CN102122674A - Crystalline silicon solar cell and preparation method thereof - Google Patents

Crystalline silicon solar cell and preparation method thereof Download PDF

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CN102122674A
CN102122674A CN2011100085716A CN201110008571A CN102122674A CN 102122674 A CN102122674 A CN 102122674A CN 2011100085716 A CN2011100085716 A CN 2011100085716A CN 201110008571 A CN201110008571 A CN 201110008571A CN 102122674 A CN102122674 A CN 102122674A
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amorphous
type substrate
phosphorus
oxide layer
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褚君浩
窦亚楠
何悦
王建禄
马晓光
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Shanghai Institute of Technical Physics of CAS
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Abstract

The invention discloses a crystalline silicon solar cell and a preparation method thereof, and the crystalline silicon solar cell comprises a pn plus junction silicon substrate, wherein a first amorphous alumina layer and an amorphous silicon nitride layer are arranged on the surface of an n plus emitter, a silver electrode penetrates the amorphous silicon nitride layer and the first amorphous alumina layer and is connected with the n plus emitter, a composite passivation medium layer is arranged on the surface of a p type substrate, the p type substrate comprises a silicon oxide layer and a second amorphous alumina layer, and a p type substrate is in contact with a back electrode. The preparation method comprises the special preparation of the composite passivation medium layer, nitric acid and hydrogen peroxide solution are adopted for processing the surface of the p type substrate, the sol-gel process is adopted for preparing the second amorphous alumina layer, and the composite passivation medium layer (4) is formed after annealing. The crystalline silicon solar cell has the advantages of simple process, low equipment investment, good passivation and anti-reflection performances of the front surface, excellent passivation effect of the composite passivation medium layer on the back surface, capability of improving the utilization efficiency of long waves, and the like.

Description

A kind of crystal-silicon solar cell and preparation method thereof
Technical field
The present invention relates to a kind of crystal-silicon solar cell and preparation method thereof, specifically is a kind of crystal-silicon solar cell with double-deck front surface passivated reflection reducing dielectric layer and back of the body surface recombination passivation dielectric layer and preparation method thereof.
Background technology
Present most commercialization crystal-silicon solar cell adopts screen printing technique, and technological process is simple, avoids widely applying vacuum equipment, is convenient to large-scale production.As shown in Figure 2, its basic procedure is: 1. remove silicon face damage, acid or alkali lye making herbs into wool and form anti-reflection structure and chemical cleaning; 2. at POCl 3Spread in the atmosphere and remove peripheral pn+ knot and phosphorosilicate glass; 3. adopt PECVD deposit SiNx:H antireflective film; 4. silk screen printing front, backplate and back of the body surface field; 5. sintering forms ohmic contact.Although adopt the large-scale production of this technology energy, the front surface of this battery and the surperficial charge carrier of the back of the body are compound serious, and the back of the body is surperficial to the infrared light difference in response, makes battery efficiency lower.That laboratory crystalline silicon peak efficiency battery and other high efficiency batteries generally adopt is surperficial SiO 2Passivating technique, effectively passivated surface reduces the charge carrier recombination velocity.Yet SiO 2Passivation layer prepares, and generally adopts the thermal oxidation method of 900-1100 ℃ high temperature, and is serious to low-quality solar energy-level silicon wafer bluk recombination influence, and wants the photoetching technique of application of expensive, and complex process is unfavorable for industrialization large-scale production.Amorphous silicon nitride layer is done the passivation layer of front surface, also is antireflection layer simultaneously, owing to the reason passivation and the antireflective effect of technology can not reach optimum effect simultaneously.Double-deck in theory silicon nitride film can effectively improve passivation and anti-reflective effect under the situation of refractive index and thickness coupling, but because of the difficulty of refractive index less than 1.9 amorphous silicon nitride preparation, is difficult to reach the antireflecting effect of bilayer film in the practical application.The graded index silicon nitride film is difficult to realize because of technological problems equally.Amorphous silicon/amorphous silicon nitride duplicature can play good passivation effect, but with follow-up silk screen printing in arriving 800 ℃ high temperature and incompatible, because amorphous silicon crystallization easily at high temperature is difficult to the passivation effect that reaches desirable after the crystallization.
Summary of the invention
The technical problem to be solved in the present invention is, uses simple technology and realizes having the effect of penetrating of two-layered medium layer passivated reflection reducing and have the crystal silicon solar energy battery of carrying on the back surface recombination dielectric layer thin film passivation, and preparation method thereof.
Crystal-silicon solar cell of the present invention as shown in Figure 1, this battery structure is: n+ emitter (301) surface in pn+ knot silicon base (3) has the first amorphous nickel/phosphorus/aluminium oxide layer (2) and amorphous silicon nitride layer (1) successively, silver electrode (6) is passed amorphous silicon nitride layer (1) and the first amorphous nickel/phosphorus/aluminium oxide layer (2) and n+ emitter (301) ohmic contact, there is composite passivated dielectric layer (4) on p type substrate (302) surface, composite passivated dielectric layer (4) is made up of the silicon oxide layer (401) and the second amorphous nickel/phosphorus/aluminium oxide layer (402), and back electrode (5) passes composite passivated dielectric layer (4) and p type substrate ohmic contact.
The described first amorphous nickel/phosphorus/aluminium oxide layer (2) is to prepare on n+ emitter (301) by sol-gel process, and thickness 10-20nm plays passivation.
Described amorphous silicon nitride layer (1) is that employing conventional P ECVD deposit 60-100nm refractive index is the amorphous silicon nitride films of 1.9-2.5.
Described composite passivated dielectric layer (4) is the double-decker of the silicon oxide layer (401) and the second amorphous nickel/phosphorus/aluminium oxide layer (402), play the effect of a chemical passivation and a passivation, wherein silicon oxide layer (401) is that 1.5-3nm is thick, and the second amorphous nickel/phosphorus/aluminium oxide layer (402) is that 10-100nm is thick.
The preparation method of crystal silicon solar energy battery of the present invention adopts in traditional handicraft
Figure BSA00000419486100021
With
Figure BSA00000419486100022
The basis on increase new technology
Figure BSA00000419486100023
With
Figure BSA00000419486100024
Figure BSA00000419486100025
Remove p type silicon base surface damage, acid or alkali lye making herbs into wool and form anti-reflection structure and chemical cleaning;
At POCl 3Spread and remove the pn+ knot silicon base (3) of peripheral pn knot and phosphorosilicate glass formation pn+ structure in the atmosphere;
Figure BSA00000419486100031
Adopt volume ratio HNO 3: H2O2=20-5: 1 mixed solution soaked p type substrate (302) surface 30 minutes; HNO wherein 3Concentration is 68%, H 2O 2For concentration is 30%;
Figure BSA00000419486100032
Adopt the alumina sol of sol-gel process preparation, its step is as follows:
(a) under strong mixing, aluminium isopropoxide is poured into hydrolysis in the boiling water that contains part nitric acid, continue to stir; Temperature drops to 85-95 ℃ after 30 minutes;
(b) add red fuming nitric acid (RFNA) after 60 minutes, promptly obtain the alumina sol clarified, natural cooling;
Figure BSA00000419486100033
The n+ emitter (301) of the pn+ knot silicon base (3) that obtains in step 3 and p type substrate (302) surface employing czochralski method or spin-coating method prepare aluminum oxide film, 400-600 ℃ of annealing is after 15-30 minute, the thickness of the first amorphous nickel/phosphorus/aluminium oxide layer (2) is 10-20nm, and the thickness of the second amorphous nickel/phosphorus/aluminium oxide layer (402) is 10-100nm;
Figure BSA00000419486100034
Adopting conventional P ECVD deposit 60-100nm refractive index is the amorphous silicon nitride films formation amorphous silicon nitride layer (1) of 1.9-2.5;
Figure BSA00000419486100035
Silk screen printing front, backplate and back of the body surface field.With traditional handicraft slightly different be, the silver of printed back electrode and electric field slurry and aluminium paste figure adopt the grid line structure, printing aluminium paste earlier, back printed silver is starched the covering aluminium paste;
Figure BSA00000419486100036
Sintering makes silver electrode (6) and n+ emitter (301) and back electrode (5) form ohmic contact with p type substrate (302).
The invention has the advantages that:
The 1 battery structure front surface first amorphous nickel/phosphorus/aluminium oxide layer of the present invention passivation emitter surface preferably, by regulating the refractive index of amorphous silicon nitride, hydrogen content and thickness can effectively improve antireflective property;
2 the present invention have n+ emitter (301) surface passivation dielectric layer and compare with the traditional silk-screened battery with the battery of p type substrate (302) surface recombination passivation dielectric layer, increase this double-layer structure, passivation battery surface preferably, especially the back of the body surface of main flow P type crystal silicon solar energy battery, composite passivated dielectric layer plays the double effects of a chemical passivation and a passivation, passivation effect is good, reduces recombination losses, and strengthens the reflection efficiency raising long wave response of infrared light.
3 the present invention adopt sol-gel process to prepare alumina sol, then at p type substrate process HNO 3And H 2O 2N+ emitter (301) surface and p type substrate (302) the surface preparation passivation dielectric layer amorphous nickel/phosphorus/aluminium oxide thin-film material of the p type silicon base (3) that mixed solution was handled, form composite passivated dielectric layer structure on p type substrate (302) surface, preparation technology is simple, equipment investment is few, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 the present invention has front surface passivated reflection reducing layer and back of the body surface recombination passivation dielectric layer crystal silicon solar energy battery structure.
Fig. 2 traditional silk-screened crystal-silicon solar cell manufacture craft flow chart, wherein:
A removes the damage of p type silicon face, making herbs into wool, cleans;
B diffusion back forms the pn+ knot;
C removes peripheral pn+ knot;
D PECVD deposited amorphous silicon nitride layer;
E silk screen printing tow sides and sintering form ohmic contact.
Fig. 3 the present invention has a kind of preparation technology's flow process of described structure solar cell, wherein:
A removes surface damage, making herbs into wool, cleans;
Form the pn+ knot after the b diffusion etching;
C p type substrate surface is handled and is formed silicon oxide layer, n+ emitter surface and p type substrate surface preparation amorphous nickel/phosphorus/aluminium oxide film;
D PECVD deposited amorphous silicon nitride layer;
E silk screen printing tow sides and sintering form ohmic contact.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
As shown in Figure 3, a kind of structure of crystal-silicon solar cell.Its preparation process is as follows:
1. remove p type silicon base surface damage, acid or alkali lye making herbs into wool and form anti-reflection structure and chemical cleaning;
2. in the POCl3 atmosphere, spread and remove peripheral pn knot and phosphorosilicate glass formation pn+ structure by etching;
3. adopt volume ratio HNO3: H2O2=10: 1 mixed solution soaked p type substrate surface 30 minutes; Wherein HNO3 concentration is 68%, and H2O2 is that concentration is 30%;
4. adopt the silica sol of sol-gel process preparation, its step is as follows:
A pours aluminium isopropoxide into hydrolysis in the boiling water that contains part nitric acid under strong mixing, continue to stir; Temperature drops to 90 ℃ after 30 minutes.
B added red fuming nitric acid (RFNA) after 60 minutes, promptly obtained the alumina sol clarified, natural cooling;
5. adopt czochralski method to prepare front surface and back of the body surface alumina oxide film on pn+ that step 3 obtains knot silicon base, 500 ℃ of annealing are after 30 minutes, the about 15nm of n+ emitter surface amorphous nickel/phosphorus/aluminium oxide thickness, the composite passivated thickness of dielectric layers 17nm of p type substrate surface;
6. adopting conventional P ECVD deposit 70nm refractive index on n+ emitter surface amorphous nickel/phosphorus/aluminium oxide layer is 2.33 amorphous silicon nitride films;
7. silk screen printing front, backplate and back of the body surface field, the silver slurry and the aluminium paste figure of printed back electrode and electric field adopt the grid line structure, printing aluminium paste earlier, back printed silver is starched the covering aluminium paste;
8. sintering makes silver electrode and n+ emitter and back electrode and p type substrate formation ohmic contact.
Embodiment 2:
With embodiment 1, prepare the amorphous nickel/phosphorus/aluminium oxide layer except adopting spin-coating method, n+ emitter surface amorphous nickel/phosphorus/aluminium oxide film thickness is 10nm, the composite passivated dielectric layer film thickness of p type substrate surface is 50nm.

Claims (2)

1. crystal-silicon solar cell, it is characterized in that: the structure of this battery is: on n+ emitter (301) surface of pn+ knot silicon base (3) thickness being arranged successively is the first amorphous nickel/phosphorus/aluminium oxide layer (2) of 10-20nm and the amorphous silicon nitride layer (1) that thickness is 60-100nm, silver electrode (6) is passed amorphous silicon nitride layer (1) and the first amorphous nickel/phosphorus/aluminium oxide layer (2) and n+ emitter (301) ohmic contact, there is composite passivated dielectric layer (4) on p type substrate (302) surface, composite passivated dielectric layer (4) is that the silicon oxide layer (401) of 1.5-3nm and the second amorphous nickel/phosphorus/aluminium oxide layer (402) that thickness is 10-100nm are formed by thickness, and back electrode (5) passes composite passivated dielectric layer (4) and p type substrate (302) ohmic contact.
2. crystal-silicon solar cell preparation method based on the described structure of claim 1 is characterized in that may further comprise the steps:
1). remove the damage of p type silicon face, acid or alkali lye making herbs into wool and form anti-reflection structure and chemical cleaning;
2). at POCl 3Spread and remove the pn+ knot silicon base (3) of peripheral pn knot and phosphorosilicate glass formation pn+ structure in the atmosphere;
3). adopt volume ratio HNO 3: H2O2=20-5: 1 mixed solution soaked p type substrate (302) surface 30 minutes; HNO wherein 3Concentration is 68%, H 2O 2For concentration is 30%;
4). adopt the alumina sol of sol-gel process preparation, its step is as follows:
(a) under strong mixing, aluminium isopropoxide is poured into hydrolysis in the boiling water that contains part nitric acid, continue to stir, temperature drops to 85-95 ℃ after 30 minutes;
(b) add red fuming nitric acid (RFNA) after 60 minutes, promptly obtain the alumina sol clarified, natural cooling;
5). the n+ emitter (301) of the pn+ knot silicon base (3) that obtains in step 3 and p type substrate (302) surface employing czochralski method or spin-coating method prepare aluminum oxide film, 400-600 ℃ of annealing is after 15-30 minute, and generating thickness is the first amorphous nickel/phosphorus/aluminium oxide layer (2) of 10-20nm and the second amorphous nickel/phosphorus/aluminium oxide layer (402) that thickness is 10-100nm;
6). adopting conventional P ECVD deposit 60-100nm refractive index on the first amorphous nickel/phosphorus/aluminium oxide layer (2) surface is the amorphous silicon nitride films formation amorphous silicon nitride layer (1) of 1.9-2.5;
7). silk screen printing front, backplate and back of the body surface field, the silver slurry and the aluminium paste figure of printed back electrode and electric field adopt the grid line structure, print aluminium paste earlier, and back printed silver slurry covers aluminium paste;
8). sintering makes silver electrode (6) and n+ emitter (301) and back electrode (5) form ohmic contact with p type substrate (302).
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Cited By (10)

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CN103311348A (en) * 2012-03-08 2013-09-18 茂迪股份有限公司 Solar energy cell and manufacturing method thereof
CN103606568A (en) * 2013-11-21 2014-02-26 常州天合光能有限公司 Film passivation structure for crystalline silica solar cell
CN104037243A (en) * 2013-03-05 2014-09-10 Lg电子株式会社 Solar Cell
CN104040701A (en) * 2012-01-06 2014-09-10 日立化成株式会社 Semiconductor substrate provided with passivation film, method for producing same, and solar cell element and method for producing same
CN106653872A (en) * 2016-11-25 2017-05-10 罗雷 Solar cell resistant to PID effect
CN107017311A (en) * 2015-11-24 2017-08-04 普兰特光伏有限公司 Sintered multilayer for integrated circuit and solar cell is stacked
CN108054242A (en) * 2017-12-15 2018-05-18 浙江晶科能源有限公司 A kind of production method of N-type single side battery
CN111710730A (en) * 2020-06-29 2020-09-25 苏州腾晖光伏技术有限公司 Novel P-type crystalline silicon solar cell and preparation method thereof
CN111834492A (en) * 2020-07-22 2020-10-27 常州时创能源股份有限公司 Preparation method of TOPCon battery
CN114944434A (en) * 2022-05-25 2022-08-26 三一集团有限公司 Crystalline silicon solar cell, preparation method thereof and photovoltaic module

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US20050194037A1 (en) * 2003-10-08 2005-09-08 Sharp Kabushiki Kaisha Method of manufacturing solar cell and solar cell manufactured thereby
CN101051657A (en) * 2006-04-05 2007-10-10 三星Sdi株式会社 Solar cell and its method of manufacture
CN101262029A (en) * 2007-03-07 2008-09-10 信越化学工业株式会社 Method for manufacturing single crystal silicon solar cell and single crystal silicon solar cell

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US20050194037A1 (en) * 2003-10-08 2005-09-08 Sharp Kabushiki Kaisha Method of manufacturing solar cell and solar cell manufactured thereby
CN101051657A (en) * 2006-04-05 2007-10-10 三星Sdi株式会社 Solar cell and its method of manufacture
CN101262029A (en) * 2007-03-07 2008-09-10 信越化学工业株式会社 Method for manufacturing single crystal silicon solar cell and single crystal silicon solar cell

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104040701A (en) * 2012-01-06 2014-09-10 日立化成株式会社 Semiconductor substrate provided with passivation film, method for producing same, and solar cell element and method for producing same
CN103311348A (en) * 2012-03-08 2013-09-18 茂迪股份有限公司 Solar energy cell and manufacturing method thereof
CN104037243A (en) * 2013-03-05 2014-09-10 Lg电子株式会社 Solar Cell
CN104037243B (en) * 2013-03-05 2016-11-02 Lg电子株式会社 Solaode
CN103606568A (en) * 2013-11-21 2014-02-26 常州天合光能有限公司 Film passivation structure for crystalline silica solar cell
CN107017311A (en) * 2015-11-24 2017-08-04 普兰特光伏有限公司 Sintered multilayer for integrated circuit and solar cell is stacked
CN107039539A (en) * 2015-11-24 2017-08-11 普兰特光伏有限公司 The method for forming the solar cell with sintered multilayer stacks of thin films
CN107017311B (en) * 2015-11-24 2019-08-02 日立化成株式会社 It is stacked for the sintered multilayer of integrated circuit and solar battery
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
CN106653872A (en) * 2016-11-25 2017-05-10 罗雷 Solar cell resistant to PID effect
CN108054242A (en) * 2017-12-15 2018-05-18 浙江晶科能源有限公司 A kind of production method of N-type single side battery
CN111710730A (en) * 2020-06-29 2020-09-25 苏州腾晖光伏技术有限公司 Novel P-type crystalline silicon solar cell and preparation method thereof
CN111834492A (en) * 2020-07-22 2020-10-27 常州时创能源股份有限公司 Preparation method of TOPCon battery
CN114944434A (en) * 2022-05-25 2022-08-26 三一集团有限公司 Crystalline silicon solar cell, preparation method thereof and photovoltaic module
CN114944434B (en) * 2022-05-25 2024-03-08 三一硅能(株洲)有限公司 Crystalline silicon solar cell, preparation method thereof and photovoltaic module

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