CN101930959A - 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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- CN101930959A CN101930959A CN2009102040394A CN200910204039A CN101930959A CN 101930959 A CN101930959 A CN 101930959A CN 2009102040394 A CN2009102040394 A CN 2009102040394A CN 200910204039 A CN200910204039 A CN 200910204039A CN 101930959 A CN101930959 A CN 101930959A
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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 for make be formed at the multilayer wired circuit turn-on on the substrate and be filled in the through hole and calcine and the copper conductive paste that uses and be filled into this copper conductive paste in the 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 the table.In this multilayer circuit substrate, the conducting that is formed at the multi-layer conductive circuit on the substrate connects to be undertaken by the through hole that is arranged on the substrate.And, particularly under the situations of thermal endurance substrate as substrate such as use ceramic substrate, utilize through hole bonding conductor circuit, generally be conductor paste to be filled in the through hole carry out.
The conductor paste of this high-temperature calcination type, for example be to contain conductive metal powder, glass powder, organic carrier etc. and the paste of preparation, after being filled into conductor paste in the through hole that is formed on the substrate, with its high-temperature calcination, can make the paste that is filled in the through hole become conductor thus, thereby carry out the connection of conductor circuit.
But when being filled into conductor paste in the through hole and calcining, there are the following problems: because of when calcining the conductive metal powder shrink, the conductor that is filled in the through hole shrinks, conductor come off in the through hole or and conductor circuit between poor flow takes place.
Therefore, in patent documentation 1, swelling agent is added in the conductor paste, expands by make swelling agent when being filled into conductor paste in the through hole and calcining, the conductor that prevents to be filled in the through hole shrinks.
But when making conductor paste contain swelling agent as mentioned above, existence may make the problem of the conductivity decline that is filled in the conductor in the through hole.In addition, swelling agent is by oxidized expansion of when calcining, need calcine in oxidizing atmosphere, under the situation of the such easy oxidation metal paste of copper conductive paste, causes conductivity significantly to descend because conductor metal is also oxidized, so can not use.
In addition, in patent documentation 2,, can reduce calcining and shrink by the ruthenium-oxide powder is added in the conductor paste.But, under the situation of silver conductor paste, can confirm to shrink the effect of minimizing, and under the situation of copper conductive paste, Fig. 3 by patent documentation 2 can find out that the calcining shrinkage of generation is more than 10%, and is little by adding the effect that calcining that the ruthenium-oxide powder reduces copper conductive paste shrinks.
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 finishes in view of the above problems, its purpose is, provide a kind of through hole to fill and use copper conductive paste, it is filled in the through hole and can reduces the generation of contraction when calcining, can prevent that copper conductor from coming off or poor flow takes place, in addition, its purpose also is to provide a kind of manufacture method of substrate of copper conductor filled in through-hole, when being filled into copper conductive paste in the through hole and calcining, prevent the generation of shrinking, can prevent that copper conductor from coming off or poor flow takes place, 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.
It is to be filled in the through hole of thermal endurance substrate and the type of calcining under non-oxidizing atmosphere that through hole of the present invention is filled with copper conductive paste, it is characterized in that, the volume change that is caused by calcining is below 8%, and the resistivity of the copper conductor after the calcining is below the 10 μ Ω cm.
According to the present invention, volume change during the copper conductive paste calcining is below 8%, be little to+8%～-8%, be filled into copper conductive paste in the through hole and can reduce the generation of contraction when calcining, prevent that copper conductor from coming off or through hole and conductor circuit generation poor flow from through hole, in addition, the resistivity of the copper conductor after the calcining is little to 10 μ Ω cm, has the favorable conductive characteristic.
In addition, through hole of the present invention is filled and is used copper conductive paste, it is characterized in that, at least contain copper powders may, glass powder, organic carrier, copper powders may is to be the mixed-powder that the powder of 1～50 μ m constitutes by the particle diameter of 10～30 quality % less than the particle diameter of the powder of 1 μ m and 70～90 quality %, and tap density is more than the 6.0g/cc, and the organic component content in the copper conductive paste is below the 8.5 quality %.
As such copper powders may, be to be the mixed-powder that the powder of 1～50 μ m constitutes less than the particle diameter of the powder of 1 μ m, 70～90 quality % by the particle diameter of 10～30 quality %, and by using tap density to be the powder more than the 6.0g/cc, 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 keeping good filling property can be produced on, the copper conductor of aforesaid low-resistivity can be sintered into.In addition, this copper conductive paste can significantly reduce and is filled in the through hole back by the contraction that solvent seasoning and high-temperature calcination cause, the volume change of copper conductor is reduced as mentioned above.
In addition, the invention is characterized in that 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 takes place, but when in air, heating by the copper conductive paste that the mixing copper powder with such average specific surface area constitutes, copper powder surperficial oxidized, along with copper becomes cupric oxide, volume adequacy expands, and can remedy paste because of removing the volume contraction of desolvating and causing.In addition, be reduced into metallic copper when being calcined under nonactive atmosphere thereafter by the copper powder of surface oxidation, in calcination process, the copper oxide on copper powder surface hinders the sintering (making it to postpone) of copper powder, and the sintering that can reduce copper powder shrinks.
In addition, the invention is characterized in, contain the cupric oxide powder of 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, the contraction of copper conductor reduces change in volume when suppressing calcining.
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 operation in the through hole that on the thermal endurance substrate, forms, under oxidizing atmosphere to being filled into that copper conductive paste in the through hole heats and the operation that makes the operation of copper powders may partial oxidation, calcine at the copper conductive paste of under the temperature more than 700 ℃, oxidation processes being crossed under the nonactive atmosphere.
According to this invention, under oxidizing atmosphere to being filled into that copper conductive paste in the through hole heats and the surface oxidation that makes copper powders may, when under nonactive atmosphere, calcining again, utilized the oxide layer on surface to suppress agglutinating property by the copper powders may of surface oxidation, be not sintered when being reduced into metallic copper significantly shrinking, can reduce the contraction that is filled into copper conductive paste in the through hole and takes place when calcining as mentioned above.Need to prove that in the present invention, what is called makes the copper powders may partial oxidation, is meant the internal oxidation that does not make copper powders may, and makes its whole surface oxidation.
In addition, the invention is characterized in that to heat the operation of carrying out oxidation processes be to implement to being filled into copper conductive paste in the above-mentioned through hole under the heating condition of 200～300 ℃ of temperature.
By heating-up temperature is set within this range, make the copper powders may 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 that above-mentioned thermal endurance substrate is the ceramic substrate.
The excellent heat resistance of ceramic substrate, simultaneously, because in the manufacturing of circuit or electronic unit, widely utilize, so obtain good effect by application of the present invention.
In addition, the invention is characterized in that above-mentioned ceramic substrate is the aluminium nitride substrate.
Excellences such as the mechanical property of aluminium nitride, electrical characteristics, heat conductivity, therefore preferred especially.
And the substrate of the copper conductor filled in through-hole of copper conductive paste making of the present invention is as mentioned above used in utilization, can make circuitry substrate, electronic unit, semiconductor packages.
According to the present invention, under oxidizing atmosphere, the copper conductive paste that is filled in the through hole is heated, make the surface oxidation of copper powders may, when under nonactive atmosphere, calcining again, significantly do not shrink and be sintered when being reduced into metallic copper in the copper powders may of surface oxidation, can prevent to be filled into copper conductive paste in the through hole and shrink when calcining, thereby can prevent that copper conductor from coming off or poor flow takes place from through hole.
Copper conductive paste of the present invention, when calcining under blanket of nitrogen, under 900 ℃, 60 minutes the condition, the volume change that can obtain being caused by calcining is below 8% and the resistivity after the calcining is copper conductor below the 10 μ Ω cm.
Embodiment
Below, describe being used to implement best mode of the present invention.
Copper conductive paste of the present invention cooperates copper powders may, glass powder, organic carrier at least and prepares.
And, in the present invention, as above-mentioned copper powders may, using the particle diameter that comprises 10～30 quality % is that powder and the tap density of 1～50 μ m is the above mixed-powder of 6.0g/cc less than the particle diameter of the powder of 1 μ m and 70～90 quality % (adding up to 100 quality %), simultaneously, the organic component content in the copper conductive paste of use is below the 8.5 quality %.Need to prove that in the present invention, particle diameter is meant 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 cooperate, be not particularly limited, but preferred softening point is the powder of about 400～750 ℃ scope.Kind for glass is not particularly limited, but the low-melting glass of harmful substances such as preferred borosilicate acids glass, zinc borosilicate class glass, bismuth class glass etc. are not leaded, cadmium.Substrate after through hole is filled need carry out under the situation of coating processing, the preferred glass with chemical-resistant that uses.The 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 in order to be suppressed to Min. by the contraction that glass melting causes, its particle diameter is 0.1～5 μ m, 0.1～3 μ m more preferably more preferably.
In addition, in the present invention,, can use organic bond is dissolved in the organic carrier that forms in the organic solvent as organic carrier.As organic bond, be not particularly limited, can use in calcination process, to make it burn mistake and the few organic compound of ash content easily, for example: acrylic compounds such as polybutyl methacrylate, polymethyl methacrylate; Cellulose families such as NC Nitroncellulose, ethyl cellulose, cellulose acetate, butyl cellulose; Polyethers such as polyformaldehyde; Polyethylene such as polybutadiene, polyisoprene base class etc., these organic bonds can also be mixed with two or more except using separately a kind.
As organic solvent, be not particularly limited, can use the organic compound of giving the suitable viscosity of copper conductive paste and after copper conductive paste being applied on the substrate, making its volatilization easily, for example: the organic solvent of higher boiling points such as carbitol, carbitol acetic acid esters, terpinol, metacresol, methylimidazole, methylimidazole alkane ketone, dimethyl formamide, diacetone alcohol, triethylene glycol, paraxylene, ethyl lactate, isophorone by dried.These organic solvents can also be mixed with two or more except using separately a kind.
Cooperate sintering inhibitor, surfactant, antioxidants etc. such as above-mentioned copper powders may, glass powder, organic carrier and oxide as required,, can prepare copper conductive paste thus these material mixing.The mixed proportion of each material is not particularly limited, and is preferably set to: with respect to copper powders may 100 mass parts, glass powder is that 1～6 mass parts, organic bond are 0.5～3 mass parts, and organic solvent is in the scope of 4～9 mass parts.At this, in copper conductive paste of the present invention,, content shared total amount in paste of the organic principle that is made of organic bond, organic solvent and other organic additives sets so that being mode below the 8.5 quality %.
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 during, 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 less than 1 mass parts.On the other hand, because glass powder fusion 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 big, might can't obtain the low-shrinkage of target.
Desolvate, also make effects such as shape is maintained after the drying removing even organic bond has the viscosity of giving the copper conductive paste appropriateness.When the use level of organic adhesive during less than 0.5 mass parts, the stability of copper conductive paste, printing descend, and are difficult to carry out good through hole and fill.On the other hand, when it surpassed 3 mass parts, the viscosity of copper conductive paste uprised, and the fillibility to through hole is descended.
In addition, because the organic principle in the copper conductive paste all is evaporated, decomposes in dry or calcining, so, if its amount is many, then 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 the copper conductive paste is set at below the 8.5 quality %.The copper conductive paste that organic principle is few is removed the contraction that causes by its burning mistake and is diminished, if but its amount is very few, and then the flowability (fillibility) as paste descends, so be preferably more than the 6.0 quality %.
In order to be formed on the conducting of the multilayer wired circuit on the thermal endurance substrate, Pei Zhi copper conductive paste of the present invention can be filled in the through hole and use thus.
As this thermal endurance substrate,, just be not particularly limited so long as can tolerate the substrate of the high temperature of calcining after being filled into copper conductive paste in the through hole.For example can enumerate: ceramic substrate, glass substrate, silicon substrate, enamel (ホ one ロ one) substrate etc.As pottery, can enumerate oxide-based potteries such as aluminium oxide, zirconia, beryllium oxide, mullite, forsterite, cordierite, lead titanates, barium titanate, lead zirconate titanate; Non-oxidized substance class potteries such as silicon nitride, aluminium nitride, carborundum etc., in these materials, because excellences such as the mechanical property of aluminium nitride, electrical characteristics, heat conductivity, so preferred especially.
In addition, on the thermal endurance substrate, form the position of wiring circuit on the two sides, form the through hole that connects substrate, copper conductive paste is filled in this through hole.Can in through hole, fill copper conductive paste with any means, for example, can implement by silk screen printing.
After being filled into copper conductive paste in the through hole like this, at first heat the solvent of removing in the copper conductive paste.Can be lower than 200 ℃ temperature, for example heat to remove under the about 150 ℃ temperature and desolvate.
By in nonactive atmosphere with temperature 700 ℃ or more calcining in through hole filled the substrate of this copper conductive paste, can obtain calcine shrinkage little copper conductor thereafter.But,, preferably copper conductive paste is carried out heated oxide and handles in order further to reduce the calcining shrinkage.This heated oxide is in order to make the part organic bond thermal decomposition in the copper conductive paste that is filled in the through hole, to make the surface oxidation of copper powders may simultaneously, carrying out in air isoreactivity atmosphere (oxidizing atmosphere).Because the volume of copper powder becomes big during copper powders may surperficial oxidized, reduce so can remedy because of solvent evaporates and organic bond decompose the volume that causes.In addition, heating-up temperature is set at more than 200 ℃.The upper limit of heating-up temperature is not particularly limited, and is preferably the temperature below 300 ℃.When the temperature of heating copper conductive paste is lower than 200 ℃, can not make the abundant oxidation of copper powders may, so can not be suppressed contractive effect fully.In addition, when the temperature of heating copper conductive paste surpassed 300 ℃, organic bond was decomposed fully, may make the shape that is filled in the copper conductive paste in the 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 conductivity is declined to a great extent.Need to prove that be not particularly limited heating time, generally be preferably about 30～180 minutes.
Then, heat thus the copper powders may of copper conductive paste is carried out after partial oxidation handles, heated substrate under nonactive atmosphere, calcining is filled in the copper conductive paste in the through hole.The heating-up temperature of this calcining is set in more than 700 ℃.At this,, can use for example blanket of nitrogen etc. as nonactive atmosphere (nonoxidizing atmosphere, reducing atmosphere).By in nonactive atmosphere copper conductive paste being heated to more than 700 ℃ like this, the surperficial as mentioned above copper powders may that forms Cu oxide is reduced, and be sintered when reverting to original metallic copper, and organic carrier takes place to decompose and remove.
When the heating-up temperature in when calcining was lower than 700 ℃, it is insufficient and sintering is also insufficient that Cu oxide is reduced into the effect of metallic copper, therefore possibly can't obtain sufficient conductivity and adaptation.The upper limit of heating-up temperature is not special to be set, and preferably calcines in the temperature below 950 ℃.Need to prove that calcination time is not particularly limited, preferably under said temperature, kept about 10～60 minutes usually.
Like this, by calcining being heated to more than 700 ℃ under the nonactive atmosphere, Cu oxide is sintered when being reduced into metallic copper, and the copper oxide on copper powder surface hinders the sintering of copper powder, and agglutinating property is reduced, and sintering is shunk reduce.Thereby, can prevent that the conductor that copper conductive paste is formed in the through hole by calcining from shrinking, can not take place that conductor comes off or conductor produces defective etc. from through hole, can prevent problems such as poor flow.
At this, among the present invention, by under the temperature more than 200 ℃, heating copper conductive paste like this, can easily make the copper powders may partial oxidation, again by under nonactive atmosphere, the copper conductive paste that this oxidation processes of temperature lower calcination more than 700 ℃ is crossed, the copper powders may that can make surface oxidation does not shrink and easily is reduced into metallic copper, as such copper powders may, can use the powder of aforesaid particle diameter by 10～30 quality % less than 1 μ m, with the particle diameter of 70～90 quality % be the mixed-powder that the powder of 1～50 μ m constitutes, its tap density is more than the 6.0g/cc, and average specific surface area is 0.3～0.6m
2/ g.
In this mixed-powder of copper, when particle diameter less than the powder of 1 μ m during less than 10 quality %, the oxidation of copper powders may is insufficient, the effect that prevents contraction under nonactive atmosphere during calcining is insufficient.In addition, when particle diameter surpasses 30 quality % less than the powder of 1 μ m, can not fully reduce during copper powders may under nonactive atmosphere behind the calcined oxide, conductivity is descended.
On the other hand, when the tap density of copper powders may during less than 6.0g/cc, the packed density of copper powders may is low, needs a large amount of solvents when making paste.Such copper conductive paste removes to desolvate in the time of can and calcining because of drying and takes place significantly to shrink, and therefore can not realize reducing the target of volume change.Preferred tap density is high more good more, and its upper limit is not particularly limited, but in the practicality on be limited to about 7.0g/cc.
In addition, when the average specific surface area of copper powders may less than 0.3m
2During/g, the oxidation of copper powders may is insufficient, and it is insufficient that calcining the time prevents to shrink, to reduce the effect of change in volume under nonactive atmosphere.Otherwise, when average specific surface area surpasses 0.6m
2During/g, can not fully reduce during copper powders may under nonactive atmosphere behind the calcined oxide, conductivity is descended.
In addition, in the present invention, except that each above-mentioned composition, can in copper conductive paste, be used cupric oxide powder.When being coupled in copper conductive paste as the part of the mixed-powder of copper cupric oxide powder like this, as mentioned above under oxidizing atmosphere when being filled into copper conductive paste in the through hole and heating, cupric oxide powder expands, can remedy 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 is lower than 0.5 quality % with respect to the copper conductive paste total amount, can not fully obtain by the effect that cooperates cupric oxide powder to produce.Otherwise, when it surpasses 10 quality % with respect to the copper conductive paste total amount,, cupric oxide powder cause the copper conductor expansion excessive because of expanding, and the change in volume of copper conductor becomes big 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 aforesaid composition, by aforesaid method copper conductive paste is filled in the through hole of substrate and calcines, the contraction in the time of can being inhibited calcining thus 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 when shrinking, copper conductor is come off from through hole or the poor flow of through hole and conductor circuit takes place.Otherwise, when copper conductor expands and cubical expansivity when surpassing+8%, copper conductor is exposed too much or through hole is destroyed by copper conductor from through hole.
In addition, by calcining 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, might fully guarantee the conductivity in through hole, in the purposes of big electric current, can't use.Preferred 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, on the thermal endurance substrate, form circuit, 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 with semiconductor element mounting to the thermal endurance substrate of this circuitry substrate and seal, can obtain semiconductor packages.
Embodiment
Below, utilize embodiment and comparative example to illustrate the present invention.
As shown in table 1, using medium particle diameter is that the copper powder 1～5 (being mining company of Mitsui Metal Co., Ltd. system) of 7.3 μ m, 4.8 μ m, 1.2 μ m, 0.83 μ m, 0.52 μ m is as copper powders may, in addition, using medium particle diameter is that the cuprous oxide powder (high-purity chemical institute system) of 4.2 μ m is as cupric oxide powder, these powder are mixed by the use level of table 2, use as mixed-powder.Need to prove 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 with 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 makes).Need to prove 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 that 565 ℃, average grain diameter are the zinc borosilicate class glass powder of 3 μ m.
In addition, as organic carrier, use by 1: 2 mass ratio organic bond acrylic resin and organic solvent carbitol/terpinol (=1: the organic carrier that 1) mixes.
Then, the use level of these compositions by table 2 cooperated, utilize blender to mix after, carry out evenly mixingly with three roller mixing rolls, obtain the copper conductive paste of embodiment 1～4 and comparative example 1～8 thus.
For this copper conductive paste, measure shrinkage and resistivity after calcining.Owing under the state that copper conductive paste is filled in the through hole, be difficult to carry out the mensuration of this shrinkage or resistivity, measure so copper conductive paste is printed onto on the surface of aluminium nitride substrate.
At first, on the surface of aluminium nitride substrate, use 250 eye mesh screens, the copper conductive paste silk screen printing with embodiment 1～4 and comparative example 1～8 becomes pattern form respectively, 150 ℃ of heating 10 minutes, removes the organic solvent in the copper conductive paste thus.Then, carried out oxidation processes in 60 minutes by in air, using continuous stove under the temperature shown in the table 2, to heat.Thereafter, use the continuous calcining stove under blanket of nitrogen, 900 ℃ down heating calcined in 60 minutes.
Then, for volume change, measure the thickness of the preceding pattern of calcining and the thickness of the pattern after the calcining respectively with the contact pin type film thickness gauge, the film thickness value before and after relatively calcining by following formula is obtained with the form of shrinkage thus.
Shrinkage (%)=[thickness before (thickness before the calcining-calcining back thickness)/calcining] * 100
When shrinkage (%) be on the occasion of the time because volume reduces, so volume change is a 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,, measure resistance value, obtain with the form of specific insulation with four terminal resistance rate testers to being formed on the foursquare pattern of the length of side 10mm after the calcining on the substrate.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 to be provided with the aluminium nitride substrate (3 inch * 3 inch * thickness 0.635mm) of a plurality of apertures as 0.15mm and these 2 kinds of through holes of 0.3mm, printing operation is filled into copper conductive paste in the through hole by hand.Then, put it in 150 ℃ the fan drying machine heating 20 minutes, carry out solvent seasoning after, utilize polishing to grind and remove the copper conductive paste that remains on the substrate surface fully.Thereafter, by this substrate is put into 220 ℃ continuous stove, oxidation processes was carried out in heating in 60 minutes in air, then, substrate was put into the continuous calcining stove, under blanket of nitrogen, 900 ℃ of calcinings 60 minutes down.
For the substrate after calcining like this, with the occupied state of stereoscopic microscope observing to through hole, confirm that conductor has or not come off (the 1st time), again substrate is put into ultrasonic unit and applied ultrasonic vibration after 20 minutes, with the occupied state of stereoscopic microscope observing, confirm that conductor has or not come off (the 2nd time) once more to through hole.Show the result in table 2.Need to prove, in table 2, "
*1 " the 1st time come off of expression, "
*2 " the 2nd time come off of expression.
As can be seen from Table 2, the volume change that causes because of calcining of the copper conductive paste of embodiment 1～4 is low is below 8%.And, carrying out oxidation processes by heating in the temperature more than 200 ℃, volume change further diminishes, and resistivity is also enough little.About the through hole fillibility, embodiment 1～4 is good, does not have also after the ultrasonic vibration in addition that conductor comes off or defective.In addition, section is carried out in the through-hole section cut-out of substrate observe, its result, it is bonding that through hole wall and filling conductor do not have the gap, do not produce defectives such as space.
Need to prove, embodiment 4 is the examples that replace 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 carrying out under 180 ℃ the temperature under the situation of oxidation processes, also can realize almost not having contraction.
On the other hand, for the copper conductive paste of comparative example 1, particle diameter is less than the ratio height at the fine copper powder end of 1 μ m, by under the temperature more than 200 ℃, carrying out oxidation processes, contraction in the time of can reducing calcining, but the copper powders may after the oxidation fully can not be reduced when calcining, 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 may is low, so the contraction in when calcining is big, conductor comes off from through hole.In addition, because the average specific surface area of copper powders may is big, so when making the copper powders may 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 of particle diameter less than 1 μ m, so tap density is also low, so when calcining takes place 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 in when calcining is big, conductor comes off from through hole.
In addition, for the copper conductive paste of comparative example 6 and comparative example 7, particle diameter is less than the ratio height at the fine copper powder end of 1 μ m, and tap density is little, and simultaneously average specific surface area is big, so be easy to generate 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, shrink also big although carry out oxidation processes.
Claims (13)
1. a through hole is filled and is used copper conductive paste, it 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 that is caused by calcining is below 8%, and the resistivity of the copper conductor after the calcining is below the 10 μ Ω cm.
2. through hole as claimed in claim 1 is filled and is used copper conductive paste, it is characterized in that, at least contain copper powders may, glass powder, organic carrier, copper powders may is to be the mixed-powder that the powder of 1～50 μ m constitutes by the particle diameter of 10～30 quality % less than the particle diameter of the powder of 1 μ m and 70～90 quality %, and tap density is more than the 6.0g/cc, and the organic component content in the copper conductive paste is below the 8.5 quality %.
3. through hole as claimed in claim 2 is filled and is used copper conductive paste, it is characterized in that the average specific surface area of the described mixed-powder of copper is 0.3～0.6m
2/ g.
4. fill as each described through hole in the claim 1～3 and use copper conductive paste, it is characterized in that, contain the cupric oxide powder of 0.5～10 quality % with respect to the copper conductive paste total amount.
5. the manufacture method of the substrate of a copper conductor filled in through-hole, it is characterized in that having: with the described copper conductive paste of claim 1 be filled into operation in the through hole that on the thermal endurance substrate, forms, under oxidizing atmosphere to being filled into that copper conductive paste in the through hole heats and the operation that makes the operation of copper powders may partial oxidation, calcine at the copper conductive paste of under the temperature more than 700 ℃, oxidation processes being crossed under the nonactive atmosphere.
6. the manufacture method of the substrate of copper conductor filled in through-hole as claimed in claim 5 is characterized in that, to heat the operation of carrying out oxidation processes be to implement under the heating condition of 200～300 ℃ of temperature to being filled into copper conductive paste in the through hole.
7. the manufacture method of the substrate of copper conductor filled in through-hole as claimed in claim 5 is characterized in that, described thermal endurance substrate is the ceramic substrate.
8. the manufacture method of the substrate of copper conductor filled in through-hole as claimed in claim 7 is characterized in that, described ceramic substrate is the aluminium nitride substrate.
9. 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 the described copper conductive paste of claim 1 constitutes in the through hole of thermal endurance substrate.
10. the substrate of a copper conductor filled in through-hole is characterized in that, forms by the described method manufacturing of claim 5.
11. a circuitry substrate, it possesses the substrate of the described copper conductor filled in through-hole of claim 9.
12. an electronic unit, it possesses the substrate of the described copper conductor filled in through-hole of claim 9.
13. a semiconductor packages, it possesses the substrate of the described copper conductor filled in through-hole of claim 9.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-254876 | 2008-09-30 | ||
| JP2008254876 | 2008-09-30 | ||
| 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 |
| JP2009-197694 | 2009-08-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101930959A true CN101930959A (en) | 2010-12-29 |
| CN101930959B CN101930959B (en) | 2013-05-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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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| Country | Link |
|---|---|
| JP (1) | JP5379609B2 (en) |
| CN (1) | CN101930959B (en) |
Cited By (3)
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| CN103559940A (en) * | 2013-11-14 | 2014-02-05 | 盐城工学院 | Copper electronic paste and preparation method and application thereof |
| 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 |
| CN104185358A (en) * | 2013-05-27 | 2014-12-03 | 三之星机带株式会社 | Hole filling substrate with surface conducting film, manufacturing method thereof, and method for inhibiting embossing or stripping |
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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 |
| 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 |
| 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 |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2009
- 2009-08-28 JP JP2009197694A patent/JP5379609B2/en active Active
- 2009-09-30 CN CN 200910204039 patent/CN101930959B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104185358A (en) * | 2013-05-27 | 2014-12-03 | 三之星机带株式会社 | Hole filling substrate with surface conducting film, manufacturing method thereof, and method for inhibiting embossing or stripping |
| CN103559940A (en) * | 2013-11-14 | 2014-02-05 | 盐城工学院 | Copper electronic paste and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101930959B (en) | 2013-05-08 |
| JP2010108917A (en) | 2010-05-13 |
| JP5379609B2 (en) | 2013-12-25 |
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