CN102762509B - Low melting glass composition and use its conducting paste material - Google Patents

Low melting glass composition and use its conducting paste material Download PDF

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Publication number
CN102762509B
CN102762509B CN201180009596.6A CN201180009596A CN102762509B CN 102762509 B CN102762509 B CN 102762509B CN 201180009596 A CN201180009596 A CN 201180009596A CN 102762509 B CN102762509 B CN 102762509B
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Prior art keywords
glass
solar cell
conductive paste
semiconductor substrate
zno
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Expired - Fee Related
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CN201180009596.6A
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CN102762509A (en
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滨田润
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Central Glass Co Ltd
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Central Glass Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • 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

Abstract

Disclosed by the invention is SiO 2-B 2o 3-ZnO-RO-R 2o system Unlead low-smelting point glass, its contain be in mass % 1 ~ 15 SiO 2, 18 ~ 30 B 2o 3, 0 ~ 10 Al 2o 3, the ZnO of 25 ~ 43, the RO(MgO+CaO+SrO+B of 8 ~ 30? aO), the R of 6 ~ 17 2o(Li 2o+Na 2o+K 2o).High current collecting efficiency can be obtained when conductive paste containing this glass is used for crystal silicon solar energy battery.

Description

Low melting glass composition and use its conducting paste material
Technical field
The present invention relates to a kind of low melting glass composition, its be especially formed crystal silicon solar energy battery electrode in, good electrical characteristic can be obtained and the unleaded conducting paste material good with the adaptation of silicon semiconductor substrate.
Background technology
As the electronic unit using silicon semiconductor substrate, there will be a known solar cell device as shown in Figure 1.As shown in Figure 1, solar cell device is that the light receiving surface side of the p-type semiconductor silicon substrate 1 of about 200 μm is formed with n-type semiconductor silicon layer 2 at thickness, be formed with the anti-reflective films 3 such as the silicon nitride film improving light receiving efficiency at light receiving surface side surface, this anti-reflective film 3 is formed the surface electrode 4 be connected with semi-conductor.In addition, in the rear side of p-type semiconductor silicon substrate 1, be similarly formed with aluminium electrode layer 5.
This aluminium electrode layer 5 is usually formed by the following method: the Aluminum Paste material using the coatings such as silk screen printing to be made up of aluminium powder form, glass powder, organic excipients containing the tackiness agent such as ethyl cellulose, acrylic resin, at the temperature of about 600 ~ 900 DEG C, carry out short period of time roasting.
In the roasting of this Aluminum Paste, aluminium is diffused in p-type semiconductor silicon substrate 1, thus formed between aluminium electrode layer 5 and p-type semiconductor silicon substrate 1 be called as BSF(BackSurfaceField) the Si-Al Eutectic Layer of layer 6, and then form the impurity layer p that the diffusion due to aluminium formed +layer 7.
This p +layer 7 has the effect of the loss caused by combining again of the current carrier suppressing to be generated by the photovoltaic effect of p-n junction, contributes to the efficiency of conversion improving solar cell device.
About this BSF effect, disclose and can obtain high effect (such as with reference to patent documentation 1,2) containing plumbous glass as the glass powder contained by Aluminum Paste by using.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-59380 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-165744 publication
Summary of the invention
the problem that invention will solve
But although lead composition makes glass be the very important composition in low melting point aspect, the harm caused human body, environment is larger.There is the problem containing lead composition in above-mentioned Japanese Unexamined Patent Publication 2007-59380 publication, glass powder disclosed in Japanese Unexamined Patent Publication 2003-165744 publication.
for the scheme of dealing with problems
The invention provides SiO 2-B 2o 3-ZnO-RO-R 2o system Unlead low-smelting point glass (the 1st glass), it is for using low melting glass contained in the conductive paste used in the solar cell of silicon semiconductor substrate, it is characterized in that, the composition of this glass does not contain lead composition in fact, and containing being the SiO of 1 ~ 15 in mass % 2, 18 ~ 30 B 2o 3, 0 ~ 10 Al 2o 3, the ZnO of 25 ~ 43, the RO(of 8 ~ 30 be selected from the summation of more than a kind in MgO, CaO, SrO, BaO) and 6 ~ 17 R 2o(is selected from Li 2o, Na 2o, K 2the summation of more than a kind in O).
1st glass may also be Unlead low-smelting point glass (the 2nd glass), it is characterized in that, its thermal expansivity at 30 DEG C ~ 300 DEG C is 80 × 10 -7/ DEG C ~ 130 × 10 -7/ DEG C, softening temperature is more than 400 DEG C and less than 550 DEG C.
In addition, the invention provides conductive paste, solar cell device or electronic material substrate, it is characterized in that, it contains the 1st glass or the 2nd glass.
Accompanying drawing explanation
Fig. 1 is the general profile chart of the common crystal silicon solar energy battery unit that can use conductive paste of the present invention.
Embodiment
By using the conducting paste material containing lead-free glass powder with low melting point of the present invention, high BSF effect can be obtained.In addition, the good adaptation with silicon semiconductor substrate can be obtained.And then, because in fact not containing lead composition, so do not work the mischief to human body, environment.
Conducting paste material of the present invention is a kind of SiO 2-B 2o 3-ZnO-RO-R 2o system Unlead low-smelting point glass, is characterized in that, this Unlead low-smelting point glass comprises aluminium powder form, organic excipients containing the tackiness agent such as ethyl cellulose, acrylic resin, also comprise glass powder, glass powder does not contain lead composition in fact, and containing being the SiO of 1 ~ 15 in mass % 2, 18 ~ 30 B 2o 3, 0 ~ 10 Al 2o 3, the ZnO of 25 ~ 43, the RO(MgO+CaO+SrO+BaO of 8 ~ 30) and 6 ~ 17 R 2o(Li 2o+Na 2o+K 2o).
In glass powder of the present invention, SiO 2glass forming constituents, by making itself and the B as other glass forming constituents 2o 3coexist, stable glass can be formed, so at 1 ~ 15%(quality %, lower with) scope in containing SiO 2.SiO 2during more than 15%, the softening temperature of glass rises, and plasticity, workability become difficulty.SiO 2be more preferably the scope of 2 ~ 14%.
B 2o 3be glass forming constituents, it makes glass melting become easy, suppresses the thermal expansivity of glass excessively to rise, and gives the mobility of glass appropriateness during sintering, the specific inductivity of glass is declined.Scope with 18 ~ 30% in glass contains B 2o 3.B 2o 3lower than 18% time, the mobility of glass becomes insufficient, and coking property is impaired.In addition, B 2o 3during more than 30%, the stability of glass is declined.B 2o 3be more preferably the scope of 19 ~ 27%.
Al 2o 3it is the composition suppressing the crystallization of glass and make its stabilization.Preferably contain Al with the scope of 0 ~ 10% in glass 2o 3.Al 2o 3during more than 10%, the softening temperature of glass rises, and plasticity, workability become difficulty.
ZnO is the composition of the softening temperature reducing glass, contains in glass with the scope of 25 ~ 43%.ZnO lower than 25% time, can not play above-mentioned effect, when ZnO is more than 43%, glass becomes instability and easily produces crystallization.ZnO is preferably the scope of 28 ~ 42%.
RO(MgO+CaO+SrO+BaO) be reduce glass softening temperature, moderately give the material of mobility, contain with the scope of 8 ~ 30% in glass.RO lower than 8% time, the decline of the softening temperature of glass is insufficient, and coking property is impaired.In addition, when RO is more than 30%, the thermal expansivity of glass becomes too high.RO is more preferably the scope of 10 ~ 27%.
R 2o(Li 2o, Na 2o, K 2o) be reduce glass softening temperature, moderately give mobility, thermal expansivity is adjusted to suitable scope in material, contain with the scope of 6 ~ 17%.R 2o lower than 6% time, the decline of the softening temperature of glass is insufficient, and coking property is impaired.In addition, R 2when O is more than 17%, then thermal expansivity is made excessively to increase.R 2o is more preferably the scope of 8 ~ 15%.
In addition, also CuO, TiO can be added 2, In 2o 3, Bi 2o 3, SnO 2, TeO 2etc. common oxide compound.
Low melting glass of the present invention is not in fact containing PbO.Herein, what is called in fact refers to containing PbO, the amount of degree of PbO for being mixed into as impurity in frit.Such as, if PbO is the scope of below 0.3 quality % in low melting glass, then there is aforesaid harm hardly, namely there is not the impact on human body, environment and the impact on insulation characterisitic etc., in fact not by the impact of PbO.
According to the present invention, provide a kind of conducting paste material, it is characterized in that, the thermal expansivity at 30 DEG C ~ 300 DEG C of aforementioned low melting glass is 80 × 10 -7/ DEG C ~ 130 × 10 -7/ DEG C, softening temperature is more than 400 DEG C and less than 550 DEG C.Thermal expansivity is not 80 × 10 -7/ DEG C ~ 130 × 10 -7/ DEG C scope time, to peel off when electrode is formed, the problem such as the warpage of substrate.Thermal expansivity at 30 DEG C ~ 300 DEG C is preferably 85 × 10 -7/ DEG C ~ 125 × 10 -7/ DEG C scope.
In addition, when softening temperature is more than 550 DEG C, because can not flow fully during roasting, so problems such as the adaptation variation of generation and silicon semiconductor substrate.Softening temperature is preferably more than 420 DEG C and less than 520 DEG C.
In addition, above-mentioned conducting paste material can be used for solar cell device or electronic material substrate.
Embodiment
Below, be described based on embodiment.
conducting paste material
First, for glass powder, according to the specific composition recorded in embodiment the various inorganic raw material of mode weighing and mix, raw materials masterbatch.This raw material masterbatch is dropped into platinum crucible, with 1000 ~ 1300 DEG C, 1 ~ 2 hour heating and melting in electrical heater, obtains the glass of the composition as shown in the comparative example 1 ~ 4 of the embodiment 1 ~ 5 of table 1, table 2.A part for glass flows in mould, is formed block, and heat supply physical property (thermal expansivity, softening temperature) measures and uses.Remaining glass utilizes the two roller forming mill of chilling to form sheet, is granulated as Powdered lower than 10 μm of median size 1 ~ 4 μm, maximum particle diameter by shredding unit.
Then, in the pasty state oil (pasteoil) be made up of alpha-terpineol and acetate of butyl carbitol, using specified proportion mixing as the ethyl cellulose of tackiness agent and above-mentioned glass powder and the aluminium powder form as electroconductive powder, preparation viscosity is the conductive pastes of 500 ± 50 pool left and right.
Be explained, softening temperature uses apparatus for thermal analysis TG-DTA(RigakuCorporation system) measure.In addition, obtained by the elongation at 30 ~ 300 DEG C when thermal expansivity is and uses dilatometer to heat up with 5 DEG C/min.
Then, p-type semiconductor silicon substrate 1 is prepared, the above-mentioned conductive paste prepared of silk screen printing at an upper portion thereof.These test films are utilized the drying machine of 140 DEG C carry out 10 minutes dry, then, by with electric furnace roasting 1 minute under 800 DEG C of conditions, obtain the structure being formed with aluminium electrode layer 5 and BSF layer 6 on p-type semiconductor silicon substrate 1.
For the sample obtained like this, utilize the surface resistivity of 4 probe-type surface resistivity testers mensuration to the influential aluminium electrode layer 5 of interelectrode ohmic resistance.
Then, be investigation aluminium electrode layer 5 and the adaptation of p-type semiconductor silicon substrate 1, scotch tape (Nichiban system) be attached on aluminium electrode layer 5, the exfoliation state of the aluminium electrode layer 5 when visual assessment is peeled off.
Then, the p-type semiconductor silicon substrate 1 being formed with aluminium electrode layer 5 is impregnated in aqueous sodium hydroxide solution, makes p by etching aluminium electrode layer 5 and BSF layer 6 +layer 7 is exposed to surface, utilizes 4 probe-type surface resistivity testers to measure p +the surface resistivity of layer 7.
P +the surface resistivity of layer 7 is relevant with BSF effect, p +the surface resistivity of layer 7 is lower, then BSF effect is higher, and the efficiency of conversion as solar cell device is higher.Herein, by p +the target value of the surface resistivity of layer 7 is set to 35 Ω/below.
result
Unlead low-smelting point glass composition and various test-results illustrate in table.
[table 1]
[table 2]
As shown in the embodiment 1 ~ 5 in table 1, in compositing range of the present invention, also good with the adaptation of p-type semiconductor silicon substrate 1.Especially relevant to the efficiency of conversion of solar cell device p +the resistance value of layer 7 is also low, and the conductive paste being suitable as crystal silicon solar energy battery uses.
In addition, softening temperature is 400 DEG C ~ 550 DEG C, has suitable thermal expansivity 80 × 10 -7/ DEG C ~ 130 × 10 -7/ DEG C.
On the other hand, exceed the comparative example 1 ~ 4 in the table 2 of compositing range of the present invention, the good adaptation with p-type semiconductor silicon substrate 1, p can not be obtained +the resistance value of layer 7 is high, or after melting, glass display goes out deliquescence etc., and the conductive paste being not suitable as crystal silicon solar energy battery uses.
description of reference numerals
1p N-type semiconductorN silicon substrate
2n N-type semiconductorN silicon layer
3 anti-reflective films
4 surface electrodes
5 aluminium electrode layers
6BSF layer
7P +layer

Claims (6)

1. using the conductive paste used in the solar cell of silicon semiconductor substrate, it is characterized in that, it is SiO 2-B 2o 3-ZnO-RO-R 2o system Unlead low-smelting point glass, comprises aluminium powder form, organic excipients and glass powder in conductive paste, and glass powder in fact not containing lead composition, and in mass %, contains:
The SiO of 1 ~ 15 2,
The B of 18 ~ 30 2o 3,
The Al of 0 ~ 10 2o 3,
The ZnO of 25 ~ 43,
The RO of 8 ~ 30, and,
The R of 6 ~ 17 2o,
Wherein RO refers to the summation of more than a kind of being selected from MgO, CaO, SrO, BaO, R 2o refers to and is selected from Li 2o, Na 2o, K 2the summation of more than a kind in O.
2. the conductive paste used in the solar cell of use silicon semiconductor substrate according to claim 1, it is characterized in that, the thermal expansivity at 30 DEG C ~ 300 DEG C of described Unlead low-smelting point glass is 80 × 10 -7/ DEG C ~ 130 × 10 -7/ DEG C, softening temperature is more than 400 DEG C and less than 550 DEG C.
3. the conductive paste that uses in the solar cell using silicon semiconductor substrate according to claim 1 and 2, is characterized in that, described Unlead low-smelting point glass contain be in mass % 2 ~ 14 SiO 2, 19 ~ 27 B 2o 3, 28 ~ 42 ZnO, the RO of 10 ~ 27, the R of 8 ~ 15 2o.
4. a solar cell device, is characterized in that, it contains the conductive paste used in the solar cell of use silicon semiconductor substrate of claim 1 or claim 2.
5. an electronic material substrate, is characterized in that, it contains the conductive paste used in the solar cell of use silicon semiconductor substrate of claim 1 or claim 2.
6. a manufacture method for solar cell device, it uses the conductive paste used in the solar cell of use silicon semiconductor substrate according to any one of claim 1 to 3.
CN201180009596.6A 2010-03-28 2011-03-18 Low melting glass composition and use its conducting paste material Expired - Fee Related CN102762509B (en)

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JP2010073963A JP5569094B2 (en) 2010-03-28 2010-03-28 Low melting point glass composition and conductive paste material using the same
JP2010-073963 2010-03-28
PCT/JP2011/056526 WO2011122369A1 (en) 2010-03-28 2011-03-18 Low-melting-point glass composition, and electrically conductive paste material produced using same

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JP5888493B2 (en) * 2011-02-10 2016-03-22 セントラル硝子株式会社 Conductive paste and solar cell element using the conductive paste
CN103915127B (en) * 2013-01-03 2017-05-24 上海匡宇科技股份有限公司 Front silver paste for high sheet resistance silicon-based solar cell and preparing method of front silver paste
JP6398351B2 (en) 2013-07-25 2018-10-03 セントラル硝子株式会社 Phosphor dispersed glass
DE102015207697A1 (en) * 2014-04-25 2015-10-29 Ceramtec Gmbh Aluminum paste for thick film hybrid
CN104402234B (en) * 2014-11-13 2016-09-21 海安建海新能源有限公司 Crystal silicon solar energy battery front side silver paste glass dust and preparation method thereof
CN110550864B (en) * 2019-09-29 2022-09-02 长沙新材料产业研究院有限公司 Low-expansion-coefficient insulating medium slurry and preparation method thereof

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TWI469944B (en) 2015-01-21
CN102762509A (en) 2012-10-31
WO2011122369A1 (en) 2011-10-06
JP5569094B2 (en) 2014-08-13
TW201141809A (en) 2011-12-01
JP2011207629A (en) 2011-10-20

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