CN1819274A - Thin-film solar battery barrier with flexible substrate and production thereof - Google Patents
Thin-film solar battery barrier with flexible substrate and production thereof Download PDFInfo
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- CN1819274A CN1819274A CNA2005101225291A CN200510122529A CN1819274A CN 1819274 A CN1819274 A CN 1819274A CN A2005101225291 A CNA2005101225291 A CN A2005101225291A CN 200510122529 A CN200510122529 A CN 200510122529A CN 1819274 A CN1819274 A CN 1819274A
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Abstract
The barrier layer of thin film solar cell with a flexible substrate is composed of a metallic nickel layer or metallic titanium layer with 30-50nm thickness. It can prevent from metallic aluminum of back electrode entering into main body of cell at preparation of cell. Forming a barrier layer between back electrode and silicon-based film of cell doesn't influence reflection of incident light, and meanwhile increases its light path action in absorbing layer of cell.
Description
Technical field
The present invention relates to the method for flexible substrate semiconductor film membrane module preparation, more particularly, relate to barrier layer of flexible substrate film solar battery and preparation method thereof.
Background technology
Solar cell is a kind of device that directly luminous energy is converted into electric energy, and wherein using more is silicon-based thin film solar cell.Usually, silicon-based thin film solar cell is pressed the P-I-N sequential aggradation on glass substrate.The solar cell production cost that with the flexible material is substrate is low, realizes overlarge area production easily, is not subjected to the restriction of area shape in the use.Polymer weight is light, can obtain very high power-weight ratio as cell substrate, and can be crooked arbitrarily.These advantages help solar cell in various application of special occasions such as satellite, spacecraft, space station, space orientation balloons.
Compare with the hard substrates silicon-based thin film solar cell, flexible substrate silicon based thin film solar battery can significantly improve power-weight ratio.Cause preparation technology's change to introduce a lot of problems owing to change substrate, wherein back electrode metallic aluminium atomic heat diffusion problem is particularly outstanding.Because of metallic aluminium is more active, when preparation multilayer silica-base film, metallic aluminium can diffuse into battery main body, causes the relatively poor or no-output of battery output.Usually the method that solves is to add one deck barrier layer (Lr) between metal back electrode aluminium and N type silica-base film, and generally the transparent conductive material zinc-oxide film is adopted on this barrier layer.But undesirable because of zinc oxide material and flexible substrate material stress coupling, caused that thin film solar cell is local be full of cracks to be occurred even come off, influenced the output characteristic and the uniformity of battery.
The principle of selective oxidation zinc barrier layer substitution material is can not influence the effect that the back electrode metallic aluminium plays projected current when stoping the diffusion of back electrode metallic aluminium.Stop the diffusion of back electrode metallic aluminium will select the material of performance rock-steady structure densification, and should select work function and the approaching material of metallic aluminium, can reduce contact berrier like this and be beneficial to carrier transport.In the theory analysis, also should consider to operate the possibility of realization.
Summary of the invention
The purpose of this invention is to provide barrier layer of a kind of flexible substrate film solar battery and preparation method thereof, can prevent that the back electrode metallic aluminium from diffusing into battery main body in the process of preparation battery, preparation one deck barrier layer between back electrode and battery silica-base film, do not influence reflection of incident light, increase the effect of its light path in the absorbed layer in battery, can also guarantee battery good output characteristics and uniformity.
The present invention also aims to provide a kind of flexible substrate film solar battery.
The barrier layer of flexible substrate film solar battery provided by the invention is metal nickel dam or layer of titanium metal, and the thickness on barrier layer is 30-50nm.
Flexible substrate film solar battery primary structure provided by the invention comprises flexible substrate, metal back electrode aluminium, metal nickel dam or layer of titanium metal barrier layer, N type silica-base film, I type silica-base film, P type silica-base film and transparent conductive oxide film.
Described N type silica-base film comprises N type microcrystalline hydrogenated silicon or N type amorphous silicon hydride;
Described I type silica-base film comprises I type microcrystalline hydrogenated silicon, I type amorphous silicon hydride or I type silane germanium alloy;
Described P type silica-base film comprises P type microcrystalline hydrogenated silicon, P type amorphous silicon hydride or P type silicon-carbon hydride alloy;
Described transparent conductive oxide film comprises Al-Doped ZnO, tin ash or transparent conductive film of In-Sn oxide;
Described flexible substrate material comprises stainless steel foil, polyimides or other organic polymer material.
The preparation method of thin-film solar battery barrier with flexible substrate of the present invention is:
1) flexible substrate behind the cleaning, drying is put into coating machine, be evacuated to 1.0 * 10
-3Pa opens the power supply of hanging the aluminium wire electrode, slowly improves transformer output voltage to 150 volt, and this moment, aluminium wire fusing evaporation transferred to zero with transformer after three minutes, and powered-down is prepared the back electrode metallic aluminium;
2) coating machine is evacuated to 1.0 * 10
-3Pa opens the power supply of hanging nickel wire electrode or titanium silk electrode, slowly improves transformer output voltage to 175 volt, and this moment, nickel wire fusing evaporation or titanium silk partly distilled, and after 30 seconds transformer were transferred to zero, powered-down, and take out the cooling back.
The preparation method of flexible substrate film solar battery of the present invention adopts radio frequency plasma to strengthen chemical vapour deposition (CVD) (RF-PECVD), very high frequency plasma enhancing chemical vapour deposition (CVD) (VHF-PECVD), hot-wire chemical gas-phase deposition (HW-CVD) or catalysis+very high frequency plasma to strengthen chemical vapour deposition (CVD) methods such as (Cat+VHF-PECVD), in corresponding system, decompose silane, phosphine, germane, borine, methane and hydrogen, according to the sequential aggradation silicon-based thin film solar cell main body of N-I-P.
The barrier layer of flexible substrate film solar battery of the present invention also can be used in hard transparent substrate silicon based thin film solar battery or the compound film solar cell.
The present invention is deposition layer of metal nickel or a titanium film between metal back electrode aluminium and N type silica-base film, replace zinc-oxide film as the barrier layer, this barrier layer can stop metal back electrode aluminium to diffuse into battery main body, simultaneously do not influence back electrode, increase the effect of its light path in battery obsorbing layer reflection of incident light.Adopt thermal evaporation to prepare barrier metal nickel or titanium, after preparation metal back electrode aluminium, in same coating machine, prepare, can avoid air oxidation and contaminating impurity.
The grid line extraction pole of the back electrode of hard transparent substrate silicon based thin film solar battery and compound film solar cell also adopts metallic aluminum material, has the problem of aluminium diffusion equally.This invention also is applicable to hard transparent substrate silicon based thin film solar battery and compound film solar cell, prepares one deck barrier metal nickel or titanium before the above-mentioned metal aluminium electrode of preparation earlier.
Flexible substrate solar battery barrier provided by the invention, can prevent that the back electrode metallic aluminium from diffusing into battery main body in the process of preparation battery, preparation one deck barrier layer between back electrode and battery silica-base film, do not influence reflection of incident light, increase the effect of its light path in battery obsorbing layer, can also guarantee battery performance, significantly improve the output characteristic and the uniformity of flexible substrate reversed structure thin film solar cell.
Description of drawings
Fig. 1: the flexible substrate silicon based thin film solar battery structural representation that comprises barrier layer of the present invention.
Fig. 2: the present invention is used for hard substrates silicon-based thin film solar cell structural representation.
Fig. 3: zinc oxide is as the output characteristic of barrier layer flexible substrate silicon based thin film solar battery.
Fig. 4: metallic nickel is as the output characteristic of barrier layer flexible substrate silicon based thin film solar battery.
Fig. 5: Titanium is as the output characteristic of barrier layer flexible substrate silicon based thin film solar battery.
Embodiment:
Describe with reference to the accompanying drawings as follows:
As shown in the figure, 1. substrate comprises flexible substrate polyimides, stainless steel foil and hard transparent substrate glass; 2. metal electrode aluminium; 3. barrier layer; 4.N type silica-base film layer; 5.I type silica-base film layer; 6.P type silica-base film layer; 7. transparent conductive film comprises zinc oxide, tin ash or transparent conductive film of In-Sn oxide.
Cleaning method routinely as heating, ultrasonic, rub method such as wipe away and clean flexible substrate.With clean, flexible substrate after the oven dry (polyimides, 50 microns) puts in the coating machine (DM-300B type, Beijing instrument plant produces), this coating machine is equipped with two groups of tungsten filament electrodes, middlely isolates with baffle plate, avoids mutual pollution.Hang aluminium wire 0.368 gram on one group of tungsten filament therein, on another group tungsten filament, hang nickel wire 0.034 gram or titanium silk 0.066 gram.Be evacuated to 1.0 * 10
-3Pa opens the power supply of hanging the aluminium wire electrode, slowly improves transformer output voltage to 150 volt, aluminium wire fusing evaporation this moment.After three minutes transformer is transferred to zero, powered-down.Be evacuated to 1.0 * 10
-3Pa opens the power supply of hanging nickel wire or titanium silk electrode, slowly improves transformer output voltage to 175 volt, and this moment, nickel wire fusing evaporation or titanium silk partly distilled.After 30 seconds transformer is transferred to zero, powered-down is treated substrate cooling back taking-up, and the thickness on barrier layer is 30-50nm.Cooled substrate is put into the preparation N-I-P of plasma enhanced chemical vapor deposition (RF-PECVD) system thin film solar cell main body.
Described tungsten filament is that helical form is mixed aluminium, and diameter is 1.5 millimeters.Described aluminium wire purity 99.995%, weight are 0.368 gram.Described nickel wire purity 99.995%, weight are 0.034 gram.Described titanium silk purity 99.999%, weight are 0.066 gram, and are repeatedly used.
The thickness on barrier layer is tested with the step instrument, and thickness is 30-50nm.
Embodiment 1:
Flexible substrate film solar battery structure such as Fig. 1, the key step of battery main body preparation is as follows:
The polyimides flexible substrate with metal aluminium electrode, metallic nickel (nickel layer thickness is about 40nm) or Titanium barrier layer for preparing is put into plasma reinforced chemical vapor deposition system, this substrate is heated to 160-180 ℃, and constant temperature 2 hours; Respectively at different three reative cell depositions N, I, three layers of silica-base film of P.Wherein N chamber reacting gas is silane, phosphine and hydrogen, and reaction power is 28W, the about 30nm of thickness; I chamber reacting gas is silane, germane and hydrogen, and reaction power is 8W, the about 500nm of thickness; P chamber reacting gas is silane, borine, methane and hydrogen, and reaction power is 30W, the about 20nm of thickness.After three layers of silica-base film deposition finished, temperature was reduced to room temperature solar cell is taken out from plasma reinforced chemical vapor deposition system, preparation Al-Doped ZnO, tin ash or transparent conductive film of In-Sn oxide.
Fig. 4: metallic nickel is as the output characteristic of barrier layer flexible substrate silicon based thin film solar battery.
Fig. 5: Titanium is as the output characteristic of barrier layer flexible substrate silicon based thin film solar battery.
The thin film solar cell the key technical indexes has: short circuit current Jsc, open circuit voltage Voc, fill factor, curve factor FF, conversion efficiency Eft.Utilize the amount of radiation of a standard sun of solar simulator simulation that thin film solar cell is effectively shone, the voltage-current characteristic of testing film solar cell output calculates above-mentioned solar cell the key technical indexes by volt-ampere characteristic.
Embodiment 2:
Transparent hard substrates thin-film solar cell structure such as Fig. 2, the key step of battery main body preparation is as follows:
The hard transparent substrate that will have transparent conductive film is put into plasma reinforced chemical vapor deposition system, deposits P, I, three layers of silica-base film of N respectively, and experiment condition is with embodiment 1.After being cooled to room temperature solar cell is taken out from plasma reinforced chemical vapor deposition system, put into coating machine plated metal nickel or Titanium barrier layer, plated metal aluminium subsequently, experiment condition is with embodiment 1, and difference is a first plated metal nickel or titanium barrier layer plated metal aluminium again.Take out after waiting to lower the temperature, the thickness on barrier layer is about 45nm.
Claims (5)
1, a kind of barrier layer of flexible substrate film solar battery is characterized in that it is metal nickel dam or layer of titanium metal, and the thickness on barrier layer is 30-50nm.
2, a kind of thin film solar cell that comprises the described barrier layer of claim 1, it is characterized in that it mainly comprises flexible substrate, metal back electrode aluminium, metal nickel dam or layer of titanium metal barrier layer, N type silica-base film, I type silica-base film, P type silica-base film and transparent conductive oxide film, above-mentioned film is by the preparation that superposes successively of thermal evaporation, chemical vapour deposition technique, magnetron sputtering method;
Described N type silica-base film is N type microcrystalline hydrogenated silicon or N type amorphous silicon hydride;
Described I type silica-base film is I type microcrystalline hydrogenated silicon, I type amorphous silicon hydride or I type silane germanium alloy;
Described P type silica-base film is a P type microcrystalline hydrogenated silicon, P type amorphous silicon hydride or P type silicon-carbon hydride alloy;
Described transparent conductive oxide film is Al-Doped ZnO, tin ash or transparent conductive film of In-Sn oxide;
Described flexible substrate material is stainless steel foil, polyimides or other organic polymer material.
3, the preparation method on the described barrier layer of claim 1 is characterized in that through following step:
1) flexible substrate behind the cleaning, drying is put into coating machine, be evacuated to 1.0 * 10
-3Pa opens the power supply of hanging the aluminium wire electrode, slowly improves transformer output voltage to 150 volt, and this moment, aluminium wire fusing evaporation transferred to zero with transformer after three minutes, and powered-down is prepared the back electrode metallic aluminium;
2) coating machine is evacuated to 1.0 * 10
-3Pa opens the power supply of hanging nickel wire electrode or titanium silk electrode, slowly improves transformer output voltage to 175 volt, and this moment, nickel wire fusing evaporation or titanium silk partly distilled, and after 30 seconds transformer were transferred to zero, powered-down, and take out the cooling back.
4, the preparation method of the described thin film solar cell of claim 2, it is characterized in that it is to strengthen chemical vapour deposition (CVD) (RF-PECVD), very high frequency plasma enhancing chemical vapour deposition (CVD) (VHF-PECVD), hot-wire chemical gas-phase deposition (HW-CVD) or catalysis+very high frequency plasma through radio frequency plasma to strengthen chemical vapour deposition (CVD) (Cat+VHF-PECVD) method decomposing silane, phosphine, germane, borine, methane and hydrogen in the system accordingly, according to the sequential aggradation silicon-based thin film solar cell main body of N-I-P.
5, the application on the described barrier layer of claim 1 is characterized in that being used for flexible substrate film solar battery, hard transparent substrate silicon based thin film solar battery or compound film solar cell.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101257056B (en) * | 2008-04-07 | 2010-06-16 | 南开大学 | Flexible substrate silicon based thin film solar battery |
| CN101894888A (en) * | 2010-07-16 | 2010-11-24 | 山东力诺太阳能电力股份有限公司 | Solar cell manufacturing process for blocking back diffusion by using mask |
| CN102142469A (en) * | 2010-12-01 | 2011-08-03 | 南开大学 | P type microcrystalline silicon carbon film material for PI flexible substrate solar cell and preparation |
| CN102312530A (en) * | 2010-07-07 | 2012-01-11 | 鸿富锦精密工业（深圳）有限公司 | Integrated solar energy tile and manufacturing method thereof |
| CN102623544A (en) * | 2011-01-27 | 2012-08-01 | Ntt电子股份有限公司 | Optical semiconductor device |
| CN103733350A (en) * | 2011-06-10 | 2014-04-16 | Posco公司 | Solar cell substrate, method for manufacturing same, and solar cell using same |
| CN104124310A (en) * | 2014-08-12 | 2014-10-29 | 北京四方继保自动化股份有限公司 | Preparation method of flexible CIGS (Copper Indium Gallium Selenide) film solar battery barrier layer |
| CN106057928A (en) * | 2016-07-27 | 2016-10-26 | 华南理工大学 | Stainless steel flexible substrate copper-indium-gallium-selenium thin-film solar cell capable of blocking spread of iron effectively and preparation method thereof |
| CN110614550A (en) * | 2018-06-20 | 2019-12-27 | 北京铂阳顶荣光伏科技有限公司 | Mechanical polishing method, device and system for stainless steel substrate and solar thin film battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003051606A (en) * | 2001-06-01 | 2003-02-21 | Daido Steel Co Ltd | Substrate for thin film formation |
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2005
- 2005-12-22 CN CNB2005101225291A patent/CN100373635C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101257056B (en) * | 2008-04-07 | 2010-06-16 | 南开大学 | Flexible substrate silicon based thin film solar battery |
| CN102312530A (en) * | 2010-07-07 | 2012-01-11 | 鸿富锦精密工业（深圳）有限公司 | Integrated solar energy tile and manufacturing method thereof |
| CN101894888A (en) * | 2010-07-16 | 2010-11-24 | 山东力诺太阳能电力股份有限公司 | Solar cell manufacturing process for blocking back diffusion by using mask |
| CN102142469A (en) * | 2010-12-01 | 2011-08-03 | 南开大学 | P type microcrystalline silicon carbon film material for PI flexible substrate solar cell and preparation |
| CN102623544A (en) * | 2011-01-27 | 2012-08-01 | Ntt电子股份有限公司 | Optical semiconductor device |
| US8916946B2 (en) | 2011-01-27 | 2014-12-23 | Nippon Telegraph And Telephone Corporation | Optical semiconductor device |
| CN103733350A (en) * | 2011-06-10 | 2014-04-16 | Posco公司 | Solar cell substrate, method for manufacturing same, and solar cell using same |
| CN104124310A (en) * | 2014-08-12 | 2014-10-29 | 北京四方继保自动化股份有限公司 | Preparation method of flexible CIGS (Copper Indium Gallium Selenide) film solar battery barrier layer |
| CN106057928A (en) * | 2016-07-27 | 2016-10-26 | 华南理工大学 | Stainless steel flexible substrate copper-indium-gallium-selenium thin-film solar cell capable of blocking spread of iron effectively and preparation method thereof |
| CN110614550A (en) * | 2018-06-20 | 2019-12-27 | 北京铂阳顶荣光伏科技有限公司 | Mechanical polishing method, device and system for stainless steel substrate and solar thin film battery |
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| CN100373635C (en) | 2008-03-05 |
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