CN103035752A - Crystalline silicon solar battery including nanometer structure antireflection film and preparation method thereof - Google Patents

Crystalline silicon solar battery including nanometer structure antireflection film and preparation method thereof Download PDF

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CN103035752A
CN103035752A CN2013100298552A CN201310029855A CN103035752A CN 103035752 A CN103035752 A CN 103035752A CN 2013100298552 A CN2013100298552 A CN 2013100298552A CN 201310029855 A CN201310029855 A CN 201310029855A CN 103035752 A CN103035752 A CN 103035752A
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film
silicon solar
crystal silicon
nanostructure
tio
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CN103035752B (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
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    • 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

A crystalline silicon solar battery including a nanometer structure antireflection film comprises a metal back surface field and a back electrode, a single crystal silicon substrate, a PN junction active layer, antireflection films and a gate electrode, which are arranged from bottom to top; and the crystalline silicon solar battery is characterized in that the layers of antireflection films are arranged and the refractive indexes of the antireflection films are gradually reduced from bottom to top. The preparation method comprises the step of using an inclined-angle incident physical deposition method to generate the antireflection films with different refractive indexes in the plurality of layers through adjusting an incident angle and a deposition material. According to the invention, the light absorption of a silicon solar cell is greatly optimized, so that the battery efficiency is increased. Through the adoption of the method provided by the invention, the photovoltaic characteristic of a silicon crystal cannot be damaged and excessive absorbed lights can be really converted into electric energy. The light conversion efficiency is increased and the development of a solar cell product is greatly promoted.

Description

Comprise crystal silicon solar energy battery of the anti-anti-film of nanostructure and preparation method thereof
Technical field
The present invention relates to a kind of way that improves the silicon solar cell transformation efficiency, particularly comprise crystal silicon solar energy battery of the anti-anti-film of nanostructure and preparation method thereof, belong to the semi-conducting material application.
Background technology
The principal element that affects solar battery efficiency mainly comprises optical loss and electricity loss.Wherein optical loss mainly comprises the shadow loss of battery front surface contact grid line, the reflection loss on surface and the non-absorption loss water of long-wave band. during sunlight incident, naked silicon face has up to the reflectivity more than 30%, and this can increase the optical loss of battery greatly.Silicon chip surface texturing that the silicon nitride passivation of individual layer and soda acid carry out is in conjunction with being common industrial production method, but this anti-anti-film only can fall reflectivity lowlyer in very narrow spectral region and very little angular range.In recent years, the anti-anti-film of sub-wavelength Fabrication of nanostructures has caused increasing concern.The characteristic of this structure is to realize extremely low reflectivity in wide spectral range and very large angular range.What but the main needs of this method solved is two aspect problems: be whether method is compatible with existing silicon solar cell flow process on the one hand, and the 2nd, the cost of this method is how.
Summary of the invention
The present invention provides a kind of crystal silicon solar energy battery that comprises the anti-anti-film of nanostructure for overcoming above deficiency, comprise from bottom to top metal back surface field and back electrode, single crystal silicon substrate, PN junction active layer, anti-anti-film, and gate electrode, wherein, described anti-anti-film has some layers, and the refractive index of anti-anti-film from bottom to top reduces gradually.
Preferably, anti-anti-film is the TiO of nanostructure 2Film, or by TiO 2Film and SiO 2Film mixes.
Preferably, anti-anti-film has 2 to 5 layers.
Preferably, the diameter of every layer of anti-anti-film nanometer rods is between 10-200nm, and porosity is between 0.1-0.9.
Preferably, TiO 2The reflectivity of film is between 2.7 to 1.3, SiO 2The reflectivity of film is between the 1.46-1.05.
Another object of the present invention also is, a kind of preparation method who comprises the crystal silicon solar energy battery of the anti-anti-film of nanostructure is provided, comprise that oblique angle incident physical deposition method generates anti-anti-film, it is characterized in that, on the PN junction active layer, deposit successively the anti-anti-film of some layers with following methods:
Step 1: the single crystal silicon substrate that will contain the PN junction active layer is fixed, and adjusts the incident direction of evaporation source and the deposition surface of PN junction active layer and forms an oblique incident angle;
Step 2: under the temperature of 20-100 degree, with the speed of 0.1nm/s-1nm/s with TiO 2Or SiO 2Be deposited on and form anti-anti-film on the PN junction active layer.
Preferably, anti-anti-film is the TiO of nanostructure 2Film, or by TiO 2Film and SiO 2Film mixes.
Preferably, anti-anti-film has 2 to 5 layers.
Preferably, the diameter of every layer of anti-anti-film nanometer rods is between 10-200nm, and porosity is between 0.1-0.9; TiO 2The reflectivity of film is between 2.7 to 1.3, SiO 2The reflectivity of film is between the 1.46-1.05.
Preferably, incident angle is between the 10-89 degree.
The present invention adopts the method for glancing angle deposition, and this crystal silicon solar energy battery that includes the anti-anti-film of concrete dynamic modulus nanostructure of reflection multilayer rate gradual change of preparation has greatly been optimized the light absorption of silicon solar cell, thereby improved battery efficiency.Other typical nanometer technology is compared such as black silicon or nanoporous silicon technology with some, and this method can not damaged the photovoltaic property of silicon crystal itself, can really the light that absorbs be converted into electric energy more.Improve phototranstormation efficiency, will greatly promote the development of solar battery product.This preparation method also possesses following advantage: 1) controlled to the technological process of production high flexible of nanostructure, the nanostructure of producing has homogeneity and the reappearance of height; 2) method is not subjected to the restriction of material substantially based on the heat deposition plated film.3) technological process is simple, can finish in the one-time process flow process preparation production of the complicated ordered nano-structure of multilayer such as column, S shape, spirality, zigzag etc., can realize producing in batches, and cost is not high yet.4) fully compatible with existing other silicon solar cell techniques, do not need extra equipment and cost.
Description of drawings
Fig. 1 is embodiment of the invention crystal silicon solar energy battery structural representation.
Fig. 2 is the structural representation of the anti-anti-film of nanostructure of embodiment of the invention reflection multilayer rate gradual change.
Fig. 3 is the schematic diagram that embodiment of the invention oblique angle incident physical deposition method is used.
Embodiment
The present invention is further described with embodiment below in conjunction with accompanying drawing.
The purpose of the embodiment of the invention is to make the anti-anti-film of nanostructure to reduce reflectivity, improves the electricity conversion of solar cell and this crystal silicon solar energy battery and manufacture method are provided.The anti-anti-film of this nanostructure can be realized extremely low reflectivity in wide spectrum and extensive angle scope.Present embodiment uses the method for oblique angle incident physical deposition, and technique is simple, and cost is lower, and the complete compatibility of technique and existing silicon solar cell flow process.
The above crystal silicon solar energy battery structure as shown in Figure 1, respectively metal back surface field and back electrode 3, p type single crystal silicon matrix 1, N-type active layer 2, anti-anti-film 4 and gate electrode 5 from bottom to top, wherein, form PN junction between p type single crystal silicon matrix 1 and the N-type active layer 2, particularly, anti-anti-film has multilayer, and the refractive index of the anti-anti-film of each layer from bottom to top reduces gradually.Usually anti-anti-film is TiO 2Film or SiO 2Film is seen Fig. 2, the anti-anti-film that is of five storeys respectively, i.e. and a to e layer, from bottom to top, ground floor a is the nanostructure TiO of refractive index 2.03 2, second layer b is the nanostructure TiO of refractive index 1.95 2, the 3rd layer of c is that refractive index is 1.65 nanostructure TiO 2, the 4th layer of d is the SiO of refractive index 1.26 2, layer 5 e is the SiO of refractive index 1.05 2, and the diameter of the nanometer rods of every one deck requires between 10-200nm, and porosity is between 0.1-0.9.Like this, nanostructure porosity and refractive index all successively increase progressively from top to bottom, have greatly promoted the effect of optimization of anti-anti-film, thereby have realized the comprehensively anti-anti-of wide spectrum and polarizers of big angle scope.Based on above analysis, the anti-anti-film of each layer can be chosen TiO 2Single formation, or by TiO 2And SiO 2Two to five layers of nano-structure film, wherein TiO mixing 2Reflectivity be between 2.7 to 1.3, SiO 2Reflectivity be between the 1.46-1.05.Wherein the nanostructure porosity of every layer of anti-anti-film is successively successively decreased from bottom to top, thus refractive index also successively successively decrease from bottom to top, and be distributed between the 1.05-2.7.
The preparation method of above embodiment crystal silicon solar energy battery structure referring to Fig. 3, adopts oblique angle incident physical deposition method.Its principle is to form an angle of inclination with the substrate of PN junction with respect to the incident direction of incident air-flow by control, between the nanometer column structure of formation certain hole is just arranged like this.And inclination angle corresponding to the anti-anti-film of every one deck, then the nanostructure porosity of the anti-anti-film of every one deck is different.The incidence angle that we adopt every one deck reflectivity successively to increase progressively from bottom to top, then porosity is successively successively decreased from bottom to top, thus reflectivity also successively successively decreases from bottom to top.Among Fig. 31 is for containing the single crystal silicon substrate of PN junction active layer, and 6 is the materials of deposition, and α is incidence angle, and 7 are the nano-pillar in the anti-anti-film microstructure.
Concrete operation step is: from bottom to top, the anti-anti-film deposition materials of ground floor a is TiO 2, the working vacuum degree is the 1e-6 holder, and incidence angle is 24 degree, namely is 24 degree angle incidents (together lower) with vertical line, and deposition velocity is 0.2nm/s, and sedimentation time is 400s, and thickness is 80nm, and refractive index is 2.03.
The anti-anti-film deposition materials of second layer b is TiO 2, the working vacuum degree is the 1e-6 holder, and incidence angle is 39 degree, and deposition velocity is 0.2nm/s, and sedimentation time is 400s, and thickness is 80nm, and refractive index is 1.95.
The 3rd layer of anti-anti-film deposition materials of c is TiO 2, the working vacuum degree is the 1e-6 holder, and incidence angle is 64 degree, and deposition velocity is 0.2nm/s, and sedimentation time is 500s, and thickness is 100nm, and refractive index is 1.65.
The 4th layer of anti-anti-film deposition materials of d is SiO 2, the working vacuum degree is the 1e-6 holder, and incidence angle is reverse 68 degree, and deposition velocity is 0.4nm/s, and sedimentation time is 375s, and thickness is 150nm, and refractive index is 1.26.
The anti-anti-film deposition materials of layer 5 e is SiO 2, the working vacuum degree is the 1e-6 holder, and incidence angle is reverse 86 degree, and deposition velocity is 0.4nm/s, and sedimentation time is 575s, and thickness is 230nm, and refractive index is 1.05.
Cardinal principle of the present invention is that the method for employing oblique angle incident physical deposition is controlled material in the form of substrate surface deposition modeling by the control substrate with respect to angle of inclination and the direction of incident air-flow.For normal depositional mode, atom and molecule can deposit more equably on whole plane, and after the inclined deposition incident angle, can cause atom and molecule the direction of certain inclination assemble many, form a structure that is similar to tree shade, the time one is long, and the zone under " tree shade " covers does not just have the atom and molecule deposition, " tree shade " then can be more long, becomes the nanostructure of preiodic type.And every layer of material is adopted different oblique incidence angles, will obtain the porosity of different nanostructures.Periodic concrete dynamic modulus nanostructure, meeting are so that the equivalent refractive index of this layer material is lower than same orthodox material, and the change porosity, it is adjustable that refractive index is continued within the specific limits, reaches our refractive index demand.Particularly, the incidence angle that adopts exactly every one deck from top to bottom successively to increase progressively, then porosity is successively successively decreased from top to bottom, thus reflectivity also successively successively decreases from top to bottom.The refractive index of the anti-anti-film of traditional individual layer can only be mated single wavelength and very little ranges of incidence angles, and this multilayer of the present invention, every layer of structure that refractive index is successively successively decreased from top to bottom then can promote the effect of optimization that resists anti-film greatly, realizes the comprehensively anti-anti-of wide spectrum and polarizers of big angle scope.
The major advantage of oblique angle incident physical deposition method is that he has overcome the limitation that other nano material prepares growth technique.For example, the common step of chemical method is tediously long, harsh to reaction condition (temperature, air pressure, acidity etc.) requirement.And based on the method apparatus expensive of template etching (miniature carving of electron beams/laser bundle), can't carry out large-scale production at present.And oblique angle incident physical deposition law technology is a kind of strong method for preparing highly controlled nanoaperture and nano structure membrane.
Present embodiment in like manner, also can be the monocrystaline silicon solar cell structure of n type single crystal silicon matrix 1 and P type active layer take p type single crystal silicon matrix and N-type active layer as example, and its preparation method is identical with the invention effect that reaches.
Although more than be that the present invention is specifically described with reference to its exemplary embodiment and shows, but will be understood by those skilled in the art that, in the situation that does not break away from the spirit and scope of the present invention that are defined by the claims, can carry out to it various changes of form and details.

Claims (10)

1. one kind comprises the crystal silicon solar energy battery that nanostructure resists anti-film, comprise from bottom to top metal back surface field and back electrode, single crystal silicon substrate, PN junction active layer, anti-anti-film, and gate electrode, it is characterized in that, described anti-anti-film has some layers, and the refractive index of anti-anti-film from bottom to top reduces gradually.
2. the crystal silicon solar energy battery that comprises the anti-anti-film of nanostructure according to claim 1 is characterized in that, described anti-anti-film is the TiO of nanostructure 2Film, or by TiO 2Film and SiO 2Film mixes.
3. the crystal silicon solar energy battery that comprises the anti-anti-film of nanostructure according to claim 2 is characterized in that, described anti-anti-film has 2 to 5 layers.
4. the crystal silicon solar energy battery that comprises the anti-anti-film of nanostructure according to claim 3 is characterized in that, the diameter of described every layer of anti-anti-film nanometer rods is between 10-200nm, and porosity is between 0.1-0.9.
5. the crystal silicon solar energy battery that comprises the anti-anti-film of nanostructure according to claim 3 is characterized in that described TiO 2The reflectivity of film is between 2.7 to 1.3, SiO 2The reflectivity of film is between the 1.46-1.05.
6. a preparation method who comprises the crystal silicon solar energy battery of the anti-anti-film of nanostructure comprises that oblique angle incident physical deposition method generates anti-anti-film, it is characterized in that, deposits successively the anti-anti-film of some layers with following methods on the PN junction active layer:
Step 1: the single crystal silicon substrate that will contain the PN junction active layer is fixed, and adjusts the incident direction of evaporation source and the deposition surface of PN junction active layer and forms an oblique incident angle;
Step 2: under the temperature of 20-100 degree, with the speed of 0.1nm/s-1nm/s with TiO 2Or SiO 2Be deposited on and form anti-anti-film on the PN junction active layer.
7. preparation method according to claim 6 is characterized in that, described anti-anti-film is the TiO of nanostructure 2Film, or by TiO 2Film and SiO 2Film mixes.
8. the crystal silicon solar energy battery that comprises the anti-anti-film of nanostructure according to claim 7 is characterized in that, described anti-anti-film has 2 to 5 layers.
9. preparation method according to claim 8 is characterized in that, the diameter of described every layer of anti-anti-film nanometer rods is between 10-200nm, and porosity is between 0.1-0.9; Described TiO 2The reflectivity of film is between 2.7 to 1.3, SiO 2The reflectivity of film is between the 1.46-1.05.
10. arbitrary described preparation method in 9 according to claim 7 is characterized in that described incident angle is between the 10-89 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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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848069A (en) * 2017-03-01 2017-06-13 常州亿晶光电科技有限公司 A kind of new TiO2Nano material and preparation method and purposes
CN111244218A (en) * 2018-11-29 2020-06-05 东泰高科装备科技有限公司 Solar cell and preparation method thereof

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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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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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848069A (en) * 2017-03-01 2017-06-13 常州亿晶光电科技有限公司 A kind of new TiO2Nano material and preparation method and purposes
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
CN111244218A (en) * 2018-11-29 2020-06-05 东泰高科装备科技有限公司 Solar cell and preparation method thereof
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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