CN1204567C - Conducting slurry for direct laser writing - Google Patents
Conducting slurry for direct laser writing Download PDFInfo
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- CN1204567C CN1204567C CN 02115939 CN02115939A CN1204567C CN 1204567 C CN1204567 C CN 1204567C CN 02115939 CN02115939 CN 02115939 CN 02115939 A CN02115939 A CN 02115939A CN 1204567 C CN1204567 C CN 1204567C
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Abstract
The present invention provides conductive slurry for laser direct writing, which comprises an adhesion phase, a conductive phase, an organic solvent and an organic film forming substance, wherein the adhesion phase is fusible glass powder of which the softening temperature T1 is larger than or equal to 200 DEG C and is smaller than or equal to 450 DEG C, and the grain diameter of the fusible glass powder is from 0.1 to 10 micrometers; the quality ratio of the adhesion phase and the conductive phase is from 1:24 to 1:1. The adhesion phase also comprises fusible metal powder of which the melting point T2 is larger than or equal to 180 DEG C and is smaller than or equal to 300 DEG C, the grain diameter of the fusible metal powder is from 0.1 to 10 micrometers, and the fusible glass powder accounts for 25 to 100% of the total quality of the adhesion phase; the present invention has the optimal technical effect under the condition that the softening temperature of the fusible glass powder T1 is larger than or equal to 200 DEG C and is smaller than or equal to 300 DEG C. By using the conductive slurry of the present invention, the bonding strength of conducting wires distributed by laser direct writing cloth and a basal plate can reach more than 5Mpa in general, and the minimum bonding strength is larger than or equal to 3Mpa. Resistivity is smaller than 10 to 4 omega cm, a laser uses a continuous laser with low power or a quasi-continuous laser with low power, wiring speed reaches as fast as 20 millimeters per second, and wire width is regulated between 2 millimeters to 10 micrometers.
Description
Technical field
The present invention relates to a kind of electrocondution slurry, be specifically related to a kind of electrocondution slurry for laser direct-writing.
Background technology
Along with electronics, electric equipment products to ultralarge scale integration, digitlization, lightweight and small lot, diversified future development, the process for making of traditional printed circuit board (PCB:Printed Circuit Board) and thick film circuit comprises that photochemical method and template (or silk screen) method of biting more and more can not satisfy requirement. Be embodied in: it is many to make operation, and high density, high accuracy printed circuit board are easily brought larger error; Minimum live width and line spacing are very limited; The conductive material of erosion removal is a lot, causes a large amount of wastes of noble metal; The solution that the operations such as plating, corrosion are used causes very large pollution etc. to environment. Yet, except serious environment pollution, the maximum weakness of above-mentioned technique is that also the flexibility degree is very low, specifically comprise: the wiring board fabrication cycle is longer, from finishing the time that finished product generally need be about 2 days to 7 days that processes that is designed into, and will give specialty manufacturing workshop and finish, can't effectively shorten the new product research and development cycle; Circuit board is in case the making completion can't be carried out necessary modification to designed conducting wire; For single-piece or small lot batch manufacture circuit board, manufacturing cost is higher. The electronics wiring of a new generation and encapsulation technology urgently need can be under without mask (or template) condition, high accuracy, connects the flexible wired technology of superchip and reparation conducting wire at a high speed, with the decrease production cost.
In the existing flexible wired technology, laser technology becomes and has one of flexible wired technology of potentiality most. Difference according to concrete technique, Laser Direct Writing roughly is divided into the laser chemistry vapour deposition, the plating of Laser Induced Liquid-phase chemistry and three kinds of modes of induced with laser solid phase reaction deposition are namely utilized induced with laser to deposit conductive materials from gas, liquid phase plating bath or solid film and are formed wire. But these technology generally exist cloth linear velocity excessively low (generally only having a few μ m/s to tens μ m/s), complex process, high in cost of production shortcoming.
1991, the people such as the Kestenbaum of U.S. AT ﹠ T Corp. adopted lacquering technique to preset first certain thickness metallo-organic compound conducting resinl at substrate surface, make compound decomposition go out the simple metal particle behind the laser irradiation. Minimum live width can reach about 1 μ m. The method utilization be photochemical reaction owing to must could control the metallo-organic compound decomposition rate by step increase laser power, so the maximum cloth linear velocity of acquisition is no more than 5 μ m/s (A.Kestenbaum, U.S.Patent, No.5064685, Nov., 1991). It is a lot of to utilize laser radiation metal organic compound conducting resinl to prepare the report of wire both at home and abroad, but generally exists the cloth linear velocity excessively slow, thinner thickness, the shortcoming that step is various.
For overcoming the shortcoming of above-mentioned laser flexible routing, we adopt the method fast direct ground connection of laser direct-writing electrocondution slurry to make and repair circuit board. So far, not yet find to have the report of same procedure both at home and abroad. Declared simultaneously the patent of invention that name is called " a kind of circuit board making and reparation method " about the method inventor who utilizes the laser direct-writing electrocondution slurry to make and repair circuit board.
Laser direct-writing electrocondution slurry Technology Need has suitable electrocondution slurry. Particularly connect up at glass and ceramic substrate, very high to the requirement of electrocondution slurry. Not only require the wire make continuously, fine and close, higher heat endurance arranged, make a concerted effort strong with substrate junction, and because glass, ceramic basal plate heated very easily break when impacting, so add man-hour in wiring, must avoid the excessive rapid heat cycle process that causes of difference variation. This just requires the heating temperature of bonding phase can not be too high. Existing electrocondution slurry is broadly divided into glass adhesion type, bonding oxide type and organic conductive slurry. The bonding material of glass is such as SiO2-PbO-B
2O
3P series glass, softening temperature are nearly all above 550 ℃. Such electrocondution slurry softening temperature is too high for laser direct-writing, has greatly limited the cloth linear velocity, strengthens the damage to the substrate surface, is easy to because substrate surface and poor excessive the breaking of substrate of causing of heart section temperature. Bonding oxide type slurry need to could keep high adhesive strength by sintering under near the temperature of melting point metal, so there be the shortcoming same with high softening temperature glass adhesion type slurry. The organic conductive slurry, also claim conducting resinl, utilize the resin solidification principle that bonding effect is provided, be applicable to organic substrate, such as epoxy resin base plate, phenolic resins substrate etc., its solidification temperature is very low, but uses temperature also very low, when generally using under being higher than 200 ℃ situation thermal decomposition will occur gradually; And the bonding intensity of resin on the substrates such as glass and pottery is not very high. So the organic conductive slurry also is not suitable for glass, pottery or semiconductor substrate. (seeing that " thick-film electronic element " Li Yaolin compiles publishing house of South China Science ﹠ Engineering University)
Summary of the invention
Purpose of the present invention aims to provide a kind of new electrocondution slurry, and this electrocondution slurry is applicable to carry out laser direct-writing at material substrates such as glass, pottery, semiconductors and makes and repair circuit board.
For achieving the above object, a kind of electrocondution slurry for laser direct-writing provided by the invention, comprise bonding phase, conductive phase, organic solvent and organic binder matter, it is characterized in that: the described bonding meltable glass powder of softening temperature in 200≤T1＜400 ℃ scope that be mutually, its particle diameter is 10 microns of 0.1-, and described bonding mass ratio with conductive phase is 1: 24 to 1: 1.
The above-mentioned bonding fusing point that also can comprise in mutually is the meltable metal powder of 180≤T2≤300 ℃, and its particle diameter is the 0.1-10 micron, and meltable metal powder accounts for the bonding mutually 10%-75% of total quality; Technique effect of the present invention is better when the softening temperature 200≤T1 of meltable glass powder≤300 ℃.
The inventor utilizes electrocondution slurry of the present invention, and through the wire that laser direct-writing cloth goes out, the intensity of being combined with substrate generally can reach more than the 5Mpa, and minimum is not less than 3Mpa. Resistivity is less than 10-4 Ω cm, and laser instrument uses the continuous or quasi-continuous laser instrument of small-power, and connecting up fastest is 20 milli metre per second (m/s)s, and live width can be regulated between 5 microns at 2 millimeters.
Concrete enforcement mode
Electrocondution slurry provided by the invention is comprised of bonding phase, conductive phase, organic solvent and organic binder matter, described bonding be that softening temperature is at the meltable glass powder of 200≤T1≤450 ℃ scope mutually, described bonding mass ratio with conductive phase is 1: 24 to 1: 1, when the softening temperature scope of meltable glass powder during in 200≤T1≤300 ℃ technique effect better. Be the meltable metal powder of 180≤T2≤300 ℃ at the bonding fusing point that can also comprise in mutually.
The preparation method of meltable glass is as shown in table 1, and composition and the content of electrocondution slurry see Table 2.
The preparation technology of table 1 glass and parameter
| Numbering | Composition and content | Melting | Softening temperature | Diameier |
| 1 # | Sb 2O 3: 65-90 gram, SiO2: 3.0 grams, PbO:23.0 gram, H3BO 3: 7.7-18.7 gram, KOH:22.8 gram, NaOH:1.6 gram, LiOH:1.1 gram | In porcelain crucible melting 10-20 minute, 550 ℃-700 ℃ of smelting temperatures, the molten glass of perfecting is poured into water and carries out shrend, uses ball mill grinding after the oven dry. | About 320-350 ℃ | Reach the 1-10 micron after general the grinding; The degree of depth reaches about 0.1 micron after grinding |
| 2 # | The Tl2O:6 gram, PbO:62.9 gram, B2O 3: 13.15 grams, Al2O 3: 1.88 grams, ZnO:14.1 gram | In corundum crucible melting 10-20 minute, 750 ℃-900 ℃ of smelting temperatures, melted glass is poured into water and carries out shrend, uses ball mill grinding after the oven dry. | About 400-450 ℃ | Reach the 1-10 micron after general the grinding; The degree of depth reaches about 0.1 micron after grinding |
| 3 # | The PbO:63 gram, TeO2: 5 grams, B2O 3: 28 grams, As2O 3: 4 grams | In porcelain crucible melting 10-20 minute, 550 ℃-650 ℃ of smelting temperatures, melted glass is poured into water and carries out shrend, uses ball mill grinding after the oven dry. | About 200 ℃ |
The embodiment of table 2 electrocondution slurry of the present invention
| Embodiment | Bonding phase | Conductive phase | Bonding phase and conductive phase mass ratio |
| 1 | 1 #Meltable glass powder, diameier 1-3 micron | Diameter is the flitter of 1-6 micron | 1∶1 |
| 2 | 2 #Meltable glass powder, diameier 1-9 micron | Diameter is the sheet silver powder of 1-6 micron | 1∶24 |
| 3 | 1 #Meltable glass powder, diameier 0.1-3 micron | Diameter is the sheet silver powder of 1-6 micron | 3∶7 |
| 4 | 2 #Meltable glass powder, diameier 1-10 micron | Diameter is the sheet silver powder of 1-6 micron | 3∶7 |
| 5 | 3 #Meltable glass powder, diameier 1-3 micron | Diameter is the sheet silver powder of 1-6 micron | 4∶6 |
| 6 | 1 #Meltable glass powder, 0.1 micron of diameier | Diameter is 0.5 micron sheet aluminium powder | 3∶7 |
| 7 | 1 #Meltable glass powder and metal Sn 63/Pb37 powder, diameier is the 1-3 micron, glass powder accounts for bonding phase quality 90% | Diameter is the sheet silver powder of 1-6 micron | 3∶7 |
| 8 | 1 #Meltable glass powder and metal Sn 63/Pb37 powder, diameier is the 1-3 micron, glass powder accounts for bonding phase quality 25% | Diameter is the sheet silver powder of 1-6 micron | 2∶8 |
| 9 | 3 #Meltable glass powder and metal Sn 63/Pb37 powder, diameier is the 1-3 micron, glass powder accounts for bonding phase quality 50% | Diameter is the sheet silver powder of 1-6 micron | 3∶7 |
| 10 | 1 #Meltable glass powder and metal Sn powder, diameier are the 1-3 micron, and glass powder accounts for bonding phase quality 50% | Diameter is the sheet silver powder of 1-6 micron | 3∶9 |
| 11 | 3 #Meltable glass powder and metal Sn 63/Pb37 powder, diameier is 0.1 micron | Diameter is 0.5 micron sheet silver powder | 3∶7 |
| 12 | 2 #Meltable glass powder, diameier 1-3 micron | Diameter is the spherical copper powder of 1-6 micron | 3∶7 |
| 13 | 1 #Meltable glass powder, diameier 1-3 micron | Diameter is the spherical nickel powder of 1-6 micron | 3∶7 |
Annotate: 1. employed conductive phase is same as the prior art among the present invention, and organic solvent is pine tar alcohol, and organic binder matter is the ethyl cellulose, and both mix with mass ratio at 19: 1.
2.1
#-3
#Meltable glass is with listed glass numbering in the table 1.
Bonding and the conductive phase of each example ingredients listed in the table 2 is prepared by described mass ratio, mixes with organic solvent and organic binder matter, be stirred well to equal one, still state after, namely make electrocondution slurry of the present invention.
Usually to adopt diameter be the inhomogeneous meltable glass of the particle size of 0.1-10 micrometer range with metal powder with low melting point as mutually bonding, because fine powder particle can be filled in the conductive phase space, so can make bond effect better.
Also can adopt other organic solvents and organic binder matter in the above-mentioned electrocondution slurry, regulate suitable viscosity by regulating solvent. With sol evenning machine electrocondution slurry is preset to the different coating of thickness at glass or ceramic substrate. To specific embodiment 1,2,3,4,5, the thickness of preset coating is 10 microns to 60 microns; For specific embodiment 6, thickness is 1 micron to 15 microns. With scribbling the substrate oven dry of slurry, remove organic solvent; Press predetermined track scanning substrate with small-power continuous laser device or quasi-continuous laser instrument again. The laser instrument kind that is suitable for is a lot, for example peak power 35w, can to focus on the minimum light spot diameter be 50 microns CO2Laser instrument; Or peak power is 5w, can focus on the minimum light spot diameter and be 3 microns Ar+ laser instrument; During laser treatment, the scanning speed that adopts be 0.25 millimeter to 20 the milli metre per second (m/s)s range regulation; After the been scanned, wash and do not scan part, directly stay the wire pattern that needs. The wire that utilizes said method to make is combined closely with substrate, and resistivity is less than 10-4Ω .Cm can reach respectively 50 microns to 2 millimeters to embodiment 1,2,3,4,5 live widths; To embodiment 6, live width is 5 microns to 100 microns.
To specific embodiment 7,8,10,12,13, the thickness of preset coating is 10 microns to 60 microns; For specific embodiment 11, thickness is 1 micron to 15 microns. With scribbling the substrate oven dry of slurry, remove organic solvent; Press predetermined track scanning substrate with small-power continuous laser device or quasi-continuous laser instrument again. The laser instrument kind that is suitable for is a lot, for example peak power 35w, can to focus on the minimum light spot diameter be 50 microns CO2Laser instrument; Or peak power is 5w, can focus on the minimum light spot diameter and be 3 microns Ar+ laser instrument; During laser treatment, the scanning speed that adopts be 0.25 millimeter to 20 the milli metre per second (m/s)s range regulation; In laser scanning simultaneously, pure industrial nitrogen protection is blown in processing place, throughput is 1-3l/min. After the been scanned, wash and do not scan part, directly stay the wire pattern that needs. The wire that utilizes said method to make is combined closely with substrate, and resistivity is less than 10-4Ω .Cm, to embodiment 7,8,10,12,13, live width can reach respectively 50 microns to 2 millimeters; To embodiment 11, live width is 5 microns to 100 microns.
Claims (3)
1. electrocondution slurry that is used for laser direct-writing, comprise bonding phase, conductive phase, organic solvent and organic binder matter, it is characterized in that: the described bonding meltable glass powder of softening temperature in 200≤T1＜400 ℃ scope that be mutually, its particle diameter is the 0.1-10 micron, and described bonding mass ratio with conductive phase is 1: 24 to 1: 1.
2. electrocondution slurry according to claim 1, it is characterized in that described bonding mutually in the softening temperature 200≤T1≤300 ℃ of meltable glass powder.
3. electrocondution slurry according to claim 1 and 2 is characterized in that the described bonding fusing point that also comprises in mutually is the meltable metal powder of 180≤T2≤300 ℃, and its particle diameter is the 0.1-10 micron, and meltable metal powder accounts for the bonding mutually 10-75% of total quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02115939 CN1204567C (en) | 2002-06-06 | 2002-06-06 | Conducting slurry for direct laser writing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02115939 CN1204567C (en) | 2002-06-06 | 2002-06-06 | Conducting slurry for direct laser writing |
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| CN1384508A CN1384508A (en) | 2002-12-11 |
| CN1204567C true CN1204567C (en) | 2005-06-01 |
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| CN 02115939 Expired - Fee Related CN1204567C (en) | 2002-06-06 | 2002-06-06 | Conducting slurry for direct laser writing |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101593570B (en) * | 2008-05-29 | 2012-02-22 | 四川虹欧显示器件有限公司 | Black conductive paste and plasma panel display using same |
| CN101604557B (en) * | 2008-06-11 | 2011-06-29 | 四川虹欧显示器件有限公司 | Conductive slurry and plasma display using same |
| TWI433341B (en) * | 2010-12-29 | 2014-04-01 | Au Optronics Corp | Method of fabricating a solar cell |
| US8956557B2 (en) * | 2012-01-24 | 2015-02-17 | E I Du Pont De Nemours And Company | Thick film silver paste containing copper and lead—tellurium—oxide and its use in the manufacture of semiconductor devices |
| CN106169344A (en) * | 2016-08-01 | 2016-11-30 | 合肥佳瑞林电子技术有限公司 | A kind of potentiometer short circuit in winding processing technique |
| CN106255323B (en) * | 2016-08-18 | 2018-04-17 | 武汉华尚绿能科技股份有限公司 | A kind of method that 3D printing prepares glass base circuit board |
| CN108032467B (en) * | 2017-12-28 | 2021-04-09 | 上海艾深斯科技有限公司 | Method for curing electronic conductive adhesive by aid of laser |
| CN108766651B (en) * | 2018-06-29 | 2019-07-09 | 北京梦之墨科技有限公司 | A kind of plastic conducting connecting part |
| CN113889293A (en) * | 2021-09-24 | 2022-01-04 | 暄泰电子(苏州)有限公司 | Conductive paste for electronic element |
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2002
- 2002-06-06 CN CN 02115939 patent/CN1204567C/en not_active Expired - Fee Related
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