电力大学 | Preparation method for conductive glass |
| CN105174742B (en) * | 2015-08-31 | 2018-02-16 | 东北电力大学 | A kind of preparation method of electro-conductive glass |
| CN108358467A (en) * | 2018-04-02 | 2018-08-03 | 威海中玻新材料技术研发有限公司 | A kind of broken colour Low emissivity sunlight controlling coated glass and preparation method thereof |
| CN108358467B (en) * | 2018-04-02 | 2020-06-23 | 威海中玻新材料技术研发有限公司 | Multi-color low-radiation sunlight control coated glass and preparation method thereof |
| CN113871539A (en) * | 2021-12-02 | 2021-12-31 | 中国华能集团清洁能源技术研究院有限公司 | Preparation method of perovskite solar cell |
| CN113871539B (en) * | 2021-12-02 | 2022-03-01 | 中国华能集团清洁能源技术研究院有限公司 | Preparation method of perovskite solar cell |
| CN116002988A (en) * | 2022-12-12 | 2023-04-25 | 玻璃新材料创新中心(安徽)有限公司 | Transparent conductive film glass for solar cell and preparation method thereof |
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Application publication date: 20101117 |