CN103035752B - Crystal silicon solar energy battery comprising nanometer structure antireflection film and preparation method thereof - Google Patents

Crystal silicon solar energy battery comprising nanometer structure antireflection film and preparation method thereof Download PDF

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CN103035752B
CN103035752B CN201310029855.2A CN201310029855A CN103035752B CN 103035752 B CN103035752 B CN 103035752B CN 201310029855 A CN201310029855 A CN 201310029855A CN 103035752 B CN103035752 B CN 103035752B
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film
crystal silicon
tio
layer
silicon solar
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CN103035752A (en
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张宇翔
朱煜
黄寓洋
宋贺伦
张耀辉
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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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
    • 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

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Abstract

A kind of crystal silicon solar energy battery comprising nanometer structure antireflection film, including metal back surface field from bottom to top and back electrode, single crystal silicon substrate, PN junction active layer, anti-film and gate electrode, it is characterized in that, if described anti-film has dried layer, the refractive index of anti-film from bottom to top is gradually reduced.Its preparation method is to use oblique angle incidence physical deposition methods, by adjusting incident angle and deposition material, generates the anti-film that multilayer refractive index is different.The present invention is greatly optimized the light of silicon solar cell and absorbs, thus improves battery efficiency.This method will not damage the photovoltaic property of silicon crystal itself, it is possible to really the light absorbed is converted into electric energy more.Improve phototranstormation efficiency, will greatly promote the development of solar battery product.

Description

Crystal silicon solar energy battery comprising nanometer structure antireflection film and preparation method thereof
Technical field
The present invention relates to a kind of way improving silicon solar cell transformation efficiency, particularly comprise nanostructured Crystal silicon solar energy battery of anti-film and preparation method thereof, belongs to semi-conducting material application.
Background technology
The principal element affecting solar battery efficiency mainly includes optical loss and electricity loss.Wherein optics Loss mainly includes the shadow loss of battery front surface contact grid line, the reflection loss on surface and long-wave band Non-absorbing is lost. and during sunshine incidence, naked silicon face has the reflectivity of up to more than 30%, and this can be greatly increased The optical loss of battery.It is common that the silicon chip surface texturing that the silicon nitride passivation of individual layer and soda acid are carried out combines Industrial production method, but this anti-film is only at the narrowest spectral region and the least angular range Interior can reflectivity drop ratio is relatively low.In recent years, the anti-film of sub-wavelength Fabrication of nanostructures causes and more comes The most concerns.The characteristic of this structure be can realize in wide spectral range and the biggest angular range extremely low Reflectivity.But what the main needs of this method solved is two aspect problems: on the one hand be method whether Compatible with existing silicon solar cell flow process, two be the cost of this method how.
Summary of the invention
The present invention provides a kind of crystal silicon solar comprising nanometer structure antireflection film electricity for overcoming above deficiency Pond, including metal back surface field from bottom to top and back electrode, single crystal silicon substrate, PN junction active layer, anti-film, And gate electrode, wherein, if described anti-film has dried layer, the refractive index of anti-film from bottom to top is gradually reduced.
Preferably, anti-film is the TiO of nanostructured2Film, or by TiO2Film and SiO2Film mixes.
Preferably, anti-film has 2 to 5 layers.
Preferably, the diameter of every layer of anti-film nanometer rods between 10-200nm, porosity 0.1-0.9 it Between.
Preferably, TiO2The reflectivity of film is between 2.7 to 1.3, SiO2The reflectivity of film is 1.46-1.05 Between.
Another object of the present invention also resides in, it is provided that a kind of comprise the crystalline silicon of nanometer structure antireflection film too The preparation method of sun energy battery, generates anti-film including oblique angle incidence physical deposition methods, it is characterised in that use If following methods is sequentially depositing dried layer anti-film on PN junction active layer:
Step 1: will fix containing the single crystal silicon substrate of PN junction active layer, adjust evaporation source incident direction with The deposition surface of PN junction active layer forms an oblique incident angle；
Step 2: at a temperature of 20-100 degree, with the speed of 0.1nm/s-1nm/s by TiO2Or SiO2Deposition Anti-film is formed on PN junction active layer.
Preferably, anti-film is the TiO of nanostructured2Film, or by TiO2Film and SiO2Film mixes.
Preferably, anti-film has 2 to 5 layers.
Preferably, the diameter of every layer of anti-film nanometer rods between 10-200nm, porosity 0.1-0.9 it Between；TiO2The reflectivity of film is between 2.7 to 1.3, SiO2The reflectivity of film is between 1.46-1.05.
Preferably, incident angle is between 10-89 degree.
The present invention uses the method for glancing angle deposition, and it is many that preparation this includes multilayer reflectivity gradual change The crystal silicon solar energy battery of hole nanometer structure antireflection film, the light being greatly optimized silicon solar cell absorbs, Thus improve battery efficiency.Other the most black silicon of typical nanometer technology or nanoporous silicon technology phase with some Ratio, this method will not damage the photovoltaic property of silicon crystal itself, it is possible to be really converted into by the light absorbed more Electric energy.Improve phototranstormation efficiency, will greatly promote the development of solar battery product.This preparation method is also Possess advantages below: 1) controlled to the technological process of production high flexible of nanostructured, the nanostructured that produced There is homogeneity and the reappearance of height；2) method is based on heat deposition plated film, is not limited by material. 3) technological process is simple, can one-time process flow process complete multilayer complexity ordered nano-structure such as column, S-shaped, The preparation of spirality, zigzag etc. produces, it is possible to achieve batch production, cost is the highest.4) with existing Other silicon solar cell techniques completely compatible, it is not necessary to extra equipment and cost.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention crystal silicon solar energy battery structural representation.
Fig. 2 is the structural representation of the nanometer structure antireflection film of embodiment of the present invention multilayer reflectivity gradual change.
Fig. 3 is the schematic diagram of embodiment of the present invention oblique angle incidence physical deposition method application.
Detailed description of the invention
Below in conjunction with accompanying drawing, by embodiment, the present invention is further described.
The purpose of the embodiment of the present invention is that the anti-film making nanostructured, to reduce reflectivity, improves the sun Can the electricity conversion of battery and this crystal silicon solar energy battery and preparation method are provided.This nano junction The anti-film of structure can realize extremely low reflectivity in the range of wide spectrum and extensive angle.The present embodiment uses oblique angle The method of incident physical deposition, technique is simple, and cost is relatively low, and technique and existing silicon solar cell stream Journey is completely compatible.
The above crystal silicon solar energy battery structure as it is shown in figure 1, be metal back surface field the most respectively with Back electrode 3, p type single crystal silicon matrix 1, N-type active layer 2, anti-film 4 and gate electrode 5, wherein, p-type Forming PN junction between single crystal silicon substrate 1 and N-type active layer 2, particularly, anti-film has multilayer, and The refractive index of each layer anti-film from bottom to top is gradually reduced.Generally anti-film is TiO2Film or SiO2Film, is shown in Fig. 2, be of five storeys anti-film respectively, i.e. a to e layer, and from bottom to top, ground floor a is refractive index 2.03 Nanostructured TiO2, second layer b is nanostructured TiO of refractive index 1.952, third layer c is that refractive index is Nanostructured TiO of 1.652, the 4th layer of d is the SiO of refractive index 1.262, layer 5 e is refractive index 1.05 SiO2, and, the diametric requirements of the nanometer rods of each layer is between 10-200nm, and porosity is at 0.1-0.9 Between.So, nanostructured porosity and refractive index are the most successively incremented by, and are greatly improved anti-reflective The effect of optimization of film, it is achieved thereby that wide spectrum and comprehensive anti-reflective of polarizers of big angle scope.Analyze based on above, Each layer anti-film can choose TiO2Single composition, or by TiO2And SiO2Two to the five layers of nanometer mixed Structural membrane, wherein TiO2Reflectivity be between 2.7 to 1.3, SiO2Reflectivity be 1.46-1.05 it Between.Wherein the nanostructured porosity of every layer of anti-film is the most successively successively decreased, thus refractive index also under Successively successively decrease on and, and be distributed between 1.05-2.7.
The preparation method of above example crystal silicon solar energy battery structure, sees Fig. 3, uses oblique angle incidence thing Reason sedimentation.Its principle is by controlling the incident direction formation relative to incident air flow of the substrate with PN junction , just there is certain hole at one angle of inclination between the nanometer column structure so formed.And each layer of anti-film Corresponding different inclination angle, the nanostructured porosity of the most each layer of anti-film is different.We use each layer The incidence angle that reflectivity is the most successively incremented by, then porosity is the most successively successively decreased, thus reflectivity The most successively successively decrease.In Fig. 31 is the single crystal silicon substrate containing PN junction active layer, and 6 is deposition Material, α is incidence angle, and 7 is the nano-pillar in anti-film microstructure.
Concrete operation step is: from bottom to top, and ground floor a anti-film deposition material is TiO2, working vacuum Spending and hold in the palm for 1e-6, incidence angle is 24 degree, is i.e. 24 degree of angles incident (lower same) with vertical line, and deposition velocity is 0.2nm/s, sedimentation time is 400s, and thickness is 80nm, and refractive index is 2.03.
Second layer b anti-film deposition material is TiO2, working vacuum degree is 1e-6 torr, and incidence angle is 39 degree, Deposition velocity is 0.2nm/s, and sedimentation time is 400s, and thickness is 80nm, and refractive index is 1.95.
Third layer c anti-film deposition material is TiO2, working vacuum degree is 1e-6 torr, and incidence angle is 64 degree, Deposition velocity is 0.2nm/s, and sedimentation time is 500s, and thickness is 100nm, and refractive index is 1.65.
4th layer of d anti-film deposition material is SiO2, working vacuum degree is 1e-6 torr, and incidence angle is reverse 68 Degree, deposition velocity is 0.4nm/s, and sedimentation time is 375s, and thickness is 150nm, and refractive index is 1.26.
Layer 5 e anti-film deposition material is SiO2, working vacuum degree is 1e-6 torr, and incidence angle is reverse 86 Degree, deposition velocity is 0.4nm/s, and sedimentation time is 575s, and thickness is 230nm, and refractive index is 1.05.
The cardinal principle of the present invention is, the method using oblique angle incidence physical deposition, relative by controlling substrate The material form at substrate surface deposition modeling is controlled in the angle of inclination of incident air flow and direction.For just Normal depositional mode, atom and molecule relatively evenly can deposit in whole plane, and when inclined deposition incident angle After, atom and molecule can be caused to assemble in certain direction tilted many, form a knot being similar to tree shade Structure, the time one is long, and the region under " tree shade " covers would not have atom and molecule to deposit, and " tree shade " then can be got over The longest, become the nanostructured of preiodic type.And every layer of material is used different oblique incidence angles, The porosity of different nanostructureds will be obtained.Periodically concrete dynamic modulus nanostructured, can make this layer of material The equivalent refractive index of material is lower than same orthodox material, and changes porosity, just makes refractive index in certain limit Interior lasting adjustable, reach our refractive index demand.Particularly, it is simply that use the most each layer by The incidence angle that layer is incremented by, then porosity is the most successively successively decreased, thus reflectivity is the most successively passed Subtract.The refractive index of traditional individual layer anti-film can only mate single wavelength and the least ranges of incidence angles, and this Bright this multilayer, the structure that every layer of refractive index is the most successively successively decreased, then can be greatly promoted anti-film Effect of optimization, it is achieved wide spectrum and comprehensive anti-reflective of polarizers of big angle scope.
The major advantage of oblique angle incidence physical deposition methods is that he overcomes other nano material and prepares growth technique Limitation.Such as, the usual step of chemical method is tediously long, to reaction condition (temperature, air pressure, acidity etc.) Require harshness.And the method apparatus expensive of (electron beams/laser bundle miniature carving) is etched based on template, at present cannot Mass produce.And incidence physical deposition law technology in oblique angle is to prepare highly controllable nanoaperture and receive The strong method of one of rice structural membrane.
The present embodiment is as a example by p type single crystal silicon matrix and N-type active layer, in like manner, it is also possible to be N-type monocrystalline The monocrystaline silicon solar cell structure of silicon substrate 1 and p-type active layer, its preparation method and the invention reached Effect is identical.
Although being that the present invention is described in detail with reference to its exemplary embodiment and shows above, but this The those of ordinary skill in field is it should be understood that without departing from the spirit of the present invention being defined by the claims and model In the case of enclosing, it can be carried out the various changes of form and details.

Claims (5)

1. comprise a crystal silicon solar energy battery for nanometer structure antireflection film, including metal backing from bottom to top Field and back electrode, single crystal silicon substrate, PN junction active layer, anti-film and gate electrode, it is characterised in that institute If stating anti-film have dried layer, the refractive index of anti-film from bottom to top is gradually reduced；Wherein, described anti-film TiO for nanostructured2Film, or by TiO2Film and SiO2Film mixes；
Wherein, the diameter of every layer of anti-film nanostructured between 10-200nm, porosity 0.1-0.9 it Between；
Wherein, described TiO2The reflectivity of film is between 2.7 to 1.3, SiO2The reflectivity of film is 1.46-1.05 Between.
The crystal silicon solar energy battery comprising nanometer structure antireflection film the most according to claim 1, it is special Levying and be, described anti-film has 2 to 5 layers.
3. comprise a preparation method for the crystal silicon solar energy battery of nanometer structure antireflection film, enter including oblique angle Penetrate physical deposition methods and generate anti-film, it is characterised in that be sequentially depositing on PN junction active layer using the following method If dried layer anti-film:
Step 1: will fix containing the single crystal silicon substrate of PN junction active layer, adjust evaporation source incident direction with The deposition surface of PN junction active layer forms an oblique incident angle；
Step 2: at a temperature of 20-100 degree, with the speed of 0.1nm/s-1nm/s by TiO2Or SiO2Deposition Anti-film is formed on PN junction active layer；
Wherein, described anti-film is the TiO of nanostructured2Film, or by TiO2Film and SiO2Film mixes；
Wherein, the diameter of every layer of anti-film nanostructured between 10-200nm, porosity 0.1-0.9 it Between；Described TiO2The reflectivity of film is between 2.7 to 1.3, SiO2The reflectivity of film be 1.46-1.05 it Between.
Preparation method the most according to claim 3, it is characterised in that described anti-film has 2 to 5 layers.
5. according to the preparation method described in claim 3 or 4, it is characterised in that described incident angle is at 10-89 Between degree.
CN201310029855.2A 2013-01-25 2013-01-25 Crystal silicon solar energy battery comprising nanometer structure antireflection film and preparation method thereof Active CN103035752B (en)

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CN106848069B (en) * 2017-03-01 2018-10-12 常州亿晶光电科技有限公司 A kind of TiO2Nano material and preparation method and purposes
CN111244218B (en) * 2018-11-29 2022-08-12 紫石能源有限公司 Solar cell and preparation method thereof

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CN101969075A (en) * 2010-08-10 2011-02-09 苏州阿特斯阳光电力科技有限公司 Double-layer anti-reflective film for crystalline silicon solar battery and preparation method thereof
CN102222704A (en) * 2011-06-27 2011-10-19 光为绿色新能源有限公司 Crystalline silicon solar battery three-layer antireflection film and preparation method thereof
CN102299185A (en) * 2010-06-24 2011-12-28 北京北方微电子基地设备工艺研究中心有限责任公司 Solar cell structure and preparation method thereof
CN102449779A (en) * 2009-03-31 2012-05-09 Lg伊诺特有限公司 Solar photovoltaic power generation apparatus and manufacturing method thereof
CN102496633A (en) * 2011-12-16 2012-06-13 中国东方电气集团有限公司 Multi-layer antireflection film for GaAs solar cell

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Publication number Priority date Publication date Assignee Title
CN102449779A (en) * 2009-03-31 2012-05-09 Lg伊诺特有限公司 Solar photovoltaic power generation apparatus and manufacturing method thereof
CN102299185A (en) * 2010-06-24 2011-12-28 北京北方微电子基地设备工艺研究中心有限责任公司 Solar cell structure and preparation method thereof
CN101969075A (en) * 2010-08-10 2011-02-09 苏州阿特斯阳光电力科技有限公司 Double-layer anti-reflective film for crystalline silicon solar battery and preparation method thereof
CN102222704A (en) * 2011-06-27 2011-10-19 光为绿色新能源有限公司 Crystalline silicon solar battery three-layer antireflection film and preparation method thereof
CN102496633A (en) * 2011-12-16 2012-06-13 中国东方电气集团有限公司 Multi-layer antireflection film for GaAs solar cell

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