CN101930959B - Copper conductive paste, method of manufacturing substrate with copper conductor filled in through-hole, circuit substrate, electronic component, semiconductor package - Google Patents
Copper conductive paste, method of manufacturing substrate with copper conductor filled in through-hole, circuit substrate, electronic component, semiconductor package Download PDFInfo
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- CN101930959B CN101930959B CN 200910204039 CN200910204039A CN101930959B CN 101930959 B CN101930959 B CN 101930959B CN 200910204039 CN200910204039 CN 200910204039 CN 200910204039 A CN200910204039 A CN 200910204039A CN 101930959 B CN101930959 B CN 101930959B
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Abstract
The invention provides copper conductive paste, method of manufacturing substrate with copper conductor filled in through-hole, circuit substrate, electronic component and semiconductor package. The copper conductive paste to be filled in through-holes is provided for preventing the fall-off or continuity failure of a copper conductor by reducing the occurrence of shrinkage when filled in the through-holes and fired. The copper conductive paste to be filled in the through-holes is of such a type that it is filled in the through-holes of a heat resistant substrate and fired under a non-oxidizing atmosphere, which is characterized in that it has a volume change rate of 8% or lower during firing, wherein the copper conductor has an electric resistivity of 10 mu ohm.cm or smaller after firing. Furthermore, the copper conductive paste to be filled in the through-holes contains at least copper powder, glass powder, and organic vehicle. The copper powder is a mixed powder consisting of one having particle sizes of smaller than 1 mu m and accounting for 10-30 mass% and one having particle sizes of 1-50 mu m and accounting for 70-90 mass%. The copper conductive paste has a tap density of 6.0 g/cc or more, and contains organic components accounting for 8.5 mass% or less.
Description
Technical field
The present invention relates to be filled in through hole in order to make to be formed at the multilayer wired circuit turn-on on substrate and calcined and the copper conductive paste that uses and by this copper conductive paste, be filled in through hole after carry out the manufacture method of substrate of the copper conductor filled in through-hole of high-temperature calcination, also relate to substrate, circuitry substrate, electronic unit, the semiconductor packages of copper conductor filled in through-hole.
background technology
For high-density installation electronic/electronic unit, use the multilayer circuit substrate of double-sided printed grade in table.In this multilayer circuit substrate, the conducting that is formed at the multi-layer conductive circuit on substrate connects to be undertaken by the through hole be arranged on substrate.And,, in the situation that the thermal endurance substrates such as use ceramic substrate, as substrate, utilize through hole bonding conductor circuit, be particularly generally that conductor paste is filled in through hole and carries out.
The conductor paste of this high-temperature calcination type, such as be contain conductive metal powder, glass powder, organic carrier etc. and the preparation paste, after conductor paste being filled in the through hole be formed on substrate, by its high-temperature calcination, can make thus the paste be filled in through hole become conductor, thereby carry out the connection of conductor circuit.
But, when being filled in through hole by conductor paste and calcining, there are the following problems: because of when calcining the conductive metal powder shrink, the conductor be filled in through hole shrinks, conductor from come off in through hole or and conductor circuit between poor flow occurs.
Therefore, in patent documentation 1, swelling agent is added in conductor paste, expands by making swelling agent in conductor paste is filled into to through hole and while being calcined, the conductor that prevents from being filled in through hole shrinks.
But, while making as mentioned above conductor paste contain swelling agent, existence may make to be filled in the problem that the conductivity of the conductor in through hole descends.In addition, swelling agent is by oxidized expansion of when calcining, need in oxidizing atmosphere, be calcined, in the situation that the such easy oxidation metal paste of copper conductive paste, because conductor metal is also oxidized and cause conductivity significantly to descend, so can not apply.
In addition, in patent documentation 2, by the ruthenium-oxide powder is added in conductor paste, can reduce calcining and shrink.But, in the situation that the silver conductor paste can confirm to shrink the effect reduced, and in the situation that copper conductive paste, Fig. 3 by patent documentation 2 can find out, the calcining shrinkage of generation is more than 10%, reduces the effect that the calcining of copper conductive paste shrinks by adding the ruthenium-oxide powder little.
Patent documentation 1: Japanese kokai publication hei 9-46013 communique
Patent documentation 2: Japanese kokai publication hei 7-94840 communique
Summary of the invention
The present invention completes in view of the above problems, its purpose is, a kind of filling through hole copper conductive paste is provided, it is filled in through hole and can reduces the generation of contraction while calcining, can prevent that copper conductor from coming off or poor flow occurs, in addition, its purpose also is to provide a kind of manufacture method of substrate of copper conductor filled in through-hole, prevent the generation of shrinking in copper conductive paste is filled into to through hole and while calcining, can prevent that copper conductor from coming off or poor flow occurs, and, its purpose also is to provide the substrate of the copper conductor filled in through-hole that uses this copper conductive paste, circuitry substrate, electronic unit, semiconductor packages.
Filling through hole copper conductive paste of the present invention is to be filled in the through hole of thermal endurance substrate and the type of calcining under non-oxidizing atmosphere, it is characterized in that, the volume change caused by calcining is below 8%, and the resistivity of the copper conductor after calcining is below 10 μ Ω cm.
According to the present invention, volume change during the copper conductive paste calcining is below 8%, be little of+8%～-8%, be filled in through hole by copper conductive paste and can reduce the generation of contraction while calcining, prevent that copper conductor from coming off from through hole or through hole and conductor circuit generation poor flow, in addition, the resistivity of the copper conductor after calcining is little to 10 μ Ω cm, has good conductive characteristic.
In addition, filling through hole copper conductive paste of the present invention, it is characterized in that, at least contain copper powders, glass powder, organic carrier, copper powders is that the particle diameter by 10～30 quality % is less than the mixed-powder that powder that the particle diameter of the powder of 1 μ m and 70～90 quality % is 1～50 μ m forms, and tap density is more than 6.0g/cc, and the organic component content in copper conductive paste is below 8.5 quality %.
As such copper powders, to be less than by the particle diameter of 10～30 quality % the mixed-powder that powder that the particle diameter of powder, 70～90 quality % of 1 μ m is 1～50 μ m forms, and be the powder more than 6.0g/cc by using tap density, and the organic component content in the use copper conductive paste is the following powder of 8.5 quality %, the high copper conductive paste of content of copper powder when can be produced on the fillibility that keeps good, can be sintered into the copper conductor of low-resistivity as above.In addition, this copper conductive paste can significantly reduce after being filled in through hole the contraction caused by solvent seasoning and high-temperature calcination, can make the volume change of copper conductor reduce as mentioned above.
In addition, the invention is characterized in, the average specific surface area of the above-mentioned mixed-powder of copper is 0.3～0.6m
2/ g.
Oxidation when heating under the medium oxidizing atmosphere of air, copper occurs, but when the copper conductive paste consisted of the mixing copper powder with such average specific surface area heats in air, the surface of copper powder is oxidized, along with copper becomes cupric oxide, volume adequacy expands, and can make up the volume contraction of paste because causing except desolventizing.In addition, while being calcined under nonactive atmosphere thereafter by the copper powder of surface oxidation, be reduced into metallic copper, in calcination process, the copper oxide of Copper Powder Surface hinders the sintering (making it to postpone) of copper powder, can reduce the sintering shrinkage of copper powder.
In addition, the invention is characterized in the cupric oxide powder that contains 0.5～10 quality % with respect to the copper conductive paste total amount.
Like this, by contain the part of cupric oxide powder as the mixed-powder of copper in copper conductive paste, can suitably suppress the agglutinating property of copper conductive paste, while suppressing calcining, the contraction of copper conductor, reduce change in volume.
In addition, the manufacture method of copper conductive paste filling vias substrate of the present invention, it is characterized in that having: above-mentioned copper conductive paste is filled into to operation in the through hole formed on the thermal endurance substrate, under oxidizing atmosphere, the copper conductive paste in being filled into through hole is heated and operation that the operation of copper powders partial oxidation, the copper conductive paste at the temperature more than 700 ℃, oxidation processes crossed are calcined under nonactive atmosphere.
According to this invention, under oxidizing atmosphere, the copper conductive paste in being filled into through hole heated and made the surface oxidation of copper powders, while calcining under nonactive atmosphere again, by the copper powders of surface oxidation, utilized surperficial oxide layer to suppress agglutinating property, be sintered when being reduced into metallic copper significantly not shrinking, can reduce as mentioned above the contraction that is filled in through hole by copper conductive paste and occurs while calcining.It should be noted that, in the present invention, what is called makes the copper powders partial oxidation, refers to the internal oxidation that does not make copper powders, and makes its whole surface oxidation.
In addition, the invention is characterized in, the operation that heats to carry out oxidation processes to being filled into copper conductive paste in above-mentioned through hole is to implement under the heating condition of 200～300 ℃ of temperature.
By heating-up temperature is set within this range, make the copper powders suitable oxidizing of copper conductive paste under the not defeated and dispersed condition of the shape of copper conductive paste that can be in being filled into through hole.
In addition, the invention is characterized in, above-mentioned thermal endurance substrate is pottery substrate processed.
The excellent heat resistance of pottery substrate processed, simultaneously, because widely utilize in the manufacture of circuit or electronic unit, so obtain good effect by application of the present invention.
In addition, the invention is characterized in, above-mentioned pottery substrate processed is aluminium nitride substrate.
The excellences such as the mechanical property of aluminium nitride, electrical characteristics, heat conductivity, therefore particularly preferably.
And, utilize the substrate that uses the copper conductor filled in through-hole that copper conductive paste of the present invention is made as mentioned above, can make circuitry substrate, electronic unit, semiconductor packages.
According to the present invention, under oxidizing atmosphere, the copper conductive paste in being filled into through hole is heated, make the surface oxidation of copper powders, while calcining under nonactive atmosphere again, significantly do not shrink and be sintered when being reduced into metallic copper in the copper powders of surface oxidation, can prevent being filled in through hole by copper conductive paste and shrink while calcining, thereby can prevent that copper conductor from coming off or poor flow occurs from through hole.
Copper conductive paste of the present invention, while calcining under blanket of nitrogen, under the condition of 900 ℃, 60 minutes, the volume change that can obtain being caused by calcining is below 8% and the resistivity after calcining is the copper conductor below 10 μ Ω cm.
Embodiment
Below, to describing for implementing best mode of the present invention.
Copper conductive paste of the present invention at least coordinates copper powders, glass powder, organic carrier and prepares.
And, in the present invention, as above-mentioned copper powders, it is the above mixed-powder of 6.0g/cc that the particle diameter that use comprises 10～30 quality % is less than powder and the tap density that the particle diameter of the powder of 1 μ m and 70～90 quality % (adding up to 100 quality %) is 1～50 μ m, simultaneously, the organic component content in the copper conductive paste of use is below 8.5 quality %.It should be noted that, in the present invention, particle diameter refers to medium particle diameter.
In addition, in the present invention, as the mixed-powder of this copper, the use average specific surface area is 0.3～0.6m
2the powder of/g.
In the present invention, glass powder is in order to improve for the wetability of substrate etc. and to improve adaptation etc. and coordinate, being not particularly limited, but preferably softening point is the about powder of scope of 400～750 ℃.Kind for glass is not particularly limited, but the preferred low-melting glass of the harmful substance such as not leaded, the cadmium such as borosilicate acids glass, zinc borosilicate class glass, bismuth class glass.In the situation that the substrate after filling through hole need to carry out the coating processing, preferably use the glass with chemical-resistant.Particle diameter and the shape of glass powder are not particularly limited, but particle diameter is preferably in the scope of 0.1～10 μ m, and for the contraction that will be caused by glass melting is suppressed to Min., its particle diameter is 0.1～5 μ m, 0.1～3 μ m more preferably more preferably.
In addition, in the present invention, as organic carrier, can use organic bond is dissolved in to the organic carrier formed in organic solvent.As organic bond, be not particularly limited, can use and in calcination process, easily make it burn mistake and the few organic compound of ash content, such as: the acrylic compounds such as polybutyl methacrylate, polymethyl methacrylate; The cellulose families such as NC Nitroncellulose, ethyl cellulose, cellulose acetate, butyl cellulose; The polyethers such as polyformaldehyde; The polyethylene such as polybutadiene, polyisoprene base class etc., these organic bonds, except using separately a kind, can also be mixed with two or more.
As organic solvent, be not particularly limited, can use and give the suitable viscosity of copper conductive paste and process by drying the organic compound that easily makes its volatilization after being applied on substrate by copper conductive paste, such as: the high boiling organic solvents such as carbitol, carbitol acetic acid esters, terpinol, metacresol, methylimidazole, methylimidazole alkane ketone, dimethyl formamide, diacetone alcohol, triethylene glycol, paraxylene, ethyl lactate, isophorone.These organic solvents, except using separately a kind, can also be mixed with two or more.
Coordinate sintering inhibitor, surfactant, the antioxidants etc. such as above-mentioned copper powders, glass powder, organic carrier and oxide as required, these materials are mixed, can prepare copper conductive paste thus.The mixed proportion of each material is not particularly limited, and is preferably set to: with respect to copper powders 100 mass parts, glass powder is that 1～6 mass parts, organic bond are 0.5～3 mass parts, in the scope that organic solvent is 4～9 mass parts.At this, in copper conductive paste of the present invention, so that being mode below 8.5 quality %, the content of the organic principle consisted of organic bond, organic solvent and other organic additives shared total amount in paste set.
Glass powder can improve the compactness of calcining copper conductor, and can improve the closing force between copper conductor and substrate.When the use level of glass powder is less than 1 mass parts, because the compactness of calcining copper conductor descends, with the bonding force of substrate also step-down, so, after calcining, copper conductor may come off from through hole.On the other hand, because glass powder melting in the high-temperature calcination of copper conductor shrinks, so, when its use level is 6 mass parts when above, the calcining of copper conductive paste is shunk and become large, likely can't obtain the low-shrinkage of target.
Even having the viscosity of giving the copper conductive paste appropriateness, organic bond also makes the effects such as shape is maintained after except desolventizing, drying.When the use level of organic bond is less than 0.5 mass parts, the stability of copper conductive paste, printing descend, and are difficult to carry out good filling through hole.On the other hand, when it surpasses 3 mass parts, the viscosity of copper conductive paste uprises, and may make the fillibility of through hole is descended.
In addition, because the organic principle in copper conductive paste all is evaporated, decomposes in dry or calcining, so, if its amount is many, may make the calcining of copper conductive paste shrink change greatly.In order to realize low-shrinkage of the present invention, the content of the organic principle in copper conductive paste is set as below 8.5 quality %.The copper conductive paste that organic principle is few is removed by its burning mistake the contraction caused and is diminished, if but its amount is very few, and the mobility (fillibility) as paste descends, so more than being preferably 6.0 quality %.
In order to be formed on the conducting of the multilayer wired circuit on the thermal endurance substrate, the copper conductive paste of the present invention of preparation can be filled in through hole and use thus.
As this thermal endurance substrate, so long as can tolerate after being filled in through hole by copper conductive paste the substrate of the high temperature of being calcined, just be not particularly limited.Can enumerate such as ceramic substrate, glass substrate, silicon substrate, enamel (ホ mono-ロ mono-) substrate etc.As pottery, can enumerate the oxide-based potteries such as aluminium oxide, zirconia, beryllium oxide, mullite, forsterite, cordierite, lead titanates, barium titanate, lead zirconate titanate; The non-oxidized substance class potteries such as silicon nitride, aluminium nitride, carborundum etc., in these materials, due to excellences such as the mechanical property of aluminium nitride, electrical characteristics, heat conductivities, so particularly preferably.
In addition, on the thermal endurance substrate, form the position of wiring circuit on two sides, form the through hole that connects substrate, copper conductive paste is filled in this through hole.Can fill copper conductive paste in through hole by any means, for example, can implement by silk screen printing.
After being filled in through hole by copper conductive paste like this, at first heat the solvent of removing in copper conductive paste.Can be in the temperature lower than 200 ℃, for example approximately heated at the temperature of 150 ℃ with except desolventizing.
By in nonactive atmosphere with temperature 700 ℃ or more calcining in through hole filled the substrate of this copper conductive paste, can obtain calcine copper conductor that shrinkage little thereafter.But, in order further to reduce the calcining shrinkage, preferably copper conductive paste is carried out to the heated oxide processing.This heated oxide is in order to make to be filled in the part organic bond thermal decomposition in the copper conductive paste in through hole, makes the surface oxidation of copper powders simultaneously, in air isoreactivity atmosphere (oxidizing atmosphere), carries out.Because the volume of the surface of copper powders copper powder when oxidized becomes large, so can make up because solvent evaporates and organic bond decompose the volume caused, reduce.In addition, heating-up temperature is set as more than 200 ℃.The upper limit of heating-up temperature is not particularly limited, and is preferably the temperature below 300 ℃.During lower than 200 ℃, can not make the abundant oxidation of copper powders, so can not obtain suppressing fully contractive effect when the temperature of Heated Copper conductor paste.In addition, when the temperature of Heated Copper conductor paste surpasses 300 ℃, organic bond is decomposed fully, may make to be filled in the shape of the copper conductive paste in through hole defeated and dispersed or come off from substrate.In addition, copper powder is excessively oxidated, and the calcination process thereafter can not fully reduce, and may make conductivity decline to a great extent.It should be noted that, be not particularly limited heating time, generally is preferably approximately 30～180 minutes.
Then, after being heated thus the copper powders of copper conductive paste being carried out to the partial oxidation processing, heated substrate under nonactive atmosphere, calcining is filled in the copper conductive paste in through hole.The heating-up temperature of this calcining is set in more than 700 ℃.At this, as nonactive atmosphere (nonoxidizing atmosphere, reducing atmosphere), can use such as blanket of nitrogen etc.By in nonactive atmosphere, copper conductive paste being heated to like this more than 700 ℃, the surperficial copper powders that forms Cu oxide is reduced as mentioned above, when reverting to original metallic copper, be sintered, and organic carrier occurs decompose and remove.
When the heating-up temperature in when calcining during lower than 700 ℃, Cu oxide is reduced into to the effect of metallic copper is insufficient and sintering is also insufficient, therefore possibly can't obtain sufficient conductivity and adaptation.The upper limit of heating-up temperature is special the setting not, preferably in the temperature below 950 ℃, calcines.It should be noted that, calcination time is not particularly limited, and usually preferably under said temperature, keeps approximately 10～60 minutes.
Like this, by under nonactive atmosphere, being heated to more than 700 ℃ and being calcined, Cu oxide is sintered when being reduced into metallic copper, and the copper oxide of Copper Powder Surface hinders the sintering of copper powder, and agglutinating property is reduced, and can make thus sintering shrinkage reduce.Thereby, can prevent that copper conductive paste from being shunk by the conductor of calcining and being formed in through hole, can not occur that conductor comes off from through hole or conductor produces defect etc., can prevent the problems such as poor flow.
At this, in the present invention, by Heated Copper conductor paste at the temperature more than 200 ℃ like this, can easily make the copper powders partial oxidation, again by under nonactive atmosphere, the copper conductive paste that this oxidation processes of temperature lower calcination more than 700 ℃ is crossed, can make the copper powders of surface oxidation not shrink and easily be reduced into metallic copper, as such copper powders, can use the particle diameter by 10～30 quality % as above to be less than the powder of 1 μ m, the mixed-powder formed with the particle diameter of 70～90 quality % powder that is 1～50 μ m, its tap density is more than 6.0g/cc, and average specific surface area is 0.3～0.6m
2/ g.
In this mixed-powder of copper, when the powder that is less than 1 μ m when particle diameter is less than 10 quality %, the oxidation of copper powders is insufficient, prevents the effect of shrinking during calcining insufficient under nonactive atmosphere.In addition, when the powder that is less than 1 μ m when particle diameter surpasses 30 quality %, during copper powders under nonactive atmosphere after calcined oxide, can not fully reduce, may make conductivity descend.
On the other hand, when the tap density of copper powders is less than 6.0g/cc, the packed density of copper powders is low, needs a large amount of solvents while making paste.Occur significantly to shrink except desolventizing when such copper conductive paste can and be calcined because of drying, therefore can not realize reducing the target of volume change.Preferably tap density is more high better, and its upper limit is not particularly limited, but in practicality on be limited to about 7.0g/cc.
In addition, the average specific surface area when copper powders is less than 0.3m
2during/g, the oxidation of copper powders is insufficient, and under nonactive atmosphere, to prevent from shrinking, reduce the effect of change in volume insufficient when calcining.Otherwise, when average specific surface area surpasses 0.6m
2during/g, during copper powders under nonactive atmosphere after calcined oxide, can not fully reduce, may make conductivity descend.
In addition, in the present invention, except each above-mentioned composition, can in copper conductive paste, be used in conjunction with cupric oxide powder.When the part of the mixed-powder using cupric oxide powder as copper is coupled in copper conductive paste like this, while under oxidizing atmosphere, the copper conductive paste in being filled into through hole being heated as mentioned above, cupric oxide powder expands, can make up volume and reduce, can suppress copper conductor contraction, reduce change in volume.In copper conductive paste, the use level of cupric oxide powder is preferably the scope of 0.5～10 quality % with respect to the copper conductive paste total amount.When it, can not fully obtain by the effect that coordinates cupric oxide powder to produce during lower than 0.5 quality % with respect to the copper conductive paste total amount.Otherwise, when it surpasses 10 quality % with respect to the copper conductive paste total amount, because expanding, cupric oxide powder cause the copper conductor expansion excessive, and the change in volume of copper conductor becomes large because of this expansion on the contrary.The particle diameter of cupric oxide powder is not particularly limited, and is preferably the scope of 0.5～20 μ m in medium particle diameter.
And, use the copper conductive paste of composition as above, by method as above, copper conductive paste be filled in the through hole of substrate and calcined, the contraction in the time of can being inhibited thus calcining and reduce volume change, the volume change that caused by calcining is the copper conductor of volume change below 8% in-8%～+ 8% scope.When volume change surpasses-8% and while shrinking, may make copper conductor come off from through hole or the poor flow of through hole and conductor circuit occurs.Otherwise, when copper conductor expands and cubical expansivity while surpassing+8%, may make copper conductor expose from through hole too much or through hole is destroyed by copper conductor.
In addition, by being calcined under nonactive atmosphere, reducing copper oxides, can make the conductivity of copper conductor improve, and can obtain resistivity is the following copper conductors of 10 μ Ω cm.When resistivity surpasses 10 μ Ω cm, likely can't fully guarantee the conductivity in through hole, in the purposes of large electric current, can't use.Preferably resistivity is the smaller the better, and its lower limit is not particularly limited, and the resistivity 1.69 μ Ω cm of fine copper are substantive lower limit.
By using the substrate of the copper conductor filled in through-hole of making as mentioned above, form circuit on the thermal endurance substrate, can obtain circuitry substrate.In addition, on the thermal endurance substrate that electronic component is installed to this circuitry substrate, can obtain electronic unit.In addition, by by semiconductor element mounting to the thermal endurance substrate of this circuitry substrate and sealed, can obtain semiconductor packages.
Embodiment
Below, utilize embodiment and comparative example to illustrate the present invention.
As shown in table 1, the copper powder 1～5 (being mining company of Mitsui Metal Co., Ltd. system) that the use medium particle diameter is 7.3 μ m, 4.8 μ m, 1.2 μ m, 0.83 μ m, 0.52 μ m is as copper powders, in addition, the cuprous oxide powder (high-purity chemical institute system) that the use medium particle diameter is 4.2 μ m is as cupric oxide powder, these powder are mixed by the use level of table 2, used as mixed-powder.It should be noted that, in the present invention, medium particle diameter (D50) is the value of measuring with laser diffraction formula particle size distribution device.The value that these numerical value adopt manufacturer to announce.In addition, in the present invention, average specific surface area is the value of measuring by the BET method, and the numerical value of table 1 is the value that manufacturer announces.In addition, in the present invention, the tap density of mixing copper powder is the value of measuring with cylinder type tap density determinator (the tap density meter " PT-DTI " that German Pharma Test company manufactures).It should be noted that, the numerical value of the various copper powders of table 1 or the tap density of cupric oxide powder is the value that manufacturer announces.
Table 1
| Copper powder № | Medium particle diameter (μ m) | Specific area (m 2/g) | Tap density (g/cc) |
| Copper powder 1 | 7.3 | 0.12 | 5.2 |
| Copper powder 2 | 4.8 | 0.21 | 5.0 |
| Copper powder 3 | 1.2 | 0.69 | 4.1 |
| Copper powder 4 | 0.83 | 1.2 | 4.1 |
| Copper powder 5 | 0.52 | 1.8 | 3.8 |
| Cuprous oxide powder | 4.2 | 0.22 | 3.5 |
In addition, as glass dust, using softening point is the zinc borosilicate class glass powder that 565 ℃, average grain diameter are 3 μ m.
In addition, as organic carrier, use by the mass ratio of 1: 2 organic bond acrylic resin and organic solvent carbitol/terpinol (=1: the organic carrier 1) mixed.
Then, the use level by these compositions by table 2 is coordinated, and after utilizing blender to be mixed, with three roller mixing rolls, carries out evenly mixingly, obtains thus the copper conductive paste of embodiment 1～4 and comparative example 1～8.
For this copper conductive paste, measure shrinkage and resistivity after calcining.Owing to being difficult to carry out the mensuration of this shrinkage or resistivity under the state in copper conductive paste is filled into to through hole, so copper conductive paste is printed onto on the surface of aluminium nitride substrate, measured.
At first, on the surface of aluminium nitride substrate, use 250 eye mesh screens, respectively the copper conductive paste silk screen printing of embodiment 1～4 and comparative example 1～8 is become to pattern form, 150 ℃ of heating 10 minutes, remove thus the organic solvent in copper conductive paste.Then, by air, with continuous stove, at the temperature shown in table 2, heating and within 60 minutes, carry out oxidation processes.Use continuous calcining stove under blanket of nitrogen, 900 ℃ under heat 60 minute calcined thereafter.
Then, for volume change, with the contact pin type film thickness gauge, measure respectively the thickness of the front pattern of calcining and the thickness of the pattern after calcining, the film thickness value before and after relatively calcining by following formula, obtain with the form of shrinkage thus.
Shrinkage (%)=[thickness before (thickness after thickness before calcining-calcining)/calcining] * 100
When shrinkage (%) be on the occasion of the time because volume reduces, so volume change is negative value.Otherwise, when shrinkage (%) is negative value because volume increases, so volume change be on the occasion of.Show the result in table 2.
In addition, for resistivity, to being formed on the foursquare pattern of the length of side 10mm after the calcining on substrate, with four terminal resistance rate testers, measure resistance values, obtain with the form of specific insulation.Show the result in table 2.
Then, for the copper conductive paste of embodiment 1～4 and comparative example 1～8, estimate fillibility and adaptation to through hole.
At first, use and be provided with the aluminium nitride substrate (3 inches * 3 inches * thickness 0.635mm) that a plurality of apertures are 0.15mm and these 2 kinds of through holes of 0.3mm, printing operation is filled into copper conductive paste in through hole by hand.Then, put it in the fan drying machine of 150 ℃ heating 20 minutes, after carrying out solvent seasoning, utilize polishing to grind and remove the copper conductive paste remained on substrate surface fully.Thereafter, by this substrate being put into to the continuous stove of 220 ℃, in air, oxidation processes is carried out in heating in 60 minutes, then, substrate is put into to the continuous calcining stove, and under blanket of nitrogen, under 900 ℃, calcining is 60 minutes.
For the substrate after being calcined like this, occupied state with stereoscopic microscope observing to through hole, confirm that conductor has or not come off (the 1st time), again substrate is put into to ultrasonic unit and applied ultrasonic vibration after 20 minutes, the occupied state to through hole with stereoscopic microscope observing, confirm that conductor has or not come off (the 2nd time) again.Show the result in table 2.It should be noted that, in table 2, "
*1 " mean the 1st time come off, "
*2 " mean the 2nd time come off.
As can be seen from Table 2, it is below 8% that the volume change that the copper conductive paste of embodiment 1～4 causes because of calcining hangs down.And, carrying out oxidation processes by the heating of the temperature more than 200 ℃, volume change further diminishes, and resistivity is also enough little.About filling through hole, embodiment 1～4 is good, after ultrasonic vibration, also without conductor, comes off or defect in addition.In addition, the through-hole section of substrate is cut off and carried out the section observation, its result, through hole wall and filling conductor gapless are bonding, do not produce the defects such as space.
It should be noted that, embodiment 4 replaces the example of the part copper powder of embodiment 3 with cupric oxide powder, by such cooperation cupric oxide powder, can further suppress the generation of shrinking, even, in the situation that carry out oxidation processes at the temperature of 180 ℃, also can realize almost without shrinking.
On the other hand, for the copper conductive paste of comparative example 1, the ratio at fine copper powder end that particle diameter is less than 1 μ m is high, by carrying out oxidation processes at the temperature more than 200 ℃, contraction in the time of can reducing calcining, but when calcining, the copper powders after oxidation fully can not be reduced, conductivity declines to a great extent, and resistivity uprises.
In addition, for the copper conductive paste of comparative example 2, because the tap density of copper powders is low, so the contraction while calcining is large, conductor comes off from through hole.In addition, because the average specific surface area of copper powders is large, so, when making the copper powders oxidation, can produce excessive expansion, conductivity declines to a great extent simultaneously.
In addition, for the copper conductive paste of comparative example 3 and comparative example 4, because do not contain the fine copper powder end that particle diameter is less than 1 μ m, so tap density is also low, so occur while calcining significantly to shrink, conductor comes off from through hole.
In addition, for the copper conductive paste of comparative example 5, because tap density is low, so the contraction while calcining is large, conductor comes off from through hole.
In addition, for the copper conductive paste of comparative example 6 and comparative example 7, the ratio at fine copper powder end that particle diameter is less than 1 μ m is high, and tap density is little, and average specific surface area is large simultaneously, so easily produce excessive expansion during oxidation processes, conductivity declines to a great extent.
In addition, for the copper conductive paste of comparative example 8, because the organic carrier amount is many, so, although carry out oxidation processes, shrink also large.
Claims (12)
1. a filling through hole copper conductive paste, it is to be filled in the through hole of thermal endurance substrate and the type of being calcined under non-oxidizing atmosphere, it is characterized in that,
The volume change caused by calcining is below 8%, and the resistivity of copper conductor after calcining is below 10 μ Ω cm,
Described filling through hole at least contains copper powders, glass powder, organic carrier with copper conductive paste, copper powders is that the particle diameter by 10～30 quality % is less than the mixed-powder that powder that the particle diameter of the powder of 1 μ m and 70～90 quality % is 1～50 μ m forms, and tap density is more than 6.0g/cc, and the organic component content in copper conductive paste is below 8.5 quality %.
2. filling through hole copper conductive paste as claimed in claim 1, is characterized in that, the average specific surface area of the described mixed-powder of copper is 0.3～0.6m
2/ g.
3. filling through hole copper conductive paste as claimed in claim 1 or 2, is characterized in that, the cupric oxide powder that contains 0.5～10 quality % with respect to the copper conductive paste total amount.
4. the manufacture method of the substrate of a copper conductor filled in through-hole, it is characterized in that having: copper conductive paste claimed in claim 1 is filled into to operation in the through hole formed on the thermal endurance substrate, under oxidizing atmosphere, the copper conductive paste in being filled into through hole is heated and operation that the operation of copper powders partial oxidation, the copper conductive paste at the temperature more than 700 ℃, oxidation processes crossed are calcined under nonactive atmosphere.
5. the manufacture method of the substrate of copper conductor filled in through-hole as claimed in claim 4, is characterized in that, the operation that heats to carry out oxidation processes to being filled into copper conductive paste in through hole is to implement under the heating condition of 200～300 ℃ of temperature.
6. the manufacture method of the substrate of copper conductor filled in through-hole as claimed in claim 4, is characterized in that, described thermal endurance substrate is pottery substrate processed.
7. the manufacture method of the substrate of copper conductor filled in through-hole as claimed in claim 6, is characterized in that, described pottery substrate processed is aluminium nitride substrate.
8. the substrate of a copper conductor filled in through-hole, is characterized in that, is filled with the copper conductor that the calcined material by copper conductive paste claimed in claim 1 forms in the through hole of thermal endurance substrate.
9. the substrate of a copper conductor filled in through-hole, is characterized in that, by method manufacture claimed in claim 4, forms.
10. a circuitry substrate, it possesses the substrate of copper conductor filled in through-hole claimed in claim 8.
11. an electronic unit, it possesses the substrate of copper conductor filled in through-hole claimed in claim 8.
12. a semiconductor packages, it possesses the substrate of copper conductor filled in through-hole claimed in claim 8.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-254876 | 2008-09-30 | ||
| JP2008254876 | 2008-09-30 | ||
| JP2009-197694 | 2009-08-28 | ||
| JP2009197694A JP5379609B2 (en) | 2008-09-30 | 2009-08-28 | Copper conductor paste for filling through hole, copper conductor through hole filling board manufacturing method, copper conductor through hole filling board, circuit board, electronic component, semiconductor package |
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| Publication Number | Publication Date |
|---|---|
| CN101930959A CN101930959A (en) | 2010-12-29 |
| CN101930959B true CN101930959B (en) | 2013-05-08 |
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| CN 200910204039 Active CN101930959B (en) | 2008-09-30 | 2009-09-30 | Copper conductive paste, method of manufacturing substrate with copper conductor filled in through-hole, circuit substrate, electronic component, semiconductor package |
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| JP (1) | JP5379609B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5376255B2 (en) * | 2010-11-18 | 2013-12-25 | ハリマ化成株式会社 | Firing type conductive copper paste |
| CN104112487A (en) * | 2013-04-18 | 2014-10-22 | 上海市灿晶电子材料有限公司 | Conductive copper slurry, preparation method and application of conductive copper slurry |
| CN104185358B (en) * | 2013-05-27 | 2018-09-07 | 三之星机带株式会社 | Hole filling substrate with surface conductance film and its manufacturing method |
| JP5973479B2 (en) | 2013-05-27 | 2016-08-23 | 三ツ星ベルト株式会社 | Hole-filled substrate having conductive film, method for producing the same, and method for suppressing swelling or peeling |
| CN103559940A (en) * | 2013-11-14 | 2014-02-05 | 盐城工学院 | Copper electronic paste and preparation method and application thereof |
| JP6406598B2 (en) * | 2014-07-24 | 2018-10-17 | 学校法人福岡大学 | Printed wiring board and manufacturing method thereof |
| JP6541530B2 (en) | 2015-09-24 | 2019-07-10 | 三ツ星ベルト株式会社 | Via-filled substrate, method for producing the same, and precursor thereof |
| JP7208619B2 (en) * | 2019-01-10 | 2023-01-19 | 株式会社マテリアル・コンセプト | Electronic component manufacturing method |
| JP7002483B2 (en) * | 2019-01-11 | 2022-01-20 | Ｊｘ金属株式会社 | Conductive composition |
| JP7424340B2 (en) * | 2021-04-02 | 2024-01-30 | 株式会社村田製作所 | Conductive paste, manufacturing method for multilayer ceramic capacitors, multilayer ceramic capacitors |
| CN116543949B (en) * | 2023-07-04 | 2023-12-22 | 乾宇微纳技术(深圳)有限公司 | Hole filling slurry and preparation method thereof |
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| JPH10112216A (en) * | 1996-08-09 | 1998-04-28 | Toray Ind Inc | Photosensitive conductive paste, electrode therewith and manufacture thereof |
| JP2004055557A (en) * | 2002-07-17 | 2004-02-19 | Ngk Spark Plug Co Ltd | Copper paste, wiring board using the same and manufacturing method of wiring board |
| JP2006196246A (en) * | 2005-01-12 | 2006-07-27 | Sumitomo Electric Ind Ltd | Conductive paste and wiring circuit board using it |
| JP4805621B2 (en) * | 2005-07-07 | 2011-11-02 | 株式会社ノリタケカンパニーリミテド | Conductive paste |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101930959A (en) | 2010-12-29 |
| JP2010108917A (en) | 2010-05-13 |
| JP5379609B2 (en) | 2013-12-25 |
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