CN102344249A - Glass material and conductive thickener and electronic components using the same - Google Patents
Glass material and conductive thickener and electronic components using the same Download PDFInfo
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- CN102344249A CN102344249A CN2011101886478A CN201110188647A CN102344249A CN 102344249 A CN102344249 A CN 102344249A CN 2011101886478 A CN2011101886478 A CN 2011101886478A CN 201110188647 A CN201110188647 A CN 201110188647A CN 102344249 A CN102344249 A CN 102344249A
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Abstract
Provided is a glass material for forming conductive partical adhesive of the conductive layer (electrode) having excellent durability against corrosive gas and so on. Substantially, the glass material does not contain Pb and Mn. The glass material, converted via oxidizing material, comprises V2O5 ranging from 20mol% to 80mol%, Zn0 ranging from 5mol% to 45mol%, BaO ranging from 0mo1% to 40mol%, Sb2O3 ranging from 0mol% to 15mol%, and P2O5 ranging from 0mol% to 40mol%, with 50% of partical size D50 ranging from 0.1micron to 5.0 microns. The invention provides a conductive thickener containing the glass material at a ratio ranging from 0.1 parts to 10 parts relative to the conductive metal powder of 100 parts by mass and containing the organic carrier as well.
Description
Technical field
The present invention relates to frit and use the conductive paste and the electron device of this frit.
Background technology
All the time, the electron device that on the semiconductor substrate of silicon (Si) etc., is formed with the conductive layer that becomes electrode is used to various uses.
This conductive layer that becomes electrode forms as follows: the conductive metal powder and the frit of aluminium (Al) or silver (Ag), copper (Cu) etc. are scattered in the organic carrier; The conductive paste of gained is coated on the semiconductor substrate, under the temperature more than the fusing point of conductive metal powder, burnt till.
All the time,, adopt the material that contains plumbous oxide, but, require to adopt lead-free composition owing to reasons such as environment protection as the frit that mixes conductive paste.In addition, the conductive layer that also requires to become electrode is good for the weather resistance of corrosive gases etc.But, use the conductive paste of frit in the past can't fully satisfy such requirement.
In addition, as the thick membrane electrode wiring material, propose to have that to comprise with the vanadium oxide be the glass composition of main component and the material of silver powder (for example with reference to patent documentation 1).
Yet the electrode wiring material that is disclosed in the patent documentation 1 is owing to comprise the MnO more than the 5 weight % in glass composition
2, the therefore easy flowability that hinders glass, the silver electrode that is formed by this electrode materials is not enough for the weather resistance of corrosive gases.
Patent documentation 1: Japanese Patent Laid is opened the 2009-209032 communique
Summary of the invention
The present invention is the invention of accomplishing in order to solve above-mentioned problem, and its purpose is to provide the electroconductive particle tackiness agent frit that can form for the weather resistance favorable conductive layer (electrode) of corrosive gases etc.
Frit of the present invention is characterised in that, does not contain Pb and Mn in fact, and converting with oxide compound comprises the V below the above 80mol% of 20mol%
2O
5, the Sb below the following above 15mol% of BaO, 0mol% of the following above 40mol% of ZnO, 0mol% of the above 45mol% of 5mol%
2O
3, the following P of the above 40mol% of 0mol%
2O
5, median size is with 50% particle diameter D
50Count below the above 5.0 μ m of 0.1 μ m.
Conductive paste of the present invention is the conductive paste that comprises conductive metal powder, frit and organic carrier; It is characterized in that; As said frit, being that the ratio below 10 mass parts comprises above-mentioned frit of the present invention more than 0.1 mass parts with respect to the said conductive metal powder of 100 mass parts.
Electron device of the present invention is to comprise semiconductor substrate and the electron device of being located at the conductive layer on the said semiconductor substrate, it is characterized in that, said conductive layer is for burning till the layer that forms through the conductive paste to the invention described above.
In the electron device of the present invention, better be that said conductive layer is for heating, burn till the layer that form with the heat-up rate more than 10 ℃/second to said conductive paste through infrared heating oven.In addition, better be in the said conductive layer, through the said frit that is contained in the said conductive paste is burnt till, there is the glass precipitate at said conductive metal particle surface.
If employing the present invention, then the frit through being used in the conductive layer that on semiconductor substrate, becomes electrode is the composition of regulation, can obtain the weather resistance favorable conductive layer for corrosive gases etc.
In addition, if adopt the present invention,, can obtain weather resistance favorable conductive layer for corrosive gases etc. then through using such frit to prepare conductive paste.
In addition, if adopt the present invention, then the sintering through such conductive paste forms conductive layer on semiconductor substrate, thereby can obtain the reliability good electron devices such as weather resistance for corrosive gases.
Description of drawings
Fig. 1 is the sectional view of an example of expression semiconducter device of the present invention.
Fig. 2 representes to use the image that is obtained by SEM of the section of the silver electrode that the frit of embodiment 2 forms.
Fig. 3 representes to use the image that is obtained by SEM of the section of the silver electrode that the frit of comparative example 2 forms.
Fig. 4 representes to use the image that is obtained by SEM of the section of the aluminium electrode that the frit of embodiment 4 forms.
Fig. 5 representes to use the image that is obtained by SEM of the section of the aluminium electrode that the frit of embodiment 7 forms.
Fig. 6 representes to use the image that is obtained by SEM of the section of the aluminium electrode that the frit of embodiment 8 forms.
Fig. 7 representes to use the image that is obtained by SEM of the section of the aluminium electrode that the frit of comparative example 2 forms.
The explanation of symbol
1 ... Semiconducter device, 2 ... Semiconductor substrate, 3 ... Conductive layer (electrode).
Embodiment
Below, the present invention is elaborated.
Frit of the present invention does not contain Pb and Mn in fact, and converting with oxide compound comprises the V below the above 80mol% of 20mol%
2O
5, the Sb below the following above 15mol% of BaO, 0mol% of the following above 40mol% of ZnO, 0mol% of the above 45mol% of 5mol%
2O
3, the following P of the above 40mol% of 0mol%
2O
5And, this frit have the above 5.0 μ m of 0.1 μ m following with 50% particle diameter D
50The median size of meter.
In the frit of the present invention, V
2O
5Be the softening temperature that reduces glass, the composition that makes mobile raising.In addition, V
2O
5Ultrared specific absorption when burning till through glass coloring is improved is so form the glass precipitate in the periphery of conductive metal particle.That is, be mixed with V
2O
5The infrared ray absorption rate of glass raise, reach a high temperature easily.Therefore, to conductive paste that conductive metal powder mixes such as this frit and silver powder are formed with infrared rays heat, when burning till, the glass volatilization also is condensed in the surface of conductive metal particle, covers the periphery of particle.Through around the conductive metal particle, forming said glass precipitate like this, improve for the weather resistance of corrosive gases etc.
This V
2O
5Ratio with below the above 80mol% of 20mol% is contained in the frit.If V
2O
5Content be lower than 20mol%, infrared ray absorption when then burning till is not enough, glass can fully not volatilize, and therefore may around the conductive metal particle, form glass coating.Better be more than 22mol%, be more preferably more than 24mol%, further be more preferably more than 55mol%.If V
2O
5Content be higher than 80mol%, then may obtain glass through crystallization.Better be below 75mol%, be more preferably below 72mol%.
ZnO is the composition that makes stabilization.This ZnO is contained in the frit with the ratio below the above 45mol% of 5mol%.When the content of ZnO is lower than 5mol% or is higher than 45mol%, may obtain glass through crystallization.From the viewpoint of the stabilization of glass, the lower value of ZnO better is more than 7mol%, is more preferably more than 8mol%.The higher limit of ZnO better is below 40mol%, is more preferably below 35mol%.
BaO is the composition that makes stabilization.This BaO is contained in the frit with the ratio below the 40mol%.When the content of BaO is higher than 40mol%, may obtain glass through crystallization.From the viewpoint of the stabilization of glass, the lower value of BaO better is more than 2mol%, is more preferably more than 4mol%.The higher limit of BaO better is below 38mol%, is more preferably below 36mol%.
Sb
2O
3It is the composition that makes the water tolerance raising of glass.This Sb
2O
3Ratio with below the 15mol% is contained in the frit.If Sb
2O
3Content be higher than 15mol%, then the softening temperature of glass rises, glass can be fully not mobile in therefore burning till, and can't around the conductive metal particle, form the glass precipitate.Therefore, may variation for the weather resistance of corrosive gases etc.Sb
2O
3More preferably content be below 13mol%, preferred content is below 12mol%.
P
2O
5It is the stability-enhanced composition that makes glass.This P
2O
5Ratio with below the 40mol% is contained in the frit.If P
2O
5Content be higher than 40mol%, then the softening temperature of glass rises, glass can be fully not mobile in therefore burning till, and can't around the conductive metal particle, form the glass precipitate.Therefore, may variation for the weather resistance of corrosive gases etc.P
2O
5More preferably content be below 35mol%, preferred content is below 33mol%.
Frit of the present invention does not contain Mn in fact.If comprise Mn, then hinder the flowability of glass easily, therefore may around electroconductive particle, form the glass precipitate, cause weather resistance variation for corrosive gases etc.
From the consideration to environment, frit of the present invention does not contain Pb in fact.
For frit of the present invention, with above-mentioned V as essential composition
2O
5BaO, Sb with ZnO and employing as required
2O
3, P
2O
5Deng difference ratio fusion raw material according to the rules, process frit.Then, behind this frit thorough mixing, for example carry out that temperature is made as more than 1100 ℃ below 1300 ℃, the time is made as the thermal treatment below 120 minutes more than 10 minutes, cool off again, pulverize, thereby can easily obtain frit of the present invention.
The median size of the frit that obtains like this is made as below the above 5.0 μ m of 0.1 μ m.Here, median size adopts accumulation median particle diameter, i.e. 50% particle diameter D
50If 50% particle diameter D
50Less than 0.1 μ m, then the compendency of frit strengthens, and frit exists as agglomeration, therefore after may be well-dispersed in the conductive metal powder in the preparation of the conductive paste stated.Consequently, burning till middle glass can't be fully mobile.In addition, 50% particle diameter D
50During greater than 5.0 μ m, the specific surface area of frit reduces, and therefore the infrared rays amount of frit absorption reduces in fact, thereby glass may fully volatilize in burning till.Consequently, can't with the glass precipitate cover the conductive metal particle around, may obtain enough weather resistance for corrosive gases etc.Also have, in this specification sheets, particle diameter adopts the value that obtains through the particle size determination device that uses laser diffraction-scattering method.
Conductive paste of the present invention comprises described frit of the present invention.Specifically, conductive paste of the present invention comprises conductive metal powder, frit and organic carrier, at least a portion of this frit, better is all to be formed by frit of the present invention.
The content of the frit in the conductive paste (ratio) better is to be more than 0.1 mass parts below 10 mass parts with respect to 100 mass parts conductive metal powder.If the content of frit is less than 0.1 mass parts with respect to 100 mass parts conductive metal powder, then may be with around the glass precipitate covering conductive metal particle.In addition, the adaptation of the semiconductor substrate through conductive paste being burnt till the conductive layer (electrode) that forms and silicon etc. may be not enough.If the content of frit is more than 10 mass parts, then the electroconductibility of the conductive layer that is formed by this conductive paste may be not enough.In addition, the dhering strength of conductive layer and semiconductor substrate is excessive, and it is big that the warpage of semiconductor substrate may become.
Conductive metal powder as contained in the conductive paste of the present invention can exemplify electroconductibility aluminium powder form, silver powder, copper powder etc.The shape of these conductive metal powder and method of manufacture do not have special qualification.In addition, the particle diameter of conductive metal powder does not have special qualification yet, can use median size with 50% particle diameter D
50Count the interior powder of relative broad range of 0.1～20 μ m.The good especially 50% particle diameter D that is to use
50It is the powder of 0.1～10 μ m.If 50% particle diameter D
50Less than 0.1 μ m or greater than 10 μ m, then can't obtain the suitable thickener of viscosity, undesirable.
As organic carrier, can use the organic binder resin that is generally used for this conductive paste, for example can use ethyl cellulose, Nitrocellulose etc.The content of organic carrier better is below the above 40 quality % of 5 whole quality % of conductive paste.If the content of organic carrier is less than 5 quality %, then paste viscosity rises, so the decline of the coating performances such as printing of conductive paste, can't form favorable conductive layer (electrode).In addition, if the content of organic carrier more than 40 quality %, then the solids component ratio of thickener reduces, generation can't obtain the problem of enough coating film thickness.
In the conductive paste of the present invention, except above-mentioned conductive metal powder, frit and organic carrier, also can comprise the various additives such as dispersion agent, softening agent, anti-sedimentation agent, thixotropic agent of the characteristic of adjusting thickener as required.The composition of additive is not particularly limited, and content better is below 10 quality %.
Conductive paste of the present invention can be processed as follows: to making organic binder resin as organic carrier be dissolved in solvent organic carrier solution in the said additive that adds conductive metal powder, frit and adopt as required, and fully mixing.
Electron device of the present invention 1 shown in Figure 1 comprises semiconductor substrate 2 and conductive layer (electrode) 3 provided thereon, and conductive layer (electrode) 3 forms through the sintering of described conductive paste.Such electronic device 1 can be by method manufacturing shown below.That is, the methods such as regulation zone passage silk screen printing at the interarea of semiconductor substrate 1 are coated with conductive metal thickener of the present invention and make its drying.Then, semiconductor substrate 1 is heated to the for example temperature below 900 ℃ more than 600 ℃, the conductive metal thickener is burnt till, thereby form conductive layer 3.
In the formation based on the conductive layer that burns till 3 of conductive metal thickener, better be in air atmosphere, to use the infrared rays firing furnace to heat with the heat-up rate more than 10 ℃/second.Be more preferably with 600～900 ℃ of top temperatures, the condition of 1～10 second top temperature hold-time and burn till.
Through heating, burn till with said condition, the frit in the conductive metal thickener of the present invention presents enough flowabilities, and the glass precipitate covers the surface of conductive metal particle.Be mixed with V
2O
5The infrared ray absorption rate of glass raise; Reach a high temperature easily; Therefore to the conductive paste that forms with the conductive metal powder mixes with infrared rays heat, when burning till, the glass volatilization also is condensed in the surface of conductive metal particle, covers the periphery of conductive metal particle.Through the glass precipitate be formed at like this conductive metal particle around, characteristic improves.That is, the conductive metal particle is under the situation of silver particles, forms said glass precipitate in the periphery of silver particles, thus to conductive paste heat, burn till and conductive layer 3 significantly improve for the weather resistance of corrosive gases etc.In addition, the conductive metal particle is under the situation of aluminum particulate, forms said glass precipitate in the periphery of aluminum particulate, thereby significantly improves for the weather resistance of moisture etc.In addition, the conductive metal particle is under the situation of copper particle, and the periphery at particle before copper is oxidized forms said glass precipitate, thereby can prevent the oxidation of copper.And, through the copper particle that surface treatment or alloying have improved, can obtain the effect that this oxidation prevents for scale resistance more significantly.
When the heat-up rate when burning till was lower than 10 ℃/second, the frit in the conductive metal thickener can fully not volatilize, and therefore can't may fully obtain the effect of improving of said characteristic with around the glass precipitate covering conductive metal particle.
Embodiment
Below, the notebook inventive embodiment.
(embodiment 1～8, comparative example 1～5)
At first, process frit with the composition shown in the table 1.That is,, in 1100～1300 ℃ electric furnace, use platinum crucible to make its fusion 1 hour, be configured as lamellar glass according to composition fusion raw material powder shown in the table 1 and mixing.Then, should pulverize by lamellar glass with ball mill, at median size D
50Be to carry out classification according to the value shown in the table 1 with airflow classification device in the scope of 0.9～2.0 μ m.Thus, process the electrode formation frit of embodiment 1～8 and comparative example 2,3 and comparative example 5.For comparative example 4, process with the ball mill pulverizing, make median size D
50Be 6.5 μ m.
The frit of comparative example 4 has the composition identical with the frit of embodiment 6.In addition, comparative example 2 and 3 frit do not contain V
2O
5, the frit of comparative example 5 comprises Mn.
Then, use the frit of embodiment 1～8 and comparative example 2～5, the conductive paste (silver-colored thickener) of processing as follows.At first, in 10 mass parts ethyl cellulose, mix 90 mass parts terpinols, process organic carrier 85 ℃ of stirrings 2 hours.Then, the organic carrier that 10 mass parts are obtained like this is mixed in 90 mass parts conductive silver powder (Dowa Electronics Materials Co (DOWA エ レ Network ト ロ ニ Network ス society) system silver powder: after AG4-8F), mixing through planetary-type mixer.Then, with respect to 100 mass parts silver powder to be the frit that the ratio of 1.1 mass parts is mixed embodiment 1～8 and comparative example 2～5, process silver-colored thickener through planetary-type mixer is mixing again.Also have, as shown in table 1, in the comparative example 1, except mixing frit, likewise do not process silver-colored thickener with above-mentioned.
Then, use the frit of embodiment 4,7,8 and comparative example 2, the conductive paste (aluminium thickener) of processing as follows.At first, in 10 mass parts ethyl cellulose, mix 90 mass parts terpinols, process organic carrier 85 ℃ of stirrings 2 hours.Then, the organic carrier that 20 mass parts are obtained like this is mixed in 80 mass parts aluminium powders (system aluminium powder: the D of Japan Aluminum Co., Ltd. (Japan ア Le ミ ニ ウ system society)
50=5 μ m) after in, mixing by planetary-type mixer.Then, to be the frit that the ratio of 1.4 mass parts is mixed embodiment 4,7,8 and comparative example 2 with respect to 100 mass parts aluminium powder forms, again through the mixing aluminium thickener of processing of planetary-type mixer.
Then; The silver-colored thickener that obtains as stated and the aluminium thickener screen printing plate with #325 is printed on 6 inches square polycrystalline silicon substrates;, in air atmosphere, burn till with 35 ℃/second of heat-up rates, 720 ℃ of top temperatures, the condition of 2 seconds top temperature hold-times after dry 10 minutes with 150 ℃ drying machines through the infrared rays firing furnace.Thus, obtain to be formed with the silicon substrate (electrode burns till substrate) of silver electrode and aluminium electrode.
Observe the electrode that obtains like this through SEM (scanning electronic microscope) and burn till the section of the silver electrode of substrate, investigate the lining state based on the glass precipitate of silver particles.Here, the section SEM image of the silver electrode that the frit of use embodiment 2 forms is shown in Fig. 2, and the section SEM image of the silver electrode that the frit of use comparative example 2 forms is shown in Fig. 3.Section SEM image by Fig. 2 can know that in the silver electrode that the frit of use embodiment 2 forms, the surface of silver particles is formed with the glass precipitate.Relative with it, can know by the section SEM image of Fig. 3, in the silver electrode that the frit of use comparative example 2 forms, around silver particles, do not find the glass precipitate.
Then, in plastic containers, add 25g ion exchanged water and 0.5g ammonium sulfide, electrode burns till substrate and the smaller slightly plastic containers of adding a cover are placed in one with being placed with, and the lid of the plastic containers in the outside is fastened.After at room temperature placing 2 hours, take out electrode and burn till substrate,, confirm on the electrode the whether corrosion of spottiness shape through the microscope visual inspection.To not see mottled corrosive sample note work zero, mottled corrosive sample note occurs to do *.Measured with detector tube and to have put into the concentration of hydrogen sulfide that electrode burns till the smaller slightly plastic containers of substrate, the result is 23ppm.
[table 1]
Can know that by table 1 the silver-colored thickener that obtains in the comparative example 1 does not contain frit, thus in the silver electrode that forms by this silver thickener, around silver particles, there is not the glass precipitate, hydrogen sulfide and silver particles surface reaction, so produce mottled corrosion.In addition, the silver-colored thickener employing of using comparative example 2 and 3 frit to process does not contain V
2O
5Frit, so in the silver electrode that forms by this silver thickener, around silver particles, do not have the glass precipitate, hydrogen sulfide and silver particles surface reaction, so produce mottled corrosion.The silver-colored thickener that obtains in the comparative example 4 adopts the composition that is regulation but size surpasses the frit of the median size (5 μ m) of regulation, so in the silver electrode that is formed by this silver thickener, be present in the glass precipitate deficiency around the silver particles, produces mottled corrosion.The silver-colored thickener that the frit of use comparative example 5 obtains adopts and contains MnO
2Frit, so in the silver electrode that forms by this silver thickener, around silver particles, do not have the glass precipitate, hydrogen sulfide and silver particles surface reaction, so produce mottled corrosion.
Relative with it; Can know that silver-colored thickener that the frit that uses embodiment 1～8 obtains comprises the frit of the median size of composition with regulation and regulation; So the printing through these silver-colored thickeners, burn till in the silver electrode that forms; Around silver particles, there is the glass precipitate, good for the tolerance of hydrogen sulfide.
Then, observe the section that electrode burns till the aluminium electrode of substrate, investigate the lining state based on the glass precipitate of aluminum particulate through SEM.Here; The section SEM image of the aluminium electrode that the frit of use embodiment 4 forms is shown in Fig. 4; The section SEM image of the aluminium electrode that the frit of use embodiment 7 forms is shown in Fig. 5; The section SEM image of the aluminium electrode that the frit of use embodiment 8 forms is shown in Fig. 6, and the section SEM image of the aluminium electrode that the frit of use comparative example 2 forms is shown in Fig. 7.Can know by Fig. 4,5 and 6 section SEM image, use in the aluminium electrode that the frit of embodiment 4,7 and 8 obtains, be formed with the glass precipitate on the surface of aluminum particulate.Relative with it, can know by the section SEM image of Fig. 7, in the aluminium electrode that the frit of use comparative example 2 forms, around aluminum particulate, do not find the glass precipitate.Can think the aluminium electrode of embodiment 4,7 and 8 owing to have the glass precipitate on the aluminum particulate surface, therefore the weather resistance for moisture etc. improves.
Claims (6)
1. an electroconductive particle tackiness agent frit is characterized in that, does not contain Pb and Mn in fact, and converting with oxide compound comprises the V below the above 80mol% of 20mol%
2O
5, the Sb below the following above 15mol% of BaO, 0mol% of the following above 40mol% of ZnO, 0mol% of the above 45mol% of 5mol%
2O
3, the following P of the above 40mol% of 0mol%
2O
5, median size is with 50% particle diameter D
50Count below the above 5.0 μ m of 0.1 μ m.
2. electroconductive particle tackiness agent frit as claimed in claim 1 is characterized in that V
2O
5Below the above 80mol% of 60mol%, ZnO is below the above 25mol% of 5mol%, and BaO is below the above 30mol% of 5mol%.
3. conductive paste; It is the conductive paste that comprises conductive metal powder, frit and organic carrier; It is characterized in that; As said frit, being that the ratio below 10 mass parts comprises claim 1 or 2 described frits more than 0.1 mass parts with respect to the said conductive metal powder of 100 mass parts.
4. electron device, it is to comprise semiconductor substrate and the electron device of being located at the conductive layer on the said semiconductor substrate, it is characterized in that, said conductive layer is for through burning till the layer that forms to the described conductive paste of claim 3.
5. electron device as claimed in claim 4 is characterized in that, said conductive layer is for heating, burn till the layer that form with the heat-up rate more than 10 ℃/second to said conductive paste through infrared heating oven.
6. like claim 4 or 5 described electron devices, it is characterized in that, in the said conductive layer,, have the glass precipitate at said conductive metal particle surface through the said frit that is contained in the said conductive paste is burnt till.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-147325 | 2010-06-29 | ||
| JP2010147325A JP5754090B2 (en) | 2010-06-29 | 2010-06-29 | Glass frit, conductive paste using the same, and electronic device |
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|---|---|
| CN102344249A true CN102344249A (en) | 2012-02-08 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014176888A1 (en) * | 2013-04-28 | 2014-11-06 | 京东方科技集团股份有限公司 | Lead-free glass powder, lead-free composite glass powder and use thereof, and display device sealed by using same |
| CN105009224A (en) * | 2013-02-05 | 2015-10-28 | E.I.内穆尔杜邦公司 | Conductive silver paste for a metal-wrap-through silicon solar cell |
| CN105142824A (en) * | 2013-04-25 | 2015-12-09 | 同和电子科技有限公司 | Silver-bismuth powder, conductive paste and conductive film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105683111B (en) * | 2013-12-04 | 2018-09-14 | 株式会社日立制作所 | The manufacturing method of seal structure and seal structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH02234308A (en) * | 1989-03-07 | 1990-09-17 | Sumitomo Metal Mining Co Ltd | Composition for conductive film formation |
| DE19945866A1 (en) * | 1999-09-24 | 2001-03-29 | Dmc2 Degussa Metals Catalysts | Process for the production of a conductive coating on glass or enamelled steel and substrates coated thereafter |
| JP5041323B2 (en) * | 2005-05-09 | 2012-10-03 | 日本電気硝子株式会社 | Powder material and paste material |
| JP4937233B2 (en) * | 2008-11-19 | 2012-05-23 | 三菱電機株式会社 | Method for roughening substrate for solar cell and method for manufacturing solar cell |
| CN102318013B (en) * | 2009-03-27 | 2014-12-03 | 株式会社日立制作所 | Conductive paste and electronic part equipped with electrode wiring formed from same |
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2010
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105009224A (en) * | 2013-02-05 | 2015-10-28 | E.I.内穆尔杜邦公司 | Conductive silver paste for a metal-wrap-through silicon solar cell |
| CN105009224B (en) * | 2013-02-05 | 2017-08-22 | E.I.内穆尔杜邦公司 | The conductive silver paste of silicon solar cell is wound for metal piercing |
| CN105142824A (en) * | 2013-04-25 | 2015-12-09 | 同和电子科技有限公司 | Silver-bismuth powder, conductive paste and conductive film |
| WO2014176888A1 (en) * | 2013-04-28 | 2014-11-06 | 京东方科技集团股份有限公司 | Lead-free glass powder, lead-free composite glass powder and use thereof, and display device sealed by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012012228A (en) | 2012-01-19 |
| JP5754090B2 (en) | 2015-07-22 |
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Application publication date: 20120208 |