CN101937947A - Aluminium and boron codoped silicon solar cell back surface field and manufacturing method thereof - Google Patents

Aluminium and boron codoped silicon solar cell back surface field and manufacturing method thereof Download PDF

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Publication number
CN101937947A
CN101937947A CN2010102830687A CN201010283068A CN101937947A CN 101937947 A CN101937947 A CN 101937947A CN 2010102830687 A CN2010102830687 A CN 2010102830687A CN 201010283068 A CN201010283068 A CN 201010283068A CN 101937947 A CN101937947 A CN 101937947A
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boron
aluminium
solar cell
silicon solar
mixed slurry
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余学功
顾鑫
杨德仁
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Zhejiang University ZJU
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Zhejiang University ZJU
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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

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Abstract

The invention discloses an aluminium and boron codoped silicon solar cell back surface field and a manufacturing method thereof. The manufacturing method comprises the following steps of: adding a baron source into aluminium slurry, and uniformly stirring to obtain mixed slurry, wherein the boron element accounts for 0.01 to 3 mass percent of the mixed slurry; and performing screen printing of the mixed slurry on the back surface of a silicon solar cell, drying, sintering at the temperature of between 650 and 950 DEG C for no more than 5 minutes. The manufacturing method has the advantages of low sintering temperature and effective reduction of warping and breakage rate of the cell. Through the manufacturing method, a more uniform back surface field is formed on the back surface of the cell; and the series resistance of the silicon solar cell with the aluminium and boron codoped back surface field manufactured by the method is obviously reduced, the shunt resistance is obviously increased, the cell efficiency is greatly improved, and the cost increase can be omitted.

Description

Silicon solar cell back of the body field that a kind of aluminium boron is mixed altogether and preparation method thereof
Technical field
The invention belongs to the Application of Solar Energy field, relate in particular to silicon solar cell back of the body that a kind of aluminium boron mixes altogether and preparation method thereof.
Background technology
Solar energy is a kind of widely distributed, nexhaustible clean energy resource.Solar cell be a kind of be the device of electric energy with conversion of solar energy, but at present still not high as the crystal silicon battery conversion efficiency of photovoltaic main market players, this has had a strong impact on the popularization and the use of solar energy.
In the conventional preparation technology of silicon solar cell, the electrode at the back side contacts except two parallel silver electrodes, and remainder (except that 1-3mm place in edge is exposed) all forms the aluminium backing layer with sintering behind the method for printing screen printing aluminium paste.A remarkable advantages of this aluminium backing layer structure is exactly: in sintering process, aluminium and pasc reaction are also outwards formed silicon layer (hereinafter referred to as heavily doped layer), alusil alloy layer and the aluminium lamination of heavily doped aluminium overleaf successively by the silicon chip matrix, heavily doped layer and alusil alloy layer make the Al-pSi that becomes Schottky contacts originally become ohmic contact, reduce series resistance greatly, thereby promoted electric property.In addition, be the solar cell of p type silicon for matrix, heavily doped layer can also form pp with matrix +The height junction structure has repulsive interaction to photo-generated carrier, thereby has reduced the surface recombination of battery, increases parallel resistance, has improved battery efficiency.Because the small electric field action of aluminium backing layer, so the aluminium back of the body field that is otherwise known as.
The performance of the aluminium back of the body is except outside the Pass the uniformity with its formation has, and is also relevant with the concentration of the displacement attitude electrically active impurity of heavily doped layer, this concentration by impurity under sintering temperature the maximum solid solution degree in silicon determine.In general, its concentration is high more, and the electrode contact of battery is good more, and just the performance of aluminium back of the body field is good more.For the battery that matrix is p type silicon, the surface recombination of battery is also more little.Yet the sintering temperature of battery is generally 650-950 ℃, and in this temperature range, the maximum solid solution degree of aluminium in silicon is 5 * 10 18Individual atom/cm -3If improve the doping content of heavily doped layer, generally need to improve sintering temperature, but this may bring surfaces nitrided silicon layer to split, the aggravation of battery warpage, transition metal impurity pollutes adverse effects such as aggravation.
Summary of the invention
The invention provides the manufacture method of the silicon solar cell back of the body that a kind of aluminium boron mixes altogether, under the prerequisite that does not change original sintering temperature, improve the doping content of heavily doped layer, thereby improved the electric property of silicon solar cell aluminium back of the body field, with low cost, the easy operating of this method.
The manufacture method of the silicon solar cell back of the body field that a kind of aluminium boron is mixed altogether comprises the steps:
(1) in aluminium paste, adds the boron source, stir, obtain mixed slurry; Wherein, the mass fraction of boron element in described mixed slurry is 0.01%-3%;
(2) at the above mixed slurry of silicon solar cell back face silk screen printing, oven dry, at 650-950 ℃ of sintering, the time is no more than 5min.
In the step (1), described boron source can be solid-state boron source or liquid boron source.Wherein, solid-state boron source can be pure boron, diboron trioxide, boric acid or borate, liquid boron source can be diboron trioxide organic solution (organic solvent can be alcohols or organic acid, but is not limited only to this) or organoboron compound (as borate, but being not limited only to borate).The granular size in solid-state boron source is 0.5～10 μ m, is preferably 1-5 μ m, makes the granular size in solid-state boron source and the solid particle size in the aluminium paste be close, and can not produce harmful effect to silk-screen printing technique.
In the step (1), described aluminium paste is a used for solar batteries aluminium paste general in the prior art, comprise aluminium powder, bonding phase glass dust, organic carrier and additive composition that mean particle size is no more than 10 μ m, can buy from the market, the blissful high post of common manufacturer (Ferro) new material company, Guangzhou Ruxing Technology Co., Ltd. etc., the AL53-110 series of the blissful high post of common model (Ferro) new material company and the RX8 of Guangzhou Ruxing Technology Co., Ltd..
In the step (1), the mass fraction of described boron element in described mixed slurry is preferably 0.05%-1%, adding may cause battery efficiency to descend greater than the boron of 1% mass fraction, and adding the boron that is less than mass fraction 0.05% does not then have positive effect to the raising of battery efficiency.
In the step (2), disclosed common process in the prior art is taked in silk screen printing;
In the step (2), described sintering temperature is preferably 700-875 ℃.This temperature is the temperature range of the current employing of solar industry.
In the step (2), described sintering time is preferably and is no more than 2min.
The present invention also provides the silicon solar cell back of the body that the aluminium boron that obtained by above-mentioned manufacture method mixes altogether.
The present invention adds boron in aluminium paste, utilize the relative aluminium of boron that the characteristics of big solid solubility are arranged in silicon, when heat treatment realizes the alloying of aluminium and silicon, boron is incorporated in the heavily doped layer, obtains the very high heavily doped layer of boron and aluminium doping content and form silicon solar cell back surface field.Based on above-mentioned back of the body field technology of preparing, can obtain having the silicon solar cell of boron aluminium codope back of the body field.
With respect to prior art, the present invention has following beneficial technical effects:
(1) in the solar cell back surface field that the aluminium boron that adopts the inventive method to obtain is mixed altogether, the doping content of heavily doped layer is higher one more than the order of magnitude in the doping content of heavily doped layer than aluminium under the identical sintering temperature, thereby reduced series resistance, reduced surface recombination, increase parallel resistance, increased battery efficiency.
(2) since boron in the time of 650 ℃ the solid solubility in silicon greater than aluminium solid solubility in silicon 950 ℃ the time, and the solid solubility of boron in silicon is being to raise with temperature below 1200 ℃, therefore, take the inventive method at low temperatures sintering obtain with common process under the suitable silicon solar cell of battery efficiency that makes, and the while low-temperature sintering has reduced the warpage of battery effectively, thereby reduced the percentage of damage of battery, reduced cost.
(3) take the inventive method, can in sintering, reduce the separating out of aluminum precipitation in the back of the body, thereby form more uniform aluminum back surface field, promote the electric property of battery at cell backside.
(4) the inventive method can be ignored to the increase of cost, every watt increase cost less than ten thousand/.
In addition, the technological process simple possible that relates among the present invention has application promise in clinical practice.
Embodiment
Describe the present invention in detail below in conjunction with embodiment, but the present invention is not limited to this.
Embodiment 1
(1) buys the aluminium paste of RX8 model from Guangzhou Ruxing Technology Co., Ltd., in aluminium paste, add diboron trioxide, stir, obtain mixed slurry; Wherein, the granular size of diboron trioxide is 1-3 μ m, and the mass fraction of boron element in mixed slurry is 0.45%;
(2) silk-screen printing technique above-mentioned mixed slurry in the silk screen printing of silicon solar cell back face routinely, oven dry, at 700 ℃ of sintering, sintering time is no more than 2min more than 650 ℃.
Heavily doped layer the doping content that this embodiment obtains the back of the body field of battery is 0.9 * 10 19Atoms/cm 3Prepare silicon solar cell based on above-mentioned back of the body field, the battery series resistance is 12m Ω, parallel resistance 80 Ω, efficient 16.9%.
Comparative Examples 1
Use common process to prepare silicon solar cell, comprising:
Silicon chip cleans, acid goes to decrease and texture, pn tie printing and the sintering that forms with edge plasma etching, silicon nitride film deposition, back of the body field and positive counterelectrode, use the Al slurry do not mix B to form the back of the body, the backing layer doping content of the battery that sintering obtains under the condition identical with embodiment 1 is 3.4 * 10 17Atoms/cm 3, the battery series resistance is 20m Ω, parallel resistance 20 Ω, efficient 15.3%.
Embodiment 2
(1) aluminium paste is identical with embodiment 1, adds the diboron trioxide ethanolic solution in aluminium paste, stirs, and obtains mixed slurry; Wherein, the granular size of diboron trioxide is 1-3 μ m, and the final mass fraction of boron element in mixed slurry is 0.1%;
(2) silk-screen printing technique above-mentioned mixed slurry in the silk screen printing of silicon solar cell back face routinely, oven dry, at 750 ℃ of sintering, sintering time is no more than 2min more than 700 ℃.
Heavily doped layer the doping content that this embodiment obtains the back of the body field of battery is 8.5 * 10 18Atoms/cm 3Prepare silicon solar cell based on above-mentioned back of the body field, the battery series resistance is 8m Ω, parallel resistance 75 Ω, efficient 17.5%.
Comparative Examples 2
Use common process to prepare silicon solar cell, comprising:
Silicon chip cleans, acid goes to decrease and texture, pn tie printing and the sintering that forms with edge plasma etching, silicon nitride film deposition, back of the body field and positive counterelectrode, use the Al slurry do not mix B to form the back of the body, the backing layer doping content of the battery that sintering obtains under the condition identical with embodiment 2 is 6.3 * 10 17Atoms/cm 3, the battery series resistance is 14m Ω, parallel resistance 35 Ω, efficient 16.7%.
Embodiment 3
(1) aluminium paste is identical with embodiment 1, adds the pure boron powder in aluminium paste, stirs, and obtains mixed slurry; Wherein, the granular size of pure boron powder is 1-3 μ m, and the final mass fraction of boron element in mixed slurry is 0.8%;
(2) silk-screen printing technique above-mentioned mixed slurry in the silk screen printing of silicon solar cell back face routinely, oven dry, at 740 ℃ of sintering, sintering time is no more than 1min more than 700 ℃.
Heavily doped layer the doping content that this embodiment obtains the back of the body field of battery is 9.2 * 10 18Atoms/cm 3Prepare silicon solar cell based on above-mentioned back of the body field, the battery series resistance is 7.5m Ω, parallel resistance 81 Ω, efficient 17.6%.
Comparative Examples 3
Use common process to prepare silicon solar cell, comprising:
Silicon chip cleans, acid goes to decrease and texture, pn tie printing and the sintering that forms with edge plasma etching, silicon nitride film deposition, back of the body field and positive counterelectrode, use the Al slurry do not mix B to form the back of the body, the backing layer doping content of the battery that sintering obtains under the condition identical with embodiment 3 is 6.3 * 10 17Atoms/cm 3, the battery series resistance is 14m Ω, parallel resistance 35 Ω, efficient 16.7%.
Embodiment 4
(1) buys the aluminium paste of AL53-110 model from good fortune high post (Ferro) new material company, in aluminium paste, add solid-state boron source potassium borate, stir, obtain mixed slurry; Wherein, the granular size scope is 0.5-4 μ m, and the mass fraction of boron element in mixed slurry is 0.7%;
(2) silk-screen printing technique above-mentioned mixed slurry in the silk screen printing of silicon solar cell back face routinely, oven dry, at 800 ℃ of sintering, sintering time is no more than 1min more than 750 ℃.
Heavily doped layer the doping content that this embodiment obtains the back of the body field of battery is 3.5 * 10 19Atoms/cm 3Prepare silicon solar cell based on above-mentioned back of the body field, the battery series resistance is 4m Ω, electric 86 Ω in parallel, efficient 17.9%.
Comparative Examples 4
Use common process to prepare silicon solar cell, comprising:
Silicon chip cleans, acid goes to decrease and texture, pn tie printing and the sintering that forms with edge plasma etching, silicon nitride film deposition, back of the body field and positive counterelectrode, use the Al slurry do not mix B to form the back of the body, the backing layer doping content of the battery that sintering obtains under the condition identical with embodiment 4 is 2 * 10 18Atoms/cm 3, the battery series resistance is 11m Ω, parallel resistance 28 Ω, efficient 16.8%.

Claims (7)

1. the manufacture method of the silicon solar cell back of the body mixed altogether of an aluminium boron is characterized in that, comprises the steps:
(1) in aluminium paste, adds the boron source, stir, obtain mixed slurry; Wherein, the mass fraction of boron element in described mixed slurry is 0.01%-3%;
(2) at the above mixed slurry of silicon solar cell back face silk screen printing, oven dry, at 650-950 ℃ of sintering, the time is no more than 5min.
2. manufacture method as claimed in claim 1, it is characterized in that, in the described step (1), described boron source is solid-state boron source or liquid boron source, described solid-state boron source is pure boron, diboron trioxide, boric acid or borate, and described liquid boron source is diboron trioxide organic solution or organoboron compound.
3. manufacture method as claimed in claim 1 is characterized in that, the granular size in described solid-state boron source is 0.5～10 μ m.
4. manufacture method as claimed in claim 1 is characterized in that, the granular size in described solid-state boron source is for being 1-5 μ m.
5. manufacture method as claimed in claim 1 is characterized in that, in the described step (1), the mass fraction of described boron element in described mixed slurry is 0.05%-1%.
6. manufacture method as claimed in claim 1 is characterized in that, in the described step (2), described sintering temperature is 700-875 ℃.
7. the silicon solar cell of being mixed altogether by the aluminium boron that obtains as the arbitrary described manufacture method of claim 1～6 is carried on the back the field.
CN2010102830687A 2010-09-16 2010-09-16 Aluminium and boron codoped silicon solar cell back surface field and manufacturing method thereof Pending CN101937947A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102368411A (en) * 2011-10-26 2012-03-07 南昌大学 Preparation method of aluminum-boron alloy powder and aluminum-boron slurry of crystalline silicon cell
CN102832268A (en) * 2012-09-10 2012-12-19 中国科学院半导体研究所 Boron-aluminum co-doped back surface field silicon solar battery and preparation method thereof
CN102842492A (en) * 2012-07-24 2012-12-26 南昌大学 Crystal silicon laser-assisted aluminum-boron co-doping and electrode preparation method
JP2015041713A (en) * 2013-08-23 2015-03-02 東洋アルミニウム株式会社 Paste composition and solar battery element
CN105702321A (en) * 2014-11-04 2016-06-22 纳幕尔杜邦公司 conductive paste for a solar cell electrode
CN106784049A (en) * 2016-12-30 2017-05-31 苏州阿特斯阳光电力科技有限公司 The preparation method and its obtained battery of a kind of local doped crystal silicon solar cell
CN107068239A (en) * 2017-02-15 2017-08-18 常州大学 A kind of method that PERC solar cell aluminium paste performances are lifted based on organic boron additive

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1901234A (en) * 2006-07-17 2007-01-24 谭富彬 Synthesizing silicon solar energy cell back field aluminum conductive size
CN101401189A (en) * 2006-03-20 2009-04-01 费罗公司 Aluminum-boron solar cell contacts
CN101730941A (en) * 2007-07-09 2010-06-09 费罗公司 Solar cell contacts containing aluminum and at least one of boron, titanium, nickel, tin, silver, gallium, zinc, indium and copper

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101401189A (en) * 2006-03-20 2009-04-01 费罗公司 Aluminum-boron solar cell contacts
CN1901234A (en) * 2006-07-17 2007-01-24 谭富彬 Synthesizing silicon solar energy cell back field aluminum conductive size
CN101730941A (en) * 2007-07-09 2010-06-09 费罗公司 Solar cell contacts containing aluminum and at least one of boron, titanium, nickel, tin, silver, gallium, zinc, indium and copper

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102368411A (en) * 2011-10-26 2012-03-07 南昌大学 Preparation method of aluminum-boron alloy powder and aluminum-boron slurry of crystalline silicon cell
CN102368411B (en) * 2011-10-26 2012-12-26 南昌大学 Preparation method of aluminum-boron alloy powder and aluminum-boron slurry of crystalline silicon cell
CN102842492A (en) * 2012-07-24 2012-12-26 南昌大学 Crystal silicon laser-assisted aluminum-boron co-doping and electrode preparation method
CN102832268A (en) * 2012-09-10 2012-12-19 中国科学院半导体研究所 Boron-aluminum co-doped back surface field silicon solar battery and preparation method thereof
CN105474409B (en) * 2013-08-23 2018-02-13 东洋铝株式会社 Paste composition and solar cell device
CN105474409A (en) * 2013-08-23 2016-04-06 东洋铝株式会社 Paste composition and solar cell element
JP2015041713A (en) * 2013-08-23 2015-03-02 東洋アルミニウム株式会社 Paste composition and solar battery element
TWI632562B (en) * 2013-08-23 2018-08-11 日商東洋鋁股份有限公司 Paste composition and solar cell components
CN105702321A (en) * 2014-11-04 2016-06-22 纳幕尔杜邦公司 conductive paste for a solar cell electrode
CN105702321B (en) * 2014-11-04 2019-12-10 纳幕尔杜邦公司 Conductive paste for solar cell electrode
CN106784049A (en) * 2016-12-30 2017-05-31 苏州阿特斯阳光电力科技有限公司 The preparation method and its obtained battery of a kind of local doped crystal silicon solar cell
CN106784049B (en) * 2016-12-30 2019-12-10 苏州阿特斯阳光电力科技有限公司 Preparation method of local doped crystalline silicon solar cell and prepared cell
CN107068239A (en) * 2017-02-15 2017-08-18 常州大学 A kind of method that PERC solar cell aluminium paste performances are lifted based on organic boron additive

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