CN101236997A - Back contact layer of film silicon solar battery - Google Patents
Back contact layer of film silicon solar battery Download PDFInfo
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- CN101236997A CN101236997A CNA2007100025738A CN200710002573A CN101236997A CN 101236997 A CN101236997 A CN 101236997A CN A2007100025738 A CNA2007100025738 A CN A2007100025738A CN 200710002573 A CN200710002573 A CN 200710002573A CN 101236997 A CN101236997 A CN 101236997A
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- Y02E10/548—Amorphous silicon PV cells
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Abstract
The invention discloses a novel design proposal of a thin film silicon solar cell back contact layer. In order to resolve the problems of diffluence and instability of a high reflectivity double thin film back contact layer of zinc oxide or silver in a thin film hydrogenation silicon solar cell and avoid the phenomenon of mutual diffusion of silver and aluminium in the zinc oxide or a silver or an aluminum back contact layer. The novel design proposal for thin film silicon solar cell back contact layer inserts a barrier layer between silver and aluminium, in order to provide a structure with high reflectivity and stability for the zinc oxide or the silver or the zinc oxide or the aluminum back contact layer in the practical photovoltaic application.
Description
Technical field
The invention belongs to photoelectricity equipment field, specially refer to hydrogenated silicon film by utilizing photoelectric device technology.
Background technology
Back contact is for the solar cell (also being called film photovoltaic or photoelectric device) of based thin film amorphous silicon hydride and nanocrystal silicon, especially it is important that the high-performance of large tracts of land photovoltaic module and reliability cause the pass, and wherein catching luminous energy power efficiently is indispensable factor for catching weak absorbing light.The effective reflective characteristic of back contact directly reflects back nonabsorbable light.Reflection is preferably carried out with a very big angle (diffuse transmission type), and light can directly enter in the silicon absorber and form photoelectric current like this.
In the laboratory, obtained efficient good film amorphous silicon and nanocrystal silicon (nano-silicon) solar cell.This solar cell uses transparent conductive oxide film and reflective metallic film, preferably with zinc oxide and silver (ZnO/Ag) as back contact.Yet the cooperation of this ZnO/Ag can produce serious negative issue.Thick silver layer can cause tangible shunting, and shunting can cause energy transformation ratio low again, thereby causes the output of photovoltaic module low.As time goes on, silver can lose the gloss of itself, and the reflecting power of the back contact that ZnO/Ag makes will reduce.The diffusivity of silver self is very strong, and this has influenced the useful life of photovoltaic module (along with silver is penetrated into silicon layer, can produce shunting gradually).At last, compare with aluminium, silver is a kind of invaluable metal.So the consumption of restriction silver helps to reduce the production cost of photovoltaic module.
When the back contact of ZnO/Ag was used for solar cell at first, people used thicker silicon layer.Because silicon thin film thicker (such as in three node solar batteries and photovoltaic module) is not obvious by the branch flow problem that silver causes.Yet in order to produce more stable photovoltaic module, photovoltaic module of today is used thin silicon thin film instead.When using ZnO/Ag (perhaps simple silver), just be easy to produce the problem of shunting like this as the back electrode material.Even it is found that the diode for small size, ZnO/Ag electrically contacts also to electrically contact than ZnO/Al and more is easy to generate the branch flow problem.Current production comprises amorphous silicon, and during the photovoltaic module of the based thin film silicon of amorphous silicon germanium alloy nano crystal silicon, ZnO/Al is the standard material of people's general choice.Different with ZnO/Ag, the back contact that ZnO/Al makes not only is difficult for causing shunting, even and produce the branch flow problem also than being easier to solve (by so-called " shunting weakens " program).We set forth this problem by a large amount of experiments, and other research has also been done relevant report to this problem with establishment.Under most of situation, use the photovoltaic module of the back contact of ZnO/Ag, lower than the photovoltaic module energy transformation ratio that uses the ZnO/Al back contact.This is that the increase of closed current has been filled the factor (and open circuit voltage) and has offset because when using ZnO/Ag as back contact.ZnO/Al is a kind of back contact material very reliably, but compares with ZnO/Ag, and its reflecting power is far short of what is expected.
In theory, ZnO/Ag can make compound back contact with other metal and/or the combination of metal oxide rete, ZnO/Ag/X, and wherein X is " protection " conductive layer, keeps stable rete (the discord silver hair is given birth to reaction) in other words conj.or perhaps.In the ZnO/Ag/X structure, a relatively thin silver layer (for example, 500
Perhaps still less) be sandwiched between zinc oxide and the X.The purpose of doing like this is when relating to laser treatment and electric machining, the part that allows ZnO/Ag extend as hydrogen amorphous silicon n layer." protection " rete X must satisfy following several condition: such as conductivity to be arranged, the shunting inhibitory action be arranged, and bonding but diffusion inside can not take place with silver.In the back contact of ZnO/Ag/X, ZnO/Ag should dominate optical property rather than the electric property that electrically contacts, and so just can make with silver-colored relevant shunting to minimize.The X layer should auxiliary electrical contact, help it to reduce the shunting that causes in intrinsic and the processing procedure.Because silver layer is added between zinc oxide and the X, the residual easy removing of drawn area silver, the laser grooving and scribing method is cleaner.So new method has solved the problem that the simple back contact of traditional Z nO/Ag type exists.We are (selecting very many) when during as the back contact material, not producing shunting action to module with X itself to the choice criteria of X.
According to the QE of small size solar cell test, compare with ZnO/Al, the back contact closed current that ZnO/Ag/X makes bigger (~ 3-5%).This mainly is because silver is higher to the reflectivity of ruddiness than aluminium.People find that also the efficient of the back contact module that ZnO/Ag/X makes is higher, may be because the non-equilibrium property of hydrogenated amorphous SiGe back of the body contact closed current is better, thereby cause fill factor, curve factor higher.
Summary of the invention
Based on above-mentioned consideration, the applicant has worked out purpose of the present invention: provide a kind of novel back contact that is applicable to thin film silicon solar cell, to improve photoelectric conversion efficiency.
Further purpose of the present invention is to use novel back contact to have the solar cell stability based on hydrogenated silicon film by utilizing of high conversion efficiency with improvement.
In order to reach the foregoing invention purpose, the present invention attempts to revise the back contact that traditional Z nO/Ag makes, and makes its shunt effect littler, keeps the advantage of ZnO/Ag high reflecting rate simultaneously, thereby increases the closed current of module, raises the efficiency.Basic is intended that by reducing silver-colored thickness and limiting " distributary phenomenon " with the auxiliary ZnO/Ag (thin Ag layer) of other conduction contact materials.Significantly selecting is exactly ZnO/Ag/Al, (Ag＜1,000 wherein
In simple ZnO/Ag electrically contacts, be approximately～2,000
Yet this combination can not be worked well.Because through high temperature (140-200 ℃) annealing the time, diffusion inside can take place in silver and aluminium.The reflecting ratio ZnO/Ag of ZnO/Ag/Al and ZnO/Al are poor like this.If the rete (~ hundreds of of zinc oxide
Be inserted between silver and the aluminium as a diffusion barrier, the back contact of the such MULTILAYER COMPOSITE of ZnO/Ag/ZnO/Al just can be brought into play its optics and electrical characteristic well, and stability and reliability are well arranged.In addition, thus can be in the same sputtering equipment large-area sputter of all retes realizes higher relatively output.Our the initial experimental data about module efficiency in the ZnO/Ag/X type back contact and branch Flow Behavior aspect is very gratifying, and wherein X is the TCO/Al duplicature.
The present invention adopts the multilayer back contact pattern of silver and aluminium, thereby has kept ZnO/Ag and ZnO/Al type back contact advantage separately well, has avoided their shortcoming.The present invention combines the higher reflecting rate of silver and the robustness of aluminium.The light reflection only needs very thin silver layer (less than 50 nanometers), it is found that such thin layer (for example 30 nanometers), more stable compared with thicker silver-colored thin layer (such as the thickness that uses in traditional ZnO/Ag back contact silver-colored thin layer between 150 and 250 nanometers), shunt effect also greatly reduces.
The more important thing is, compared with simple ZnO/Ag back contact (wherein the thickness of silver layer be～2000
Or 200 nanometer), it is so not serious that the branch flow problem of large-area module becomes after having used the compound back contact of ZnO/Ag/X.With different as the module of back contact with ZnO/Ag, major part has the photovoltaic module of ZnO/Ag/X back contact not have distributary phenomenon, perhaps has only faint distributary phenomenon.Though the compound back contact of the ZnO/Ag/X type still back contact shunt effect than ZnO/Al type is strong, compared with traditional ZnO/Ag type back contact, its shunt effect has weakened greatly.Therefore, for the production of module, the compound back contact of ZnO/Ag/X is a very promising potential procedure.In our discussion, X generally is ZnO/Al, but also may be other metallic film or transparent conductive oxide/metal or metal/metal.
The shunt effect of the back contact of ZnO/Ag/ZnO/Al type is little, and is functional, possesses the advantage of ZnO/Ag type back contact.General composition form is ZnO/Ag/X/Al, and wherein X represents a barrier layer, and it is zinc oxide in the above example.Barrier layer between this silver and the aluminium only needs 10 to 30 nanometer thickness just can be very effective, though thicker zinc-oxide film can be more strong.In this patent, zinc oxide refers to the zinc oxide of aluminium doping type, is in order to make it that stronger conductivity be arranged like this.Certainly, other transparent conductive oxide also can be used as the X (diffusion impervious layer) of ZnO/Ag/X/Al type back contact, for example (ITO) and the suitably SnO of doping
2
The back contact of the MULTILAYER COMPOSITE that other is similar can be made of reflectance height, the large tracts of land based on silane that conductivity is strong, high performance photovoltaic module.The extension of above-mentioned notion comprises: ZnO/Ag/Ni, ZnO/Ag/NiV, ZnO/Ag/Ti or ZnO/Ag/Cr.This back contact is structurally simpler than ZnO/Ag/ZnO/Al, but the conductivity of these alternative metals is not as aluminium.The Stability Analysis of Structures that these electrically contact, reflectance is better, can deposit simply by traditional filming equipment and program.
Description of drawings
The present invention will be further described below in conjunction with drawings and Examples.
Accompanying drawing is the structure of solar cell of the use ZnO/Ag/ZnO/Al type back contact of a based thin film silicon.
Embodiment
For interior doping (spreading the in other words) problem that solves in the back contact silver and aluminium, we have embedded diffusion barrier (zinc oxide) between silver and aluminium lamination.As shown in drawings, a structure of using p-i-n type thin film silicon unijunction solar cell of the present invention comprises following part successively: glass substrate 1, the preceding contact layer (tin oxide) 2 of electrically conducting transparent, based on the photovoltaic cells 8 that constitutes by p layer, i layer and n layer of hydrogenated silicon film by utilizing with by the back contact that plural layers constitute, comprise first zinc-oxide film 22, silver-colored film 45, second zinc-oxide film 32 and aluminium film 55.The wherein silver-colored film 45 and second zinc-oxide film 32 all are extremely thin films, and their thickness is about tens of microns.A concrete example is, the thickness of this ZnO/Ag (approaching)/ZnO (approaching)/each film of Al (thick) back contact is respectively 100 nanometers, 50 nanometers, 10 nanometers and 200 nanometers, the silver-colored film 45 of 50 nanometer thickness is enough to provide the light reflective that is similar to extremely thick silver-colored film, and second zinc-oxide film 32 that has only 10 nanometer thickness does not have the phenomenon of phase counterdiffusion yet between sufficient to guarantee silver and the aluminium film.The back contact of this ZnO/Ag (approaching)/ZnO (approaching)/Al (thick) combined type can effectively be used in the multijunction solar cell that is formed by stacking by a plurality of p-i-n type photovoltaic cells equally.
The large-area vacuum film plating process of all available maturation of each film in the back contact of the present invention forms under lower temperature with two-forty, so the present invention has good industrial prospect.
Claims (8)
1. film photoelectric device comprises:
A) the preceding electric contacting layer of an electrically conducting transparent, this preceding electric contacting layer comprises the transparent conductive oxide as doped tin oxide or doping type zinc oxide, comprises the tin oxide (SnO that fluorine mixes
2: F) and the zinc oxide (ZnO:Al) that mixes of aluminium;
B) a single p-i-n type photovoltaic element or a plurality of p-i-n type photovoltaic element that overlaps comprise p type, intrinsic i type and n N-type semiconductor N film based on silane;
C) reflective conduction back of the body electric contacting layer is characterized in that: comprise successively:
I. a transparent conductive oxide film comprises the zinc oxide (ZnO:Al) that aluminium mixes;
Ii. silver-colored film, its thickness is less than 60 nanometers;
Iii. a diffusion barrier film has good electrical conductivity, comprises the zinc oxide (ZnO:Al) that aluminium mixes, and its thickness is no more than 50 nanometers;
Iv. aluminium film, its thickness is greater than 100 nanometers.
2. film photoelectric device according to claim 1 is characterized in that: described film photoelectric device is in parallel with one or more other photoelectric devices or be cascaded, and forms a photoelectric device that power output is bigger.
3. film photoelectric device according to claim 1 is characterized in that: the thin layer of p-i-n type film photoelectric device is made of different silicon and silicon alloy film, and the structure of these films is noncrystal, nanocrystal, mixed-phase or allosome atomic structure.
4. film photoelectric device according to claim 1 is characterized in that: described aluminium film is substituted by one or more other metallic films, as nickel, and copper, the metal material that gold is such or the alloy of conduction.
5. film photoelectric device according to claim 1 is characterized in that: this film photoelectric device is placed on hard substrate or the flexible substrate.
6. film photoelectric device according to claim 1 is characterized in that: described transparent conductive oxide film or diffusion barrier film have chemical composition heterogeneous.
7. film photoelectric device according to claim 1 is characterized in that: described transparent conductive oxide film or diffusion barrier film have thickness heterogeneous.
8. film photoelectric device according to claim 1 is characterized in that: described diffusion barrier film is made of one or several transparent conductive metal oxides, comprises gallium or boron doped zinc oxide, tin oxide, titanium oxide and tin indium oxide (ITO).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100025738A CN101236997A (en) | 2007-01-29 | 2007-01-29 | Back contact layer of film silicon solar battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100025738A CN101236997A (en) | 2007-01-29 | 2007-01-29 | Back contact layer of film silicon solar battery |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101800262A (en) * | 2008-08-21 | 2010-08-11 | 应用材料股份有限公司 | Solar cell substrates and methods of manufacture |
| CN102024857A (en) * | 2010-10-28 | 2011-04-20 | 杭州天裕光能科技有限公司 | Back electrode for thin film solar cell |
| CN102484149A (en) * | 2009-09-04 | 2012-05-30 | 三菱电机株式会社 | Solar battery and method of manufacturing the same |
| CN102779944A (en) * | 2012-08-06 | 2012-11-14 | 上海电力学院 | Transparent conductive thin film and preparation method thereof |
| CN102800742A (en) * | 2011-05-27 | 2012-11-28 | 苏州阿特斯阳光电力科技有限公司 | Method for manufacturing back contact crystalline silicon solar battery piece |
| CN103069578A (en) * | 2010-10-05 | 2013-04-24 | Lg伊诺特有限公司 | Photovoltaic device and method for manufacturing same |
| CN103151394A (en) * | 2012-12-14 | 2013-06-12 | 广东志成冠军集团有限公司 | Thin-film solar cell and manufacture method thereof |
| WO2020015021A1 (en) * | 2018-07-16 | 2020-01-23 | 南通天盛新能源股份有限公司 | Preparation method for back electrode of solar cell and application |
| CN111276553A (en) * | 2015-11-24 | 2020-06-12 | 日立化成株式会社 | Method of forming a solar cell with a sintered multilayer thin film stack |
| WO2020252827A1 (en) * | 2019-06-19 | 2020-12-24 | 南通天盛新能源股份有限公司 | Method for fabricating p-type crystalline silicon back electrode |
-
2007
- 2007-01-29 CN CNA2007100025738A patent/CN101236997A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101800262A (en) * | 2008-08-21 | 2010-08-11 | 应用材料股份有限公司 | Solar cell substrates and methods of manufacture |
| CN102484149B (en) * | 2009-09-04 | 2015-06-10 | 三菱电机株式会社 | Solar battery and method of manufacturing the same |
| CN102484149A (en) * | 2009-09-04 | 2012-05-30 | 三菱电机株式会社 | Solar battery and method of manufacturing the same |
| CN103069578B (en) * | 2010-10-05 | 2016-08-10 | Lg伊诺特有限公司 | Photovoltaic device and manufacture method thereof |
| CN103069578A (en) * | 2010-10-05 | 2013-04-24 | Lg伊诺特有限公司 | Photovoltaic device and method for manufacturing same |
| CN102024857A (en) * | 2010-10-28 | 2011-04-20 | 杭州天裕光能科技有限公司 | Back electrode for thin film solar cell |
| CN102800742A (en) * | 2011-05-27 | 2012-11-28 | 苏州阿特斯阳光电力科技有限公司 | Method for manufacturing back contact crystalline silicon solar battery piece |
| WO2012162903A1 (en) * | 2011-05-27 | 2012-12-06 | 苏州阿特斯阳光电力科技有限公司 | Method for manufacturing back contact crystalline silicon solar battery piece |
| CN102800742B (en) * | 2011-05-27 | 2016-04-13 | 苏州阿特斯阳光电力科技有限公司 | Back contacts crystal silicon solar cell sheet manufacture method |
| CN102779944B (en) * | 2012-08-06 | 2015-04-15 | 上海电力学院 | Transparent conductive thin film |
| CN102779944A (en) * | 2012-08-06 | 2012-11-14 | 上海电力学院 | Transparent conductive thin film and preparation method thereof |
| CN103151394A (en) * | 2012-12-14 | 2013-06-12 | 广东志成冠军集团有限公司 | Thin-film solar cell and manufacture method thereof |
| CN111276553A (en) * | 2015-11-24 | 2020-06-12 | 日立化成株式会社 | Method of forming a solar cell with a sintered multilayer thin film stack |
| WO2020015021A1 (en) * | 2018-07-16 | 2020-01-23 | 南通天盛新能源股份有限公司 | Preparation method for back electrode of solar cell and application |
| US11791425B2 (en) | 2018-07-16 | 2023-10-17 | Nantong T-Sun New Energy Co., Ltd. | Preparation method for solar cell back electrode and application thereof |
| WO2020252827A1 (en) * | 2019-06-19 | 2020-12-24 | 南通天盛新能源股份有限公司 | Method for fabricating p-type crystalline silicon back electrode |
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Open date: 20080806 |