CN102800739B - Manufacturing method of selective emitter monocrystalline silicon solar cell - Google Patents

Manufacturing method of selective emitter monocrystalline silicon solar cell Download PDF

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Publication number
CN102800739B
CN102800739B CN201110136009.1A CN201110136009A CN102800739B CN 102800739 B CN102800739 B CN 102800739B CN 201110136009 A CN201110136009 A CN 201110136009A CN 102800739 B CN102800739 B CN 102800739B
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solar cell
single crystal
cleaning
selective emitter
crystal silicon
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CN102800739A (en
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周利荣
刘祯
马贤芳
裴骏
张忠卫
张玮
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SHANGHAI SHENZHOU NEW ENERGY DEVELOPMENT Co Ltd
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SHANGHAI SHENZHOU NEW ENERGY DEVELOPMENT Co Ltd
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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 provides a manufacturing method of a selective emitter monocrystalline silicon solar cell. The method comprises the following steps of: cleaning the surface of a P-type monocrystalline silicon piece and making wool; performing ion implantation of phosphorus on one surface to form a PN junction; annealing and growing an oxide layer; continuously depositing a layer of passivation and antireflection film on the N-type surface; cleaning the positions of a main grid and an auxiliary grid; performing heavy doping by an ion implantation method and quickly annealing; cleaning the surface and removing the protection film; performing silk-screen printing of a back electrode electric field and drying; manufacturing a positive electrode by silk-screen printing equipment or an electroplating method; and finally sintering to obtain the product. Compared with the prior art, the method has the advantages of good controllability, low reaction temperature, relatively flat junction surface, flexible technology, high uniformity and repeatability and the like.

Description

A kind of preparation method of selective emitter single crystal silicon solar cell
Technical field
The present invention relates to solar cell, particularly relate to a kind of preparation method of selective emitter single crystal silicon solar cell.
Background technology
Solar cell is a kind of is the device of electric energy by transform light energy, accounts for the share of the solar cell occuping market more than 90% of crystal silicon material at present.Crystal silicon battery is mainly divided into monocrystalline silicon battery and polycrystal silicon cell, because the purity of monocrystalline silicon and crystal mass are higher than polysilicon, so the photoelectric conversion efficiency of monocrystalline silicon battery is generally higher than polysilicon solar cell.
At present, conventional business crystal silicon solar energy battery processing technology routine is as follows: first carry out supplied materials sorting, then cleaned up by the damage layer of surface of crystalline silicon, and carry out making herbs into wool to form certain matte to reduce surface of crystalline silicon reflectivity; Carry out High temperature diffusion again and obtain PN junction; Adopt PECVD method to deposit the thick silicon nitride film of 70 ~ 80nm at the diffusingsurface of battery, play the effect of anti-reflection and passivation; The mode of silk screen printing is finally adopted to prepare metal electrode and back surface field, obtained crystalline silicon solar cell piece after sintering.Adopt the Monocrystalline silicon cell piece efficiency of producing in this way generally at about 16%-17%.In the market competition be growing more intense, increasing silicon solar cell sheet production firm has turned one's attention to selective emitter silicon solar cell, selective emitting electrode structure can improve the short wave response of solar cell, reduce recombination-rate surface and series resistance losses, thus improve single crystal silicon solar cell efficiency to 18%-19%.Selective emitting electrode structure is as shown below, and it has two features: (1) under gate electrode line and near the highly doped dark diffusion region of formation; (2) low-doped shallow diffusion region is formed in other regions.
The process can preparing selective emitting electrode structure at present has the modes such as twice diffusion method, the diffusion+selective corrosion of painting source, phosphorous electrode slurry, laser doping.Wherein, twice diffusion method due to its technique comparatively complicated, and multiple high temp can bring harm to material itself.Diffusion+selective corrosion method in painting source is evenly coated with source at silicon chip surface and spreads, and ties relatively dark; And selective corrosion can impact electrode contact after metallization.The method of printing phosphorous slurry cannot form desirable heavy dopant concentration and distribution.Dry laser doping in antireflection layer surface spin coating one deck doped source, then must scan by certain figure with laser in advance, adulterates at the inswept part generation partial melting of hot spot.But often easily produce the unsteadiness of overlay capacity in the process in spin coating phosphorus source, the damage of dry laser process generation is larger in addition.
The method having document also to disclose grooving and grid burying prepares selective emitter, achieves higher conversion efficiency in laboratory; But the document exists structure relative complex, technique realizes difficulty shortcoming.
Summary of the invention
Object of the present invention, exactly in order to provide a kind of controllability good, reaction temperature is low, more smooth, the technique in knot face flexibly, the preparation method of uniformity and reproducible selective emitter single crystal silicon solar cell.
In order to achieve the above object, present invention employs following technical scheme: a kind of preparation method of selective emitter single crystal silicon solar cell, it is characterized in that, the method comprises the following steps:
(1) cleaning and texturing is carried out to p type single crystal silicon sheet surface;
(2) then ion implantation P elements is carried out to its one side and form PN junction;
(3) carry out annealing and growing oxide layer;
(4) deposition one deck passivation and antireflective film is continued on N-type surface;
(5) main grid and secondary grid present position are cleaned, adopt the method for ion implantation to carry out heavy doping and short annealing;
(6) clean surface, removes diaphragm;
(7) then silk screen printing backplate electric field dry, adopt screen printing apparatus or electro-plating method to prepare positive electrode;
(8) finally sinter, obtain product.
Cleaning and texturing described in step (1) adopts the mixture of NaOH, isopropyl alcohol, making herbs into wool additive and deionized water to cleaning monocrystalline silicon; The mass concentration of described NaOH is 1% ~ 3%, and described making herbs into wool additive is commercially available making herbs into wool additive DY-810, and in described mixture, the volume ratio of NaOH, isopropyl alcohol, making herbs into wool additive and deionized water is 5: 9: 1: 150.
Ion implantation described in step (2) P elements impurity ionization is become ion and is focused into ion beam, and accelerate in the electric field and after obtaining high kinetic energy, be injected in silicon and realize doping, implantation temperature is 200 DEG C ~ 400 DEG C.
The CONCENTRATION DISTRIBUTION of described doping is 10 18cm 3~ 10 20/ cm 3, the degree of depth of doping is 0.15 μm ~ 0.4 μm.
Annealing temperature described in step (3) is 600 DEG C ~ 700 DEG C.
Passivation described in step (4) and antireflective film prepare single-layer silicon nitride silicon thin film or the dual-layer silicon nitride film of 70nm ~ 90nm by reacting gas ammonia and silane by plasma enhanced chemical vapor deposition method.
The cleaning to main grid and secondary grid described in step (5) adopts the method cleaning of ink-jet or the agent of silk screen printing sour corrosion or laser ablation; Described heavily doped CONCENTRATION DISTRIBUTION is 10 19cm 3~ 10 21/ cm 3, the degree of depth is 0.5 μm ~ 2 μm; Described short annealing temperature is 600 DEG C ~ 700 DEG C, and the time is 1 ~ 10 minute.
Described sour corrosion agent is hydrofluoric acid or nitric acid, and described laser ablation adopts the laser of 532nm or 1064nm wavelength.
The rinsing that clean surface described in step (6) adopts low concentration acid solution to carry out 1 ~ 5 minute, described low concentration acid solution is the hydrofluoric acid of 1% ~ 5%.
The temperature of the sintering described in step (8) is 500 DEG C ~ 900 DEG C.
Compared with prior art, the present invention has the following advantages:
1, controllability is good: the CONCENTRATION DISTRIBUTION of the accurate controlled doping of ion implantation energy and doping depth, thus go for the requirement of selective emitting electrode structure two kinds of different levels of doping distributions.
2, reaction temperature is low: in invention, implantation temperature is generally no more than 400 DEG C, and annealing temperature, at about 650 DEG C, avoids the adverse effect that pyroprocess is brought, as knot passing, thermal defect, silicon chip distortion etc.; Avoid a large amount of high temperature energy consumptions simultaneously, reduce the cost of manufacture of selective emitter silion cell.
4, face of tying is more smooth: the knot of the PN junction prepared by the ion implantation face that this invention adopts is comparatively smooth, is conducive to the electrical property improving selective emitter battery.
5, technique is flexible: can penetrate in the substrate that surface film is injected into below, multiple material also can be adopted to make masking film, as SiO 2, SiNx or photoresist etc.;
6, uniformity and reproducible: this ensure that the product quality of selective emitter silicon solar cell in large-scale production and application.
Accompanying drawing explanation
Fig. 1 is selective emitter silicon solar cell structural representation of the present invention;
Fig. 2 is the A portion enlarged drawing of Fig. 1.
Embodiment
Embodiment 1
As shown in Figure 1-2, a kind of preparation method of selective emitter single crystal silicon solar cell, the method comprises the following steps:
(1) carry out cleaning and texturing to p type single crystal silicon sheet 5 surface, cleaning and texturing adopts the mixture of NaOH, isopropyl alcohol, making herbs into wool additive and deionized water to cleaning monocrystalline silicon; The mass concentration of described NaOH is 1% ~ 3%, and described making herbs into wool additive is commercially available making herbs into wool additive DY-810, and in described mixture, the volume ratio of NaOH, isopropyl alcohol, making herbs into wool additive and deionized water is 5: 9: 1: 150;
(2) then ion implantation P elements is carried out to its one side and form N-type silicon 4, then N-type silicon 4 and p type single crystal silicon sheet 5 form formation PN junction 12, ion implantation P elements impurity ionization is become ion and is focused into ion beam, to accelerate in the electric field and after obtaining high kinetic energy, be injected in silicon and realize doping, implantation temperature is 200 DEG C, and the CONCENTRATION DISTRIBUTION of doping is 10 18cm 3, the degree of depth of doping is 0.15 μm;
(3) carry out annealing and growing oxide layer SiO at 600 DEG C ~ 700 DEG C 2film 3;
(4) deposition one deck passivation and antireflective film and SiN is continued by reacting gas ammonia and silane on N-type surface by plasma enhanced chemical vapor deposition method xfilm 2, SiN xfilm 2 (SiN xmiddle x is 1 ~ 3) be the single-layer silicon nitride silicon thin film of 70nm;
(5) adopt ink-jet or silk screen printing sour corrosion agent hydrofluoric acid or nitric acid to clean to main grid and secondary grid present position, adopt the method for ion implantation to carry out heavy doping and short annealing, form lateral junction 11, heavily doped CONCENTRATION DISTRIBUTION is 10 19cm 3, the degree of depth is 0.5 μm; Described short annealing temperature is 600 DEG C, and the time is 1 minute;
(6) adopt mass concentration be 1% hydrofluoric acid carry out the rinsing of 1 minute, clean surface, remove diaphragm;
(7) then silk screen printing backplate back of the body electric field 7 dry, adopt screen printing apparatus or electro-plating method to prepare positive electrode 1;
(8) finally sinter at 500 DEG C, p type single crystal silicon sheet 5 and back of the body electric field 7 form the P that one deck mixes Al in the middle of oversintering +namely type silicon obtain product.
Ion implantation is a kind of method of adulterating to semiconductor.Impurity ionization become ion and is focused into ion beam, accelerate in the electric field and after obtaining high kinetic energy, be injected in silicon and realize doping.Be injected into acceptor in semiconductor or donor impurity major part all rests on interstitial site place, through the annealing in process of proper temperature, the whole of implanted dopant atom or major part can be made to enter displacement position from interstitial site and discharge charge carrier, thus change the electrical characteristics of semiconductor; Annealing in process also can reduce implant damage simultaneously.
Present invention utilizes the high controllability of ion implantation, make to form predetermined doping concentration distribution and doping depth in p type single crystal silicon sheet, and inject formation selective emitting electrode structure by secondary ion.
Embodiment 2
A preparation method for selective emitter single crystal silicon solar cell, the method comprises the following steps:
(1) carry out cleaning and texturing to p type single crystal silicon sheet surface, cleaning and texturing adopts the mixture of NaOH, isopropyl alcohol, making herbs into wool additive and deionized water to cleaning monocrystalline silicon; The mass concentration of described NaOH is 1% ~ 3%, and described making herbs into wool additive is commercially available making herbs into wool additive DY-810, and in described mixture, the volume ratio of NaOH, isopropyl alcohol, making herbs into wool additive and deionized water is 5: 9: 1: 150;
(2) then ion implantation P elements is carried out to its one side and form N-type silicon, then N-type silicon and p type single crystal silicon sheet form formation PN junction, ion implantation P elements impurity ionization is become ion and is focused into ion beam, to accelerate in the electric field and after obtaining high kinetic energy, be injected in silicon and realize doping, implantation temperature is 400 DEG C, and the CONCENTRATION DISTRIBUTION of doping is 10 20/ cm 3, the degree of depth of doping is 0.4 μm;
(3) carry out annealing and growing oxide layer SiO at 700 DEG C 2film;
(4) deposition one deck passivation and antireflective film and SiN is continued by reacting gas ammonia and silane on N-type surface by plasma enhanced chemical vapor deposition method xfilm, SiN xfilm is the dual-layer silicon nitride film of 90nm;
(5) adopt the laser of 532nm or 1064nm wavelength to carry out laser ablation cleaning to main grid and secondary grid present position, adopt the method for ion implantation to carry out heavy doping and short annealing, form lateral junction, heavily doped CONCENTRATION DISTRIBUTION is 10 21/ cm 3, the degree of depth is 2 μm; Described short annealing temperature is 700 DEG C, and the time is 10 minutes;
(6) rinsing adopting the hydrofluoric acid of 5% to carry out 5 minutes, clean surface, removes diaphragm;
(7) then silk screen printing backplate back of the body electric field dry, adopt conventional screen printing apparatus or common electro-plating method to prepare positive electrode;
(8) finally sinter at 900 DEG C, p type single crystal silicon sheet and back of the body electric field form the P that one deck mixes Al in the middle of oversintering +namely type silicon obtain product.

Claims (7)

1. a preparation method for selective emitter single crystal silicon solar cell, is characterized in that, the method comprises the following steps:
(1) cleaning and texturing is carried out to p type single crystal silicon sheet surface;
(2) then ion implantation P elements is carried out to its one side and form PN junction;
(3) carry out annealing and growing oxide layer;
(4) deposition one deck passivation and antireflective film is continued on N-type surface;
(5) main grid and secondary grid present position are cleaned, adopt the method for ion implantation to carry out heavy doping and short annealing;
(6) clean surface, removes diaphragm;
(7) then silk screen printing backplate electric field dry, adopt screen printing apparatus or electro-plating method to prepare positive electrode;
(8) finally sinter, obtain product;
Cleaning and texturing described in step (1) adopts the mixture of NaOH, isopropyl alcohol, making herbs into wool additive and deionized water to cleaning monocrystalline silicon; The mass concentration of described NaOH is 1% ~ 3%, and described making herbs into wool additive is commercially available making herbs into wool additive DY-810, and in described mixture, the volume ratio of NaOH, isopropyl alcohol, making herbs into wool additive and deionized water is 5:9:1:150;
Ion implantation described in step (2) P elements impurity ionization is become ion and is focused into ion beam, and accelerate in the electric field and after obtaining high kinetic energy, be injected in silicon and realize doping, implantation temperature is 200 DEG C ~ 400 DEG C;
Annealing temperature described in step (3) is 600 DEG C ~ 700 DEG C.
2. the preparation method of selective emitter single crystal silicon solar cell according to claim 1, is characterized in that, the CONCENTRATION DISTRIBUTION of described doping is 10 18cm 3~ 10 20/ cm 3, the degree of depth of doping is 0.15 μm ~ 0.4 μm.
3. the preparation method of selective emitter single crystal silicon solar cell according to claim 1, it is characterized in that, the passivation described in step (4) and antireflective film prepare single-layer silicon nitride silicon thin film or the dual-layer silicon nitride film of 70nm ~ 90nm by reacting gas ammonia and silane by plasma enhanced chemical vapor deposition method.
4. the preparation method of selective emitter single crystal silicon solar cell according to claim 1, it is characterized in that, the cleaning to main grid and secondary grid described in step (5) adopts the method cleaning of ink-jet or the agent of silk screen printing sour corrosion or laser ablation; Described heavily doped CONCENTRATION DISTRIBUTION is 10 19cm 3~ 10 21/ cm 3, the degree of depth is 0.5 μm ~ 2 μm; Described short annealing temperature is 600 DEG C ~ 700 DEG C, and the time is 1 ~ 10 minute.
5. the preparation method of selective emitter single crystal silicon solar cell according to claim 4, is characterized in that, described sour corrosion agent is hydrofluoric acid or nitric acid, and described laser ablation adopts the laser of 532nm or 1064nm wavelength.
6. the preparation method of selective emitter single crystal silicon solar cell according to claim 1, it is characterized in that, the rinsing that clean surface described in step (6) adopts low concentration acid solution to carry out 1 ~ 5 minute, described low concentration acid solution is the hydrofluoric acid of 1% ~ 5%.
7. the preparation method of selective emitter single crystal silicon solar cell according to claim 1, is characterized in that, the temperature of the sintering described in step (8) is 500 DEG C ~ 900 DEG C.
CN201110136009.1A 2011-05-24 2011-05-24 Manufacturing method of selective emitter monocrystalline silicon solar cell Expired - Fee Related CN102800739B (en)

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CN103066135B (en) * 2013-01-17 2016-03-02 中山大学 Selective emitter solar battery that a kind of front electrode main grid line and silicon substrate are isolated and preparation method thereof
CN103426973B (en) * 2013-09-05 2015-12-09 常州天合光能有限公司 The method of isolation liner bottom two sides film and heterojunction solar battery preparation technology
CN104051570A (en) * 2014-06-09 2014-09-17 山东力诺太阳能电力股份有限公司 Manufacturing method of solar cell
CN108258082B (en) * 2018-01-10 2021-06-04 张家港协鑫集成科技有限公司 Preparation method of solar cell

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CN101976711A (en) * 2010-10-27 2011-02-16 晶澳太阳能有限公司 Method for making solar batteries by adopting ion injection method

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DE10150040A1 (en) * 2001-10-10 2003-04-17 Merck Patent Gmbh Etching passivating and antireflection layers made from silicon nitride on solar cells comprises applying a phosphoric acid and/or etching medium containing a salt of phosphoric acid the surface regions to be etched
US8106291B2 (en) * 2004-05-07 2012-01-31 Mitsubishi Electric Corporation Solar battery and manufacturing method therefor

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CN101976711A (en) * 2010-10-27 2011-02-16 晶澳太阳能有限公司 Method for making solar batteries by adopting ion injection method

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