CN103906352A - Thick-film electric-conduction synthetic material and method for manufacturing multilayer circuit - Google Patents
Thick-film electric-conduction synthetic material and method for manufacturing multilayer circuit Download PDFInfo
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- CN103906352A CN103906352A CN201410135765.6A CN201410135765A CN103906352A CN 103906352 A CN103906352 A CN 103906352A CN 201410135765 A CN201410135765 A CN 201410135765A CN 103906352 A CN103906352 A CN 103906352A
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- thick
- synthetic material
- multilayer circuit
- tio2
- film conductor
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Abstract
The invention is suitable for the technical field of multilayer circuit manufacturing, and discloses a thick-film electric-conduction synthetic material and a method for manufacturing a multilayer circuit. The thick-film electric-conduction synthetic material comprises electric conduction powder, inorganic bonding agents and organic media, the inorganic bonding agents comprise TiO2 and Ti-contained compounds capable of generating the TiO2 after being sintered, and the mass proportion of the inorganic bonding agents to the whole synthetic materials ranges from 0.6% to 2%. The method for manufacturing the multilayer circuit includes the step that a layer of thick-film electric-conduction synthetic materials with patterns are printed on the surface of green tape. The thick-film electric-conduction synthetic material can be used in the LTCC technology, the green tape and various pasted electronic elements can be pasted to the thick-film electric-conduction synthetic materials, and a multilayer circuit system can be manufactured; after multiple oxides are doped, the bonding performance of the green tape and the heat stability of a welding connector under the heat preservation condition and the heat circulation condition can be improved, cracking of the welding connector is prevented, the good bonding performance can be kept, and the product reliability is high.
Description
Technical field
The invention belongs to multilayer circuit preparing technical field, relate in particular to a kind of thick-film conductor synthetic material and adopt the method for preparing multilayer circuit of this thick-film conductor synthetic material.
Background technology
An interconnective LTCC(low temperature co-fire ceramics, LTCC) design circuit board, be a series of complicated multilayer circuit systems that are made up of the miniature electric components and parts of electrical connection and mechanical connection, each conductive layer directly separates with dielectric layer.Between conductive layer, interconnect by the through hole on dielectric layer.Such sandwich construction makes circuit compacter, is conducive to reduce size.
Because LTCC green material strip has sandwich construction, flexible design, and in preparation process, adopt burning technology altogether, thereby be widely used in the field such as automotive electronics, communication.A key element of this material successful Application is that (general low temperature range is at-55～-40 DEG C in heat ageing (at 150 DEG C, constant temperature is deposited) and thermal cycle, high temperature range is at 100～150 DEG C) in environment, the surface conductance layer of green material strip remains good welding caking property.When material is exposed in above environment, the welding point place of connection substrate and electronic component there will be stress, and its reason is that the thermal coefficient of expansion of the various materials (as pottery, conducting metal, weld metal etc.) due to welding point place is inconsistent.By careful layout designs with rationally utilize underfill, can make stress distribution more even, prevent that stress from concentrating on some joints.But wanting thoroughly eliminates stress is impossible.When material is exposed in said temperature environment, in order to keep good welds caking property, the material of joint must both can absorb stress and not produce permanent or irreversible mechanical damage simultaneously.
Welding point modal damage situation in Thermal Cycling is that conductive layer periphery produces cracking, and along with the increase of thermal cycle time, crack will be transmitted to dielectric layer.In some situation, cracking phenomena has just occurred in thermal cycle 10 times.And under normal circumstances, obvious cracking phenomena does not appear in General Requirements green material strip after 500 temperature cycles yet, or caking property between conductive layer and dielectric layer can obviously not decline.
At present, in prior art, also do not have technology can make green material strip after 500 temperature cycles, still keep good caking property and not occur obvious cracking phenomena, the poor heat stability of green material strip welding point, product reliability is low.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of thick-film conductor synthetic material is provided and has prepared the method for multilayer circuit, it can improve the thermal stability of green material strip welding point, and product reliability is high.
Technical scheme of the present invention is: a kind of thick-film conductor synthetic material for LTCC technology, comprise conductive powder body, inorganic bond and organic medium, and described inorganic bond comprises TiO
2with after sintering, can produce TiO
2containing Ti compound, the proportion that the quality of wherein said inorganic bond accounts for whole synthesis material quality is 0.6%～2%.
Alternatively, be made up of a kind of metal-powder also can be by the mixture of at least one metal-powder, at least one alloy composition for described conductive powder body.
Alternatively, the diameter <10 μ m of described conductive powder body.
Alternatively, described is divalence, trivalent or higher valence state containing the Ti in Ti compound.
Alternatively, described TiO
2mass percent in synthetic material is less than 2%.
The present invention also provides a kind of method of preparing multilayer circuit, comprises the following steps,
(a): prepare via-hole array pattern at multi-layer green ceramic material strip;
(b): on the green band obtaining in (a) operation, carry out filling perforation;
(c): on the green belt surface obtaining in (b) operation, print the patterned thick-film conductor synthetic material of one deck, described thick-film conductor synthetic material composition comprises:
(1) conductive powder body;
(2) inorganic bond, described inorganic bond comprises TiO
2with after sintering, can produce TiO
2containing Ti compound, the proportion that the quality of wherein said inorganic bond accounts for whole synthesis material quality is 0.6%～2%;
(3) organic medium;
(d): the green band that (c) operation is obtained carries out lamination, to form the aggregate that comprises circuit layer and green band;
(e): the aggregate that (d) operation is obtained carries out common burning.
Alternatively, the diameter <10 μ m of described conductive powder body.
Alternatively, described is divalence, trivalent or higher valence state containing the Ti in Ti compound
Alternatively, described TiO
2mass percent in synthetic material is less than 2%.
Alternatively, described TiO
2mass percent in synthetic material is 0.5～1.6%.
Thick-film conductor synthetic material provided by the invention and prepare the method for multilayer circuit, this thick-film conductor synthetic material can be used for LTCC(low-temp ceramics and burns altogether) paste green material strip and various electronic component sticked in technique, make multilayer circuit system; For soldered elements, this electrically conductive synthetic material is especially applicable.When carrying out after many oxide mixes, can improving the caking property of green material strip and be welded to connect the thermal stability of head under heat-retaining condition and thermal cycle conditions, prevent that cracking phenomena from appearring in welding point, and can keep good caking property, product reliability is high.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
A kind of thick-film conductor synthetic material for LTCC technology that the embodiment of the present invention provides, comprises conductive powder body, inorganic bond and organic medium, and described inorganic bond comprises TiO
2with after sintering, can produce TiO
2containing Ti compound, the proportion that the quality of wherein said inorganic bond accounts for whole synthesis material quality is 0.6%～2%.In concrete application, inorganic bond, its composition is mainly TiO
2with after sintering, can produce TiO
2compound, and other oxides mix.Wherein to account for the proportion of whole synthetic material be 0.6%～2% to the total quality of inorganic bond.Organic medium, i.e. the solution of polymer, separately has a small amount of additive, as surfactant.Thick-film conductor synthetic material for LTCC technology provided by the present invention, it can be used for LTCC green material strip, when carrying out after many oxide mixes, can improve the caking property of green material strip and be welded to connect the thermal stability of head under heat-retaining condition and thermal cycle conditions, and then improve the reliability of product.
Particularly, be made up of a kind of metal-powder also can be by the mixture of at least one metal-powder, at least one alloy composition for described conductive powder body.For example gold, silver, platinum, palladium, and any two or two or more mixtures in them.Particularly, the size and shape of conductive powder body is not strict with, the diameter <10 μ m of general described conductive powder body.
Particularly, described is divalence, trivalent or higher valence state containing the Ti in Ti compound.
Particularly, described TiO
2mass percent in synthetic material, less than 2%, is generally 0.5～1.6%.
Particularly, inorganic bond also can comprise following compound: Sb
2o
3, Co
3o
4, PbO, Fe
2o
3, SnO
2, MnO, CuO neutralizes any one or any at least two kinds of their mixtures.
Particularly, can in organic medium, mix inorganic compound, to form viscosity synthetic, i.e. binding agent.In thick-film conductor synthetic material, conventionally use the inorganic constituents of 50～95 wt% and the organic medium of 5～50 wt%, the ratio of organic medium and inorganic constituents depends on the using method of binding agent and the purposes of organic medium.
The present invention also provides a kind of method of preparing multilayer circuit, comprises the following steps,
(a): prepare via-hole array pattern at multi-layer green ceramic material strip;
(b): on the green band obtaining in (a) operation, carry out filling perforation;
(c): on the green belt surface obtaining in (b) operation, print the patterned thick-film conductor synthetic material of one deck, described thick-film conductor synthetic material composition comprises:
(1) conductive powder body;
(2) inorganic bond, described inorganic bond comprises TiO
2with after sintering, can produce TiO
2containing Ti compound, the proportion that the quality of wherein said inorganic bond accounts for whole synthesis material quality is 0.6%～2%;
(3) organic medium;
(d): the green band that (c) operation is obtained carries out lamination, to form the aggregate that comprises circuit layer and green band;
(e): the aggregate that (d) operation is obtained carries out common burning.
Particularly, the size and shape of conductive powder body is not strict with, the diameter <10 μ m of general described conductive powder body.
Particularly, described is divalence, trivalent or higher valence state containing the Ti in Ti compound.Described TiO
2mass percent in synthetic material, less than 2%, is generally 0.5～1.6%.
Particularly, described TiO
2mass percent in synthetic material, less than 2%, is generally 0.5～1.6%.。
Particularly, inorganic bond also can comprise following compound: Sb
2o
3, Co
3o
4, PbO, Fe
2o
3, SnO
2, MnO, CuO neutralizes any one or any at least two kinds of their mixtures.
Particularly, can in organic medium, mix inorganic compound, to form viscosity synthetic, i.e. binding agent.In thick-film conductor synthetic material, conventionally use the inorganic constituents of 50～95 wt% and the organic medium of 5～50 wt%, the ratio of organic medium and inorganic constituents depends on the using method of binding agent and the purposes of organic medium.
In concrete application, the main component of thick-film conductor synthetic material is conductive powder body and is distributed in the titanium oxide in organic medium.Specific as follows:
Inorganic constituents:
Inorganic constituents in thick-film conductor synthetic material of the present invention comprises that (1) has conductive powder body and (2) inorganic bond of conducting function: its main component is titanium oxide or the compound that can produce titanium oxide through sintering.Inorganic bond also comprises some other inorganic oxide additive.
Conductive powder body:
Conductive powder body in thick-film conductor synthetic material can be a kind of metal-powder and can be also the mixture of metal-powder, alloy or the compound that contains several compositions, for example gold, silver, platinum, palladium, and their mixture.The size and shape of powder here seems and is not very important, and general D50 is of a size of <10um.
Inorganic bond---titanium oxide:
The present invention's titanium oxide used has three kinds of potential effects.One, can be used as adhesive and provide cementability to conductive layer and green band; Two, the sintering rate of adjustable conductor layer is to reduce stress in green band; Three, TiO
2can improve the mechanical strength of green band.The present invention's titanium oxide used can be directly oxide, can be also through sintering can produce titanium oxide containing Ti compound, as Ti metal, organic titanate, or from the crystallized product of frit.Compound containing Ti can be divalence, trivalent or higher valence state.TiO
2quality percentage in synthetic material, less than 2%, is generally 0.5～1.6%.
Optional inorganic bond composition
TiO
2or can produce TiO through sintering
2compound be to contribute to improve green band integrality and improve the close-burning main active ingredient after thermal cycle.Meanwhile, some oxides are as Sb
2o
3, Co
3o
4, PbO, Fe
2o
3, SnO
2, MnOx, CuOx etc., after mixing with titanium oxide, also can improve caking property to a certain extent.
Organic medium
One typical organic medium is the solution of polymer.The most frequently used polymer is ethyl cellulose, and other also comprise ethylhexyl cellulose, wood rosin, the mixture of ethyl cellulose and phenolic resins, polymethacrylates of low alcohol content etc.In thick film synthetic, the widest solvent of the scope of application is ester alcohol and loose alkene, as alpha-or beta-terpineol or the two and kerosene, dibutyl maleate, DEGMBE, ethylene glycol, and higher boiling point alcohol and alcohol ester.The multiple combination formula of above compound and other solvents can be used to obtain required viscosity and volatility.
In thick-film conductor synthetic material, the ratio of organic medium and inorganic constituents depends on the using method of binding agent and the purposes of organic medium.Conventionally use the inorganic constituents of 50～95 wt% and the organic medium of 5～50 wt%, to obtain good coating.
Thick-film conductor synthetic material of the present invention can be used for pasting green band and other various stickup elements, thereby forms multilayer circuit system.The effect of green band is as the dielectric substance in multilayer circuit.Green band is lead-free.
Green band carries out compressing tablet after being located by location hole, and location hole is positioned at the corner of green band, and its size is more bigger than the actual size of circuitous pattern.In order to couple together formation multilayer circuit by each layer, need on green band, make through hole.The early stage general method that uses apparatus punching realizes, and, in order to realize high-precision punching, uses more the method for laser drill now.
The method that employing goes out to clog thick-film conductor synthetic at through hole realizes each layer interconnecting.This conductive compounds is usually used in standard screen printing technique.By the circuit of every layer of silk screen printing wire producing.Meanwhile, can make resistance or capacitance circuit element at selected layer printed resistor slurry or high-k slurry.Wire, resistance, electric capacity and other electronic components all can be made by screen printing technique.
Thick-film conductor synthetic material of the present invention can be applicable to front end operation or the rear end operation of laminated process, by screen printing technique, synthetic is printed on to the top one deck of circuit layer.The superiors directly contact with electronic component.These elements are generally fixed to circuit layer surface by techniques such as coiling, bonding or welding.For soldered elements, conductive compounds of the present invention is especially applicable, can significantly improve the caking property of welding point after heat ageing and thermal cycle.
After the circuit production of every layer completes, every layer is aimed at and lamination, utilize isostatic pressing technology to guarantee every layer of exactitude position.After lamination, then obtain suitable size through cutting edge.Blank after utilizing conveyer belt sintering furnace or van-type sintering furnace setting heating schedule to lamination carries out sintering.
" sintering " word in literary composition, here refer in oxidizing atmosphere (as air) integrated blank heating is arrived to certain temperature, and be incubated the sufficiently long time, thus make organic material volatilization, make the inorganic constituents in green band and conductor compositions produce chemical reaction.After sintering, lamination blank forms fine and close multilayer circuit element, generally can be used for communication and vehicle electric field.
" functional layer " refers to the green band after printing, has electricity and leads, resistance, the functions such as electric capacity.On a typical green band, can print multiple electronic components such as producing wire, conductive through hole, resistance and electric capacity simultaneously.
A kind of thick-film conductor synthetic material for LTCC technology provided by the invention, this material burns altogether for LTCC(low-temp ceramics) technique pastes green material strip and various electronic component sticked, making multilayer circuit system; For soldered elements, this electrically conductive synthetic material is especially applicable.When carrying out after many oxide mixes, can improving the caking property of green material strip and be welded to connect the thermal stability of head under heat-retaining condition and thermal cycle conditions, prevent that cracking phenomena from appearring in welding point, and can keep good caking property, product reliability is high.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace or improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the thick-film conductor synthetic material for LTCC technology, it is characterized in that, comprise conductive powder body, inorganic bond and organic medium, described inorganic bond comprise can produce after TiO2 and sintering TiO2 containing Ti compound, the proportion that the quality of wherein said inorganic bond accounts for whole synthesis material quality is 0.6%～2%.
2. the thick-film conductor synthetic material for LTCC technology as claimed in claim 1, is characterized in that, described conductive powder body is made up of a kind of metal-powder also can be by the mixture of at least one metal-powder, at least one alloy composition.
3. the thick-film conductor synthetic material for LTCC technology as claimed in claim 1, is characterized in that, the diameter <10 μ m of described conductive powder body.
4. the thick-film conductor synthetic material for LTCC technology as claimed in claim 1, is characterized in that, described is divalence, trivalent or higher valence state containing the Ti in Ti compound.
5. the thick-film conductor synthetic material for LTCC technology as claimed in claim 1, is characterized in that, the mass percent of described TiO2 in synthetic material is less than 2%.
6. a method of preparing multilayer circuit, is characterized in that, comprises the following steps,
(a): prepare via-hole array pattern at multi-layer green ceramic material strip;
(b): on the green band obtaining in (a) operation, carry out filling perforation;
(c): on the green belt surface obtaining in (b) operation, print the patterned thick-film conductor synthetic material of one deck, described thick-film conductor synthetic material composition comprises:
(1) conductive powder body;
(2) inorganic bond, described inorganic bond comprise can produce after TiO2 and sintering TiO2 containing Ti compound, the proportion that the quality of wherein said inorganic bond accounts for whole synthesis material quality is 0.6%～2%;
(3) organic medium;
(d): the green band that (c) operation is obtained carries out lamination, to form the aggregate that comprises circuit layer and green band;
(e): the aggregate that (d) operation is obtained carries out common burning.
7. the method for preparing multilayer circuit as claimed in claim 6, is characterized in that, the diameter <10 μ m of described conductive powder body.
8. the method for preparing multilayer circuit as claimed in claim 6, is characterized in that, described is divalence, trivalent or higher valence state containing the Ti in Ti compound.
9. the method for preparing multilayer circuit as claimed in claim 6, is characterized in that, the mass percent of described TiO2 in synthetic material is less than 2%.
10. the method for preparing multilayer circuit as claimed in claim 9, is characterized in that, the mass percent of described TiO2 in synthetic material is 0.5～1.6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410135765.6A CN103906352A (en) | 2014-04-07 | 2014-04-07 | Thick-film electric-conduction synthetic material and method for manufacturing multilayer circuit |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410135765.6A CN103906352A (en) | 2014-04-07 | 2014-04-07 | Thick-film electric-conduction synthetic material and method for manufacturing multilayer circuit |
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|---|---|
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|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0581206A2 (en) * | 1992-07-31 | 1994-02-02 | Hughes Aircraft Company | Low-temperature-cofired-ceramic (LTCC) tape structures including cofired ferromagnetic elements, drop-in components and multi-layer transformer |
| EP1534053A2 (en) * | 2003-11-19 | 2005-05-25 | E.I. du Pont de Nemours and Company | Thick film conductor paste compositions for LTCC tape |
| CN1913044A (en) * | 2005-04-25 | 2007-02-14 | E.I.内穆尔杜邦公司 | Thick film conductor composition, and its use in ltcc circuit and device |
-
2014
- 2014-04-07 CN CN201410135765.6A patent/CN103906352A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0581206A2 (en) * | 1992-07-31 | 1994-02-02 | Hughes Aircraft Company | Low-temperature-cofired-ceramic (LTCC) tape structures including cofired ferromagnetic elements, drop-in components and multi-layer transformer |
| EP1534053A2 (en) * | 2003-11-19 | 2005-05-25 | E.I. du Pont de Nemours and Company | Thick film conductor paste compositions for LTCC tape |
| CN1913044A (en) * | 2005-04-25 | 2007-02-14 | E.I.内穆尔杜邦公司 | Thick film conductor composition, and its use in ltcc circuit and device |
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Application publication date: 20140702 |