CN103951262B - Lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of glass paste - Google Patents
Lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of glass paste Download PDFInfo
- Publication number
- CN103951262B CN103951262B CN201410150480.XA CN201410150480A CN103951262B CN 103951262 B CN103951262 B CN 103951262B CN 201410150480 A CN201410150480 A CN 201410150480A CN 103951262 B CN103951262 B CN 103951262B
- Authority
- CN
- China
- Prior art keywords
- leaded
- tellurium
- tellurium bismuth
- bismuth glass
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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 discloses lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of the glass paste. The lead-tellurium-bismuth-containing glass paste is prepared by heating a mixture of 10-40% of PbO, 10-45% of TeO2 and 0.1-5% of Bi2O3 until the mixture is molten, carrying out quenching and ball milling on the obtained product so as to obtain glass particles, adding the glass particles into 10-79% of an organic medium, uniformly stirring the obtained mixture, grinding the obtained mixture until the granularity of the mixture is below 5 mu m, so that lead-tellurium-bismuth-containing glass paste is prepared. The lead-tellurium-bismuth-containing glass paste can replace traditional high-lead-content glass powder, and has the advantages of low lead content, low melting point, good adhesion, low contact resistance, high conversion efficiency and good reliability and the like; after the lead-tellurium-bismuth-containing glass paste is applied to front electrode slurry of crystalline silicon solar cells, solar cells with performances and characteristics comparable to, even more excellent than, the performances and characteristics of conventional solar cells, and the application ratio of the lead-tellurium-bismuth-containing glass paste in positive electrode slurry of solar cells is 0.1-50%.
Description
Technical field
The present invention relates to silicon wafer area of solar cell, more particularly to a kind of solaode anelectrode is with leaded tellurium bismuth
Glass paste and its preparation and application.
Background technology
General silicon wafer solaode by p-type silicon crystalline substance Semiconductor substrate, n-type diffusion layer, antireflective coating, backplate and
Front electrode etc. forms.Front electrode is usually by the way of silk screen printing, slurry to be printed on antireflective coating through 500-
At 900 DEG C, Fast Sintering is formed.The front electrode slurry that industrialized production adopts is mainly by silver, glass material and organic carrier
Form etc. component rolling.In sintering process, the effect of glass material in front electrode slurry is to melt antireflective coating and remove
Go, obtain the point contact between front electrode and n-type diffusion layer, this process is commonly referred to burn (fire-through).
In sintering process, glass material is very big on solar cell properties impact.When front electrode does not run through antireflective coating
When, the problems such as adhesion strength fluctuation being caused and stable ohmic can not be obtained between front electrode and n-type diffusion layer and contact,
Not enough Ohmic contact can cause loss during exporting, thus lead to the relatively low transformation efficiency of solaode and electric current/
The decline of voltage characteristic.If but front electrode runs through below n-type diffusion layer after running through antireflective coating and invades Semiconductor substrate,
Then p-n junction may damage, and can be adversely affected by the fill factor, curve factor that current/voltage characteristic measurement obtains.
In order to obtain suitable burn-through, preferred pair antireflective coating has the glass material of good solubility as anode silver paste
In frit.Glass material warp wherein containing lead oxide to form electrode frequently as the frit in conventional silver paste, because
The softening point of lead bearing glass can easily be accommodated, and has good adhesion with silicon substrate, can more thoroughly burn antireflective coating, preparation
Solar cell properties are good.But, recently as the raising of people's environmental consciousness, the glass material containing lead oxide is due to it
Toxicity and pollution problem, limit it and apply further.
Content of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of low lead tolerance, low melting point and stability preferably contain
Lead tellurium bismuth glass slurry and its methods for making and using same, leaded tellurium bismuth glass material and organic media are prepared by mixing into leaded by the present invention
Tellurium bismuth glass is starched, and it is advantageous in that slurry preparation is convenient, is conducive to control and the storage of glass powder particles degree, by glass powder particles
Degree is reduced to less than 5 microns, has a certain proportion of nano bismuth oxide powder simultaneously, advantageously reduces vitreous body and prepare disposed slurry
With the contact resistance of silicon chip, the glass paste adhesive force of the present invention is good, contact resistance is low, high conversion efficiency, good reliability.
The present invention be the technical scheme is that to solve its technical problem
The invention provides a kind of solaode anelectrode is starched with leaded tellurium bismuth glass, starch by described leaded tellurium bismuth glass
Total weight percent meter, its component and content are as follows:
Pbo:10-40%；
teo2: 10-45%；
bi2o3: 0.1-5%；
Organic media: 10-79%.
Further say, organic media therein can be in rosin resin, acrylic resin and celluosic resin
Kind.
Further say, the softening temperature of described leaded tellurium bismuth glass slurry is 200-400 DEG C, described leaded tellurium bismuth glass slurry
Thermal coefficient of expansion in the range of 25-300 DEG C is 100 × 10-7/℃-200×10-7/℃.
Further say, bi in described leaded tellurium bismuth glass slurry2o3Grain diameter be 10nm-5000nm, preferably
30nm-3000nm, more preferably 200nm-500nm.In described leaded tellurium bismuth glass slurry, glass powder particles degree is less than 5 μm.
Present invention also offers the preparation method that above-mentioned solaode anelectrode is starched with leaded tellurium bismuth glass, preparation process
Carry out in the steps below:
First, get the raw materials ready: according to the weight percentage of raw materials, proportioning raw materials are as follows: pbo:10-40%；teo2: 10-45%；bi2o3:
0.1-5%；Organic media: 10-79%；
2nd, by described pbo, teo2And bi2o3Heating at compound is placed in 700-1000 DEG C melts, and obtains melten glass liquid；
3rd, Quenching Treatment is carried out to described melten glass liquid, obtain granular glass；
4th, described granular glass is carried out ball milling, after sieve, obtain leaded tellurium bismuth glass material；
5th, described leaded tellurium bismuth glass material is added in described organic media, be ground after stirring, grind control
Granularity processed to less than 5 μm, starched with leaded tellurium bismuth glass by prepared solaode anelectrode.
Further say, in step 4, ball milling and after sieving particle size control at 0.2-20 μm.
Further say, in step 5, stirred using homogenizer, reuse three-roll grinder and be ground.
Present invention also offers the application process that above-mentioned solaode anelectrode is starched with leaded tellurium bismuth glass, described leaded
Use ratio in solaode anelectrode slurry for the tellurium bismuth glass slurry is 0.1-50%, preferably 2-30%, more preferably 6-
15%.
The invention has the beneficial effects as follows: the leaded tellurium bismuth glass of the present invention is starched with pbo and teo2Component is major glass shape
Adult, has the advantages that low melting temperature, highly durable and be easy to for silver to be dissolved in solid solution；And teo2There is the pole with silicon oxide
Hypoergia and wider infrared transmission area, high photoelectric coupling coefficient, preferable corrosion resistance, higher refractive index,
A series of features such as relatively low glass melting temperature, low phonon energy and preferable chemical stability.Additionally, in leaded tellurium glass material
Adding in the formula of material has bi2o3, the energy of phonon and the vitrification reducing glass material in glass material can be effectively improved
Transition temperature, can reduce the contact resistance of silicon chip of solar cell and glass paste again.Starched due to above-mentioned leaded tellurium bismuth glass and have
Higher heat stability, chemical stability and stronger corrosion resistance, and higher, anti-to silicon oxide to silver-colored solid content
Answering property is relatively low, and the softening temperature of glass material is 200-400 DEG C, and the thermal coefficient of expansion in the range of 25-300 DEG C is 100 × 10-7/℃-200×10-7/ DEG C, therefore this leaded tellurium bismuth glass slurry can substitute traditional high lead tolerance glass dust, in silicon wafer too
Sun can be applied in battery front side electrode slurry, can obtain the performance with performance and characteristic and routine solar energy electrode and characteristic phase
When even more excellent solaode.
Specific embodiment
The specific embodiment of the present invention is described below by way of specific instantiation, those skilled in the art can be by this theory
Content disclosed in bright book understands advantages of the present invention and effect easily.The present invention other different modes can also give reality
Apply, i.e. do not depart from disclosed under the scope of, different modifications and change can be given.
Embodiment:
1. weigh each raw material components according to the weight/mass percentage composition data of embodiment each in table 1 below；
2. each raw material load weighted in step 1 is mixed using ball mill, after mixing, loaded vitreous silica or corundum
In crucible, heat in high temperature furnace, temperature control, at 700-1000 DEG C, forms melten glass liquid；
3. melten glass liquid is poured into water quick cooling, then dries and obtain granular glass；
4. granular glass ball mill is milled to 0.2-20 μm (preferably 0.5-3 μm), the glass dust mistake after ball milling
Sieve, obtains the leaded tellurium bismuth glass material of powdery；
5. take in the leaded tellurium bismuth glass material addition organic media of powdery that step 4 obtains, homogenizer stirring is all
After even, using three-roll grinder, its granularity is down to less than 5 microns.Wherein, organic media can be in rosin resin, acrylic acid
Resin and this several big apoplexy due to endogenous wind of celluosic resin are chosen.Wherein, bi2o3Grain diameter be 10nm-5000nm, preferably
30nm-3000nm, more preferably 200nm-500nm.
The leaded tellurium bismuth glass material taking the powdery that step 4 obtains adopts differentia scanning calorimetry (dsc method) in right amount
Test softening point temperature, result see table 1.
Table 1
Above-mentioned glass paste instead of traditional lead bearing glass with the lead tellurium bismuth glass of low melting temperature, the glass material obtaining
Eutectic and stability is preferable.The softening temperature of this leaded tellurium bismuth glass slurry is 200-400 DEG C.
Above-mentioned leaded tellurium bismuth glass is starched with pbo and teo2Component is main glass former, has low melting temperature, highly
Durable and be easy to the advantage that silver is dissolved in solid solution；And teo2Have infrared with silicon oxide extremely low reactive and wider
Cross area, high photoelectric coupling coefficient, preferable corrosion resistance, higher refractive index, relatively low glass melting temperature, low phonon energy
A series of features such as amount and preferable chemical stability.Additionally, add in the formula of leaded tellurium glass material thering is bi2o3, permissible
Effectively improve the energy of phonon and the glass transition temperature reducing glass material in glass material, solar-electricity can be reduced again
Pond silicon chip and the contact resistance of glass paste.Starched due to above-mentioned leaded tellurium bismuth glass and there is higher heat stability, chemical stability
And stronger corrosion resistance, and, the softening temperature of glass material higher, relatively low to the reactivity of silicon oxide to silver-colored solid content
Spend for 200-400 DEG C, the thermal coefficient of expansion in the range of 25-300 DEG C is 100 × 10-7/℃-200×10-7/ DEG C, therefore this contains
Lead tellurium bismuth glass slurry can substitute traditional high lead tolerance glass dust, should in silicon wafer front electrode of solar battery slurry
With the performance with performance and characteristic and conventional solar energy electrode and the suitable even more excellent solaode of characteristic can be obtained.
Use ratio in solaode anelectrode slurry for the described leaded tellurium bismuth glass slurry is 0.1-50%, preferably
2-30%, more preferably 6-15%.
Embodiment described above only have expressed the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Therefore limiting the scope of the invention can not be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, some deformation can also be made and improve, these broadly fall into the guarantor of the present invention
Shield scope.Therefore, protection scope of the present invention should be defined by claim.
Claims (8)
1. a kind of solaode anelectrode is starched with leaded tellurium bismuth glass it is characterised in that starch total by described leaded tellurium bismuth glass
Weight 100% percentages, its component and content are as follows:
Pbo:10-40%；
teo2: 10-45%；
bi2o3: 0.1-5%；
Organic media: 60-79%；
The softening temperature of described leaded tellurium bismuth glass slurry is 200-400 DEG C, and described leaded tellurium bismuth glass is starched in 25-300 DEG C of scope
Interior thermal coefficient of expansion is 100 × 10-7/℃-200×10-7/℃；
Bi in described leaded tellurium bismuth glass slurry2o3Grain diameter be 10nm-5000nm, glass in described leaded tellurium bismuth glass slurry
Powder particles degree is less than 5 μm.
2. solaode anelectrode as claimed in claim 1 is starched it is characterised in that described organic Jie with leaded tellurium bismuth glass
Matter is one of rosin resin, acrylic resin and celluosic resin.
3. the preparation method that a kind of solaode anelectrode is starched with leaded tellurium bismuth glass is it is characterised in that preparation process is pressed
State step to carry out:
First, get the raw materials ready: according to the weight percentage of raw materials, proportioning raw materials are as follows: pbo:10-40%；teo2: 10-45%；bi2o3:
0.1-5%；Organic media: 60-79%；
2nd, by described pbo, teo2And bi2o3Heating at compound is placed in 700-1000 DEG C melts, and obtains melten glass liquid；
3rd, Quenching Treatment is carried out to described melten glass liquid, obtain granular glass；
4th, described granular glass is carried out ball milling, after sieve, obtain leaded tellurium bismuth glass material；
5th, described leaded tellurium bismuth glass material is added in described organic media, be ground after stirring, grinding control
Granularity to less than 5 μm, starched with leaded tellurium bismuth glass by prepared solaode anelectrode.
4. solaode anelectrode as claimed in claim 3 is starched with leaded tellurium bismuth glass preparation method it is characterised in that
In step 4, ball milling and after sieving particle size control at 0.2-20 μm.
5. solaode anelectrode as claimed in claim 3 is starched with leaded tellurium bismuth glass preparation method it is characterised in that
In step 5, stirred using homogenizer, reuse three-roll grinder and be ground.
6. the application side that the solaode anelectrode as described in a kind of any one as claim 1 to 5 is starched with leaded tellurium bismuth glass
Method is it is characterised in that use ratio in solaode anelectrode slurry for the described leaded tellurium bismuth glass slurry is 0.1-50%.
7. solaode anelectrode as claimed in claim 6 is starched with leaded tellurium bismuth glass application process it is characterised in that
Use ratio in solaode anelectrode slurry for the described leaded tellurium bismuth glass slurry is 2-30%.
8. solaode anelectrode as claimed in claim 7 is starched with leaded tellurium bismuth glass application process it is characterised in that
Use ratio in solaode anelectrode slurry for the described leaded tellurium bismuth glass slurry is 6-15%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410150480.XA CN103951262B (en) | 2014-04-15 | 2014-04-15 | Lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of glass paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410150480.XA CN103951262B (en) | 2014-04-15 | 2014-04-15 | Lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of glass paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103951262A CN103951262A (en) | 2014-07-30 |
| CN103951262B true CN103951262B (en) | 2017-01-25 |
Family
ID=51328654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410150480.XA Expired - Fee Related CN103951262B (en) | 2014-04-15 | 2014-04-15 | Lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of glass paste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103951262B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101696985B1 (en) | 2014-12-30 | 2017-01-17 | 삼성에스디아이 주식회사 | Composition for forming solar cell electrode and electrode prepared using the same |
| US20170144920A1 (en) * | 2015-11-20 | 2017-05-25 | Giga Solar Materials Corp. | Crystalline oxides, preparation thereof and conductive pastes containing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354544A (en) * | 2011-09-21 | 2012-02-15 | 江苏泓源光电科技有限公司 | Silver conductive paste for front electrode of crystalline silicon solar cell and preparation method thereof |
| CN103000249A (en) * | 2012-12-28 | 2013-03-27 | 上海匡宇电子技术有限公司 | Solar cell front-side silver paste and preparation method thereof |
| CN103400634A (en) * | 2013-07-22 | 2013-11-20 | 上海玻纳电子科技有限公司 | Conductive silver paste used for crystalline silicon solar cell front electrode and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101569567B1 (en) * | 2010-05-04 | 2015-11-16 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Thick-film pastes containing lead-tellurium-boron-oxides, and their use in the manufacture of semiconductor devices |
| CN102097183B (en) * | 2011-02-24 | 2012-05-30 | 苏州晶银新材料股份有限公司 | Process for preparing conductive slurry for crystalline silicon solar cell front electrode |
-
2014
- 2014-04-15 CN CN201410150480.XA patent/CN103951262B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354544A (en) * | 2011-09-21 | 2012-02-15 | 江苏泓源光电科技有限公司 | Silver conductive paste for front electrode of crystalline silicon solar cell and preparation method thereof |
| CN103000249A (en) * | 2012-12-28 | 2013-03-27 | 上海匡宇电子技术有限公司 | Solar cell front-side silver paste and preparation method thereof |
| CN103400634A (en) * | 2013-07-22 | 2013-11-20 | 上海玻纳电子科技有限公司 | Conductive silver paste used for crystalline silicon solar cell front electrode and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| xTeO2-(98-x)PbO-2Bi2O3玻璃的结构表征及在硅太阳能电池正面银浆中的应用;皮鑫鑫 等;《人工晶体学报》;20130715;第42卷(第7期);摘要、2.1节、2.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103951262A (en) | 2014-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107746184B (en) | Glass powder composition, conductive silver paste containing glass powder composition and preparation method of conductive silver paste | |
| CN101271928B (en) | Method for producing high-viscosity solar cell front side silver paste and the same | |
| CN100446277C (en) | Aluminum back-surface-field conductive paste composition in silicon solar cell and method for preparing same | |
| CN102898024A (en) | Tellurium-containing glass material and preparation method and application thereof | |
| WO2020220393A1 (en) | Glass powder and silver aluminum paste comprising the same and used on front side of n-type double-sided solar cell | |
| CN101425545A (en) | Environment protection type silicon solar cell back electric field aluminum pulp and producing method thereof | |
| CN106458708A (en) | Conductor for a solar cell | |
| CN102629496A (en) | Crystalline silicon solar battery front side electrode lead-free conductive lead slurry and preparation method of crystalline silicon solar battery front side electrode lead-free conductive lead slurry | |
| CN104681122B (en) | Silver paste for front surface of solar battery and preparation method of silver paste | |
| CN104376894B (en) | Solar cell conductive front side silver paste | |
| CN102354545A (en) | Sliver electrode slurry for back electric field of silicon solar cell and preparation method thereof | |
| EP2847139A1 (en) | Glass composition and its use in conductive silver paste | |
| CN102956283A (en) | Novel lead-free sliver slurry for high-efficiency crystalline silicon solar battery as well as preparation and application thereof | |
| CN102496418B (en) | Crystalline silicon solar cell back surface field aluminum alloy slurry and preparation method thereof | |
| CN109180008A (en) | Cryogenic glass powder, preparation method and the front electrode silver slurry containing the glass powder | |
| CN106098144A (en) | A kind of glass dust and with its solar cell front side silver paste prepared and preparation method thereof | |
| CN110364286A (en) | A kind of two-sided PERC cell backside electrode silver plasm of monocrystalline and preparation method thereof | |
| CN105000806A (en) | Lead-free glass powder for back silver paste of silicon-based solar battery and preparation method of lead-free glass powder | |
| CN104478222A (en) | Lead-free glass powder applicable to crystalline silicon solar cell back silver paste and preparation method of lead-free glass powder | |
| CN110289121B (en) | Alloy aluminum paste for back of PERC solar cell | |
| CN106504814B (en) | Glass dust, positive silver paste and preparation method thereof | |
| CN113035975A (en) | Glass powder and preparation method thereof, conductive silver paste and preparation method and application thereof | |
| CN103531266A (en) | Wafer solar battery back electrode silver paste and preparing method thereof | |
| CN103951262B (en) | Lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of glass paste | |
| CN102760511B (en) | Crystalline silicon solar cell BSF (back surface field) lead-free aluminum electroconductive slurry and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170125 Termination date: 20190415 |