CN101800180B - Method for forming projection electrode and substituted gold plating solution - Google Patents
Method for forming projection electrode and substituted gold plating solution Download PDFInfo
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- CN101800180B CN101800180B CN2009102606104A CN200910260610A CN101800180B CN 101800180 B CN101800180 B CN 101800180B CN 2009102606104 A CN2009102606104 A CN 2009102606104A CN 200910260610 A CN200910260610 A CN 200910260610A CN 101800180 B CN101800180 B CN 101800180B
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- gold plating
- plating liquid
- immersion gold
- gold
- electrode
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- 229910000838 Al alloy Inorganic materials 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GKSYFVIEBZCLEQ-UHFFFAOYSA-N OS(O)=O.N.[Au+3] Chemical compound OS(O)=O.N.[Au+3] GKSYFVIEBZCLEQ-UHFFFAOYSA-N 0.000 description 1
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- MOXADUNKHOQYSJ-UHFFFAOYSA-N [K].[K].[K].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN Chemical compound [K].[K].[K].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN MOXADUNKHOQYSJ-UHFFFAOYSA-N 0.000 description 1
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- 150000002611 lead compounds Chemical class 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
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- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- -1 sulfurous acid ion Chemical class 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 150000003476 thallium compounds Chemical class 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/10—Bump connectors ; Manufacturing methods related thereto
- H01L24/11—Manufacturing methods
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/11—Manufacturing methods
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/151—Die mounting substrate
- H01L2924/156—Material
- H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
- H01L2924/15788—Glasses, e.g. amorphous oxides, nitrides or fluorides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention provides a method for forming a projection electrode simplified with low cost and a substituted gold plating solution using the same. The invention relates to a method for forming a bump (2), comprising a covering working procedure of covering the substituted gold plating solution containing potassium sulfite and derivatives thereof on the surface of a conductive core (21) formed on the electrode (12); in one covering working procedure, a golden film (22) with the thickness of 0.1 to 0.5 microns is formed on the surface of the core (21). Therefore, repeated covering treatment is unnecessary in order to form the golden film (22) for forming.
Description
[technical field]
The present invention relates to become formation method and the immersion gold plating liquid of the projected electrode of the splicing ear in the semiconductor device.
[background technology]
Semiconductor device is because the size of its transistor and distribution is dwindled, and the integrated level of its unit are is high, will reduce manufacturing cost.On the other hand, the function of semiconductor device is just in large-scale and variation.In the manufacturing cost of semiconductor device, although the cost in the operation (hereinafter referred to as the first half procedure) of manufacturing semiconductor chip greatly reduces, but in order to finish as electronic unit, how the cost in the operation of the electronic loop substrate of packing, pack into (hereinafter referred to as later half procedure) does not reduce.Cost in this later half procedure occupies larger proportion in the manufacturing cost of semiconductor device tendency strengthens gradually, becomes the key factor of the manufacturing cost reduction that hinders semiconductor device.
Liquid crystal panel drives in the semiconductor device of usefulness, except low price is strict with in market, also requires high-quality and sub-ization of multiterminal, in order to tackle these requirements, so that the cost in the later half procedure accounts for all more than half parts.And the noble metal price continues surging in recent years.Therefore, liquid crystal panel drives the projected electrode that forms on the semiconductor chip in the semiconductor device of usefulness (below be also referred to as projection (bump)), by all being consisted of this and consisted of by gold (Au) of projection in the past, the main formation section that changes over gradually projection is base metal, only the new mode that is made of gold of surface consists of.As the method for the projection that forms this new mode, known main formation section take projection is as nickel (Ni) alloy, use electroless plating technology to implement gold-plated method to its surface, and the method is regarded as being conducive to reduce the method for cost.It should be noted that gold-plated in the projection, the engagement characteristics when making installation thereafter is good, is preferably formed the above golden tunicle (smearing thick (thick pair of け)) of thickness 0.1 μ m.
In the past, in the gold plating method of Ni or Ni alloy surface, known usually at first by the thin golden tunicle (smearing thin (thin pair of け)) of immersion gold plating formation 0.03～0.05 μ m, follow the method (with reference to patent documentation 1) of the golden tunicle of the thickness that passes through the gold-plated formation expectation of reduction.
In addition, in patent documentation 2, put down in writing and contained complexant, Shui Rong Silver compound, and then contained arbitrarily the displacement electroless gold plating solution of water-soluble thallium compound, water-soluble lead compound, water-soluble copper compound, water-soluble nickel compound or its combination.In the patent documentation 2, also put down in writing by immersion gold plating with golden tunicle smear thin after, use same gold plating liquid to smear golden tunicle thick.
In the patent documentation 3, put down in writing with the self-catalysis type smear thick electroless gold plating as substrate, be used for golden tunicle is smeared thin displacement electroless gold plating solution, as substrate with golden tunicle smear thin after, in order to form the golden tunicle of expectation thickness, further carry out gold-plated processing.
Patent documentation 4 discloses in order to reduce the erosion of gold-plated middle base metal, and improves the adaptation of gold-plated tunicle and base metal, uses the electroless gold plating solution that is added with polymine.
[prior art document]
[patent documentation]
[patent documentation 1] Unexamined Patent 6-232136 communique (on August 19th, 1994 is open)
[patent documentation 2] international No. 02/16668 brochure (on February 28th, 2002 is open) that disclose
[patent documentation 3] Unexamined Patent 4-314870 (on November 6th, 1992 is open)
[patent documentation 4] JP 2003-13248 (on January 15th, 2003 is open)
[summary of the invention]
In the above-mentioned existing gold plating method, the thickness of the golden tunicle that forms in gold-plated process is below the 0.1 μ m, on projected electrode, golden tunicle smeared thick thickness 0.1 μ m when above of being by gold-plated, gold-plated process (smearing thick operation etc. after smearing thin operation) that must be more than 2 times.Thus, the problem that worker is complicated, be difficult to reduce manufacturing cost is arranged.
The object of the invention is to, immersion gold plating operation with once only is provided, can smears on the surface of jut formation method and the immersion gold plating liquid of projected electrode that thickly has good engagement characteristics, contains the film (golden film) of gold, the result, can simplify manufacturing process, reduce cost.
The formation method of the projected electrode that the present invention relates to is characterised in that, be included on the surface of jut of the conductivity that forms on the electrode, form by the coating operation of overlay film with the immersion gold plating liquid that comprises potassium sulfite and polymine or derivatives thereof, in above-mentioned coating operation once, form on the surface of above-mentioned jut more than the thickness 0.1 μ m below the 0.5 μ m by overlay film.
If above-mentioned formation, then owing to come the surface of the jut of the conductivity that forms on the covering electrodes with the immersion gold plating liquid that contains potassium sulfite and polymine or derivatives thereof, therefore in coating operation once, can form on the surface of above-mentioned jut more than the thickness 0.1 μ m below the 0.5 μ m, have good engagement characteristics by overlay film.That is, for form projected electrode can the coating by once process form film fully thick by overlay film, need not the repetition coating and process.As a result, can simplify the manufacturing process of projected electrode, reduce manufacturing cost.
What form in the formation method of the projected electrode that the present invention relates to is more than the 0.1 μ m by overlay film, therefore can by this film with the complete coating of jut, the resistance value as projected electrode can be kept lower.In addition, what form in the formation side of the projected electrode that the present invention relates to is below the 0.5 μ m by overlay film, therefore possesses the sufficient function as jut, can reduce manufacturing cost simultaneously.
The immersion gold plating liquid that uses in the formation method of the projected electrode that the present invention relates to contains potassium sulfite, and this potassium sulfite improves the speed of separating out of gold thus, therefore only can form fully thick golden film with once coating operation.Immersion gold plating liquid further contains the polymine or derivatives thereof, can form thus the golden film of the excellent homogeneous such as outward appearance, engagement characteristics.Therefore, only with once coating operation, can smear the golden film with homogeneous of abundant thickness, good appearance thick on the surface of jut.
In the formation method of the projected electrode that the present invention relates to, above-mentioned immersion gold plating liquid preferably contains below the above 500mg/L of above-mentioned potassium sulfite 50mg/L.
If the contained potassium sulfite of the immersion gold plating liquid that uses in the formation method of the projected electrode that the present invention relates to is as more than the 50mg/L, then can obtain sufficient plating speed, if be below the 500mg/L, it is unstable that plating solution can not become, can not cause selfdecomposition, therefore can more stably be formed for forming the required abundant thick golden film of projected electrode.
In the formation method of the projected electrode that the present invention relates to, above-mentioned immersion gold plating liquid preferably contains below the above 10mg/L of above-mentioned polymine or derivatives thereof 0.01mg/L.
If the contained polymine or derivatives thereof of the immersion gold plating liquid that uses in the formation method of the projected electrode that the present invention relates to is as more than the 0.01mg/L, then the outward appearance of the golden film of institute's coating is better, if be below the 10mg/L, then the speed of separating out of gold can not reduce, and then can not cause that the surface of jut is bad with the driving fit of gold.The golden film of the homogeneous that therefore, easier formation outward appearance, engagement characteristics etc. are better.
In the formation method of the projected electrode that the present invention relates to, above-mentioned immersion gold plating liquid preferably further contains as the gold amount and is equivalent to sulphite and the edetate below the above 50g/L of 10g/L beyond the potassium sulfite below the above 70g/L of golden salt, 10g/L below the above 5.0g/L of 0.1g/L.
If the immersion gold plating liquid that uses in the formation method of the projected electrode that the present invention relates to contains as the gold amount and is equivalent to golden salt more than the 0.1g/L, then can suitably keep the speed of separating out of gold, be equivalent to the following golden salt of 5.0g/L if contain, then can further improve the surface of jut and the adaptation of gold.In addition, because sulphite has the effect of stabilisation gold ligand, the immersion gold plating liquid that uses in the formation method of the projected electrode that therefore the present invention relates to is except potassium sulfite, if contain more than the sulphite 10g/L, then gold can more stably exist, if contain below the sulphite 70g/L, then can not reduce the speed of separating out of gold, can keep high productivity.If the immersion gold plating liquid that uses in the formation method of the projected electrode that the present invention relates to contains edetate, when then consisting of the metal dissolving of jut in the coating operation, the complexant that can be used as this metal works.If contain more than the edetate 10g/L, then can reduce the impact of this metal of stripping, therefore can form the more coating of good appearance.The concentration of edetate is below the 50g/L, then can form projected electrode with lower cost.
In the formation method of the projected electrode that the present invention relates to, the above pH8 of the preferred pH6 of above-mentioned immersion gold plating liquid is following, more than 45 ℃ below 70 ℃.
The pH of the immersion gold plating liquid that uses in the formation method of the projected electrode that the present invention relates to is more than 6, does not then have the anxiety of immersion gold plating liquid selfdecomposition.PH is below 8, and then the speed of separating out of gold increases, and can obtain sufficient plating speed.The immersion gold plating liquid that uses is used under the condition more than 45 ℃, then can obtain sufficient plating speed, can form at short notice the film of preferred thickness.If under the condition below 70 ℃, use, then can reduce the possibility of immersion gold plating liquid selfdecomposition, therefore can improve the stability of this plating solution.
The immersion gold plating liquid that the present invention relates to, for the surface of the jut of the conductivity that is used for forming at electrode, in coating operation once, form the above 0.5 μ m of thickness 0.1 μ m following by the immersion gold plating liquid of overlay film, it is characterized in that, contain potassium sulfite and polymine or derivatives thereof.
The immersion gold plating liquid that the present invention relates to is the surface for the jut of the conductivity that forms at electrode, in coating operation once, form being used by overlay film below the 0.5 μ m more than the thickness 0.1 μ m, owing to contain potassium sulfite and polymine or derivatives thereof, if therefore use it for the formation of projected electrode, then can the coating by once process be formed for forming the required sufficient thickness of projected electrode, have good engagement characteristics by overlay film, need not repeatedly to carry out coating and process.As a result, can simplify the manufacturing process of projected electrode, reduce manufacturing cost.
The immersion gold plating liquid that the present invention relates to therefore by improving the speed of separating out of gold, can form fully thick golden film owing to contain potassium sulfite.Therefore the immersion gold plating liquid that the present invention relates to can form the golden film of the good homogeneous such as outward appearance, engagement characteristics owing to contain the polymine or derivatives thereof.
Be used to form in the coating operation once that the present invention relates to the above 0.5 μ m of thickness 0.1 μ m following by the immersion gold plating liquid of overlay film, preferably contain below the above 500mg/L of above-mentioned potassium sulfite 50mg/L.
If the contained potassium sulfite of the immersion gold plating liquid that the present invention relates to is more than the 50mg/L, then can obtain sufficient plating speed, if be below the 500mg/L, then this plating solution can not become unstable, can not cause selfdecomposition, therefore can stably form fully thick golden film.
Be used to form in the coating operation once that the present invention relates to the above 0.5 μ m of thickness 0.1 μ m following by the immersion gold plating liquid of overlay film, preferably contain below the above 10mg/L of above-mentioned polymine or derivatives thereof 0.01mg/L.
If the contained polymine or derivatives thereof of the immersion gold plating liquid that the present invention relates to is more than the 0.01mg/L, then gold-plated outward appearance becomes better, below 10mg/L, then the speed of separating out of gold can not reduce, and can not cause that the surface of jut is bad with the driving fit of gold.Therefore, can easier formation outward appearance, the golden film of homogeneous that engagement characteristics etc. is better.
Be used to form in the coating operation once that the present invention relates to the above 0.5 μ m of thickness 0.1 μ m following by the immersion gold plating liquid of overlay film, preferably further contain as the gold amount and be equivalent to sulphite and the edetate below the above 50g/L of 10g/L below the above 70g/L of golden salt, 10g/L below the above 5.0g/L of 0.1g/L.
If the immersion gold plating liquid that the present invention relates to contains as the gold amount and is equivalent to golden salt more than the 0.1g/L, then can suitably keep the speed of separating out of gold, be equivalent to the following golden salt of 5.0g/L if contain, then can improve the surface of jut and the adaptation of gold.In addition because sulphite has the effect that makes golden ligand stabilisation, if the immersion gold plating liquid that therefore the present invention relates to contains except potassium sulfite more than the sulphite 10g/L, then gold can more stably exist, if contain below the sulphite 70g/L, then the speed of separating out of gold can not reduce, and can keep higher productivity.If the immersion gold plating liquid that the present invention relates to contains edetate, when then consisting of the metal dissolving of jut in the gold-plated process, can play the effect of the complexant of this metal.If the immersion gold plating liquid that the present invention relates to contains more than the edetate 10g/L, then can reduce the impact of this metal of stripping, therefore can form the coating of better outward appearance.If contain below the edetate 50g/L, then can be with more low-cost formation coating.。
The formation method of the projected electrode that the present invention relates to, as mentioned above, be included in the surface of the jut of the conductivity that forms on the electrode, the immersion gold plating liquid that use contains potassium sulfite and polymine or derivatives thereof forms by the coating operation of overlay film, in above-mentioned coating operation once, form on the surface of above-mentioned jut more than the thickness 0.1 μ m below the 0.5 μ m by overlay film, therefore can process by coating once, be formed for forming the required sufficient thickness of projected electrode, have good engagement characteristics by overlay film, need not repeatedly to carry out coating and process.As a result, can simplify manufacturing process, reduce cost.
The immersion gold plating liquid that the present invention relates to is the surface of the jut of the conductivity that forms at electrode, in coating operation once, be used to form following being used by overlay film of the above 0.5 μ m of thickness 0.1 μ m, contain potassium sulfite and polymine or derivatives thereof, if therefore use it for the formation of projected electrode, then can the coating by once process be formed for forming the required sufficient thickness of projected electrode by overlay film, need not repeatedly to carry out coating and process.As a result, can simplify the manufacturing process of projected electrode, reduce manufacturing cost.
[description of drawings]
Fig. 1 (a) is the sectional view of the operation in the execution mode of formation method that schematically shows the projection that the present invention relates to.
Fig. 1 (b) is the sectional view of the operation in the execution mode of formation method that schematically shows the projection that the present invention relates to.
Fig. 1 (c) is the sectional view of the operation in the execution mode of formation method that schematically shows the projection that the present invention relates to.
[symbol description]
2 projections (projected electrode)
12 electrodes
21 cores (jut)
22 gold medal films (by overlay film)
[embodiment]
The formation method of the projected electrode that the present invention relates to has the coating operation on surface of coming the jut of the conductivity that forms on the covering electrodes with the immersion gold plating liquid that contains potassium sulfite and polymine or derivatives thereof.In this specification, projected electrode refers to be electrically connected on the electrode of the projection of electrode, such as being splicing ear that is arranged at by semiconductor device etc. etc., sometimes can be described as projection.
For the execution mode in the formation method of the projected electrode that the present invention relates to, referring to Fig. 1 (a)～(c) describe, but the present invention is not limited to this execution mode.Fig. 1 (a)～(c) is the sectional view that schematically shows each operation in the execution mode of formation method of the projection (projected electrode) 2 that the present invention relates to.
(core (core) forms operation)
At first, for the following explanation of operation (core formation operation) of the core (jut) 21 that forms projection 2.It should be noted that in the present embodiment, before the above-mentioned coating operation, describe for the example that carries out core formation operation, among the present invention, also can prepare in addition the core 21 of the conductivity of formation on the electrode 12, carry out coating operation described later.
Form in the operation of core 21, at first, shown in Fig. 1 (a), preparation surface is provided with the substrate 1 of electrode 12.The one side of the substrate 1 of contact electrode 12 not, the mode of exposing with its part is insulated film 11 and covers.Substrate 1 also can be by applyings such as adhesives with electrode 12.
As substrate 1, for example can be normally used substrate in the semiconductor device, can use silicon substrate, glass substrate etc. ideally.As electrode 12, can be normally used electrode in the semiconductor device, can use ideally the electrode slice of pad (pad) shape etc.Electrode 12 can use by such as the aluminium alloy of, aluminium (Al), copper (Cu) or aluminium-silicon alloys (Al-Si), Al-zn-mg-cu alloy (Al-Cu), al-si-cu alloy (Al-Si-Cu) etc., etc. constitutor.
Then, shown in Fig. 1 (b), form core 21 at electrode 12 and dielectric film 11.Core 21 is made of the metal with conductivity, forms in the mode that is electrically connected on electrode 12.
As the metal that consists of core 21, the preferred metal of giving birth to displacement in the plating that utilizes immersion gold plating liquid with golden hair that uses is such as listing nickel (Ni), nickel alloy, tin (Sn), copper (Cu) etc.If consist of core 21 with these metals, then can in coating operation thereafter, carry out efficiently gold-plated.The shape of the core 21 that forms is not particularly limited, and when projection is connected in outside terminal etc., is preferably the shape that can be connected with this terminal.
It should be noted that, the method that forms core 21 is unqualified, for example, can use known photolithography technology, on substrate 1, form the mask pattern of the part opening that makes core 21 formation by insulant, use the method for known electrolysis coating technology formation core 21 etc.
(coating operation)
Then, shown in Fig. 1 (c), carry out forming on the surface of core 21 the coating operation of golden film (by overlay film) 22.Thus, can form the projection 2 that contains core 21 and golden film 22.
In the coating operation, use the immersion gold plating liquid that the present invention relates to that contains potassium sulfite and polymine or derivatives thereof, with the surface of golden film 22 coating cores 21.In the coating operation, the immersion gold plating liquid that the Surface Contact of core 21 be the present invention relates to makes gold separate out in the surface of core 21 by the displacement plating.Displacement plating is a kind of for electroless plating, separates out to by the method for plating face from plating solution for making metal.
The method that contacts with the immersion gold plating liquid that the present invention relates to as the surface that makes core 21, for example can use surface impregnation with core 21 in the method for immersion gold plating liquid, immersion gold plating liquid is sprayed in the method on the surface of core 21, by with the axle of substrate 1 quadrature that is formed with core 21 centered by, make substrate 1 rotation, the immersion gold plating drop is added on the method etc. on the surface of core 21.
Among the present invention, when using the immersion gold plating liquid that the present invention relates to that core 21 displacements are plated, core 21 preferably is made of than the high metal of gold ionization tendency.For example, when core 21 is made of nickel or nickel alloy, because the ionization tendency of metal that consists of core 21 is than Jin Genggao, if therefore contact with immersion gold plating liquid, then consists of metal release electronics of core 21 on its surface and dissolve.As a result, the gold in the plating solution is accepted this electronics, separates out in core 21 surfaces.Thus, the surface of core 21 can form golden film 22 efficiently.
In the coating operation, if use the immersion gold plating liquid that the present invention relates to form golden film 22 on core 21 surfaces, then can with coating operation once, form the golden film 22 with thickness below the 0.5 μ m more than the 0.1 μ m on the surface of core 21.That is, in this coating operation, only once use the immersion gold plating of above-mentioned immersion gold plating liquid to process, can form sufficient golden film 22 as projection 2, therefore need not to repeat this immersion gold plating and process with built up film., if golden film 22 to 0.1 μ m are thin, the thoroughly anxiety on the surface of coating core 21 is arranged then herein, fully during coating, rise as the resistance value of projection 2, therefore not preferred.Therefore, as golden film 22, be preferably more than the 0.1 μ m, more preferably more than the 0.2 μ m.When gold film 22 to 0.5 μ m are thick, cause the rising of manufacturing cost, thus not preferred.The thickness of gold film 22 can regulate the time of the Surface Contact immersion gold plating liquid of core 21 by adjusting.Therefore, can be set based on the ideal thickness of golden film 22 time of core 21 contact immersion gold plating liquid.
(immersion gold plating liquid)
Herein, surface for the jut of the conductivity that the present invention relates to, form at electrode, in coating operation once, be used to form the above 0.5 μ m of thickness 0.1 μ m following by the following explanation of the immersion gold plating liquid of overlay film (being designated hereinafter simply as for convenience of description, " the displacement plating solution that the present invention relates to ").The immersion gold plating liquid that the present invention relates to can in coating operation once, form in the following golden film 22 of the above 0.5 μ m of thickness 0.1 μ m and use on the surface that is formed at the core 21 on the electrode 12, contains potassium sulfite and polymine or derivatives thereof.The immersion gold plating liquid that the present invention relates to is owing to comprise sulfurous acid ion, thereby to be also referred to as sulfurous acid be immersion gold plating liquid.
Immersion gold plating liquid refers to as main constituent for using gold by the plating solution of cover plating thing by the displacement plating, contains: the salt, pH buffer and the complexant that contain gold.Immersion gold plating liquid also can add the crystallization of the gold of separating out for modification, the additive of promotion speed of separating out except above-mentioned.Immersion gold plating liquid, gold-plated plating solution (reduction gold plating liquid) is the same as being used for reducing, and need not to contain by autocatalysis to make the reducing agent that gold separates out or the stabilizer of the selfdecomposition that suppresses plating solution etc., forms simply, thereby easily modulation, can modulate with low cost simultaneously.
The reduction gold plating liquid causes variation that liquid forms and unstable easily, sometimes also separates out gold beyond the surface of projection.Relative therewith, immersion gold plating liquid is compared more stable with the reduction gold plating liquid, need not the management of reductant concentration etc., thereby has the easy advantage of management.
(potassium sulfite)
The amount of the potassium sulfite that the immersion gold plating liquid that the present invention relates to is contained is preferably below the above 500mg/L of 50mg/L.Potassium sulfite has the effect of the speed of separating out that improves gold, if but potassium sulfite is less than 50mg/L, the anxiety that can't fully obtain its effect is then arranged.If more than 500mg/L, then speed of separating out accelerates, and it is unstable that plating solution becomes, and the anxiety of the selfdecomposition of causing is arranged.Therefore, if be above-mentioned concentration, then will stably form easilier fully thick golden film 22.Thus, because the immersion gold plating liquid that the present invention relates to contains potassium sulfite, so after the surface of core 21 gold of being separated out covers, also continue to separate out gold, can form fully thick golden film 22.
(polymine or derivatives thereof)
The contained polymine of the immersion gold plating liquid that the present invention relates to can be the polymer with the ethylenimine polymerization.For example, as this polymine, can use the polymine of patent documentation 4 (JP 2003-13248) record etc.Polymine also can be its derivative.
The immersion gold plating liquid that the present invention relates to preferably contains below the above 10mg/L of polymine or derivatives thereof 0.01mg/L.The concentration that contains of polymine or derivatives thereof is less than 0.01mg/L, and then the outward appearance of coating is general red, and then becomes thick crystallization, sometimes produces the bad situation of function as the projection that forms.On the other hand, if the polymine or derivatives thereof contain concentration more than 10mg/L, then the speed of separating out of gold reduces, and then it is bad with the driving fit of gold sometimes to consist of the metal of core 21.The polymine or derivatives thereof has the effect that the outward appearance of coating is adjusted into lemon yellow.Therefore, if use immersion gold plating liquid among the present invention, then can form the golden film 22 of the good homogeneous such as outward appearance, engagement characteristics.
The immersion gold plating liquid that the present invention relates to can on the surface of the core that electrode 12 forms, in coating operation once, form the following golden film 22 of the above 0.5 μ m of thickness 0.1 μ m.That is, if the immersion gold plating liquid that the present invention relates to is used for the formation of projection 2, then only process by the immersion gold plating that once uses this immersion gold plating liquid, can form sufficient golden film 22 as projection 2, need not to repeat this immersion gold plating and process with built up film.
(golden salt)
The immersion gold plating liquid that the present invention relates to preferably further contains golden salt.As this golden salt, be not particularly limited, such as listing gold sodium sulfide, sulfurous acid gold potassium, sulfurous acid gold ammonium etc.The conduct gold amount that the immersion gold plating liquid that the present invention relates to preferably contains in this plating solution is equivalent to the following golden salt of the above 5.0g/L of 0.1g/L.Gold amount is less than 0.1g/L, and then the speed of separating out of gold significantly reduces, and more than 5.0g/L, the anxiety that makes the metal that consists of jut 21 and the adaptation reduction of gold is arranged then.
(sulphite)
The immersion gold plating liquid that the present invention relates to preferably further contains the sulphite beyond the potassium sulfite.As sulphite, be not particularly limited, for example can list sodium sulfite, ammonium sulfite.The immersion gold plating liquid that the present invention relates to preferably except potassium sulfite, contains below the above 70g/L of sulphite 10g/L.Sulphite has the effect that makes golden ligand stabilisation, if sulphite is less than 10g/L, then gold becomes unstable, and the anxiety that produces precipitation is arranged, and more than 70g/L, then gold becomes too stable, and the speed of separating out of gold reduces, and productivity reduces.
(edetate)
The immersion gold plating liquid that the present invention relates to preferably further contains edetate.As edetate, can list ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, ethylenediamine tetra-acetic acid tripotassium etc.The immersion gold plating liquid that the present invention relates to preferably contains below the above 50g/L of edetate 10g/L.Edetate is less than 10g/L, then sometimes is subjected to from the impact of the metal of core 21 strippings, and degraded appearance, more than 50g/L, then the required cost of material increases.Edetate is served as conduct from the role of the complexant of the metal ion of core 21 strippings in the coating operation, form ligand and make the metal ion stabilisation by being combined with metal ion, the place of this metal ion beyond on the object of plating separated out.Therefore, can form the more coating of good appearance.
The immersion gold plating liquid that the present invention relates to preferably uses 45 ℃～70 ℃ scope, more preferably about 55 ℃.During than 45 ℃ lower, can't obtain sufficient plating speed, in order to form the golden film 22 of preferred thickness, the essential long period.When surpassing 70 ℃, the stability degradation of immersion gold plating liquid has the anxiety of the selfdecomposition that produces this plating solution.
The immersion gold plating liquid that the present invention relates to preferably uses with the state of neutrality, and preferably the state with pH6～8 uses.PH is lower than at 6 o'clock, and the contained complexant of immersion gold plating liquid may oxidation Decomposition, and then this plating solution has the anxiety of selfdecomposition.PH is higher than at 8 o'clock, and the speed of separating out of gold reduces, and is difficult to obtain the possibility height of sufficient plating speed.
The present invention is not limited to above-mentioned execution mode, can do various changes in the scope shown in the claim.That is the means of the technology that, will in the scope shown in the claim, suitably change combination and the execution mode that obtains is also contained in the technical scope of the present invention.
[embodiment]
In the present embodiment, at first, form operation by core, on the aluminium electrode of the surface of the semiconductor element that silicon substrate forms setting, form the core that comprises nickel.Afterwards, by the coating operation golden film is coated on core, forms projection.For the golden film of its projection, thickness, outward appearance and engagement characteristics have been estimated.
Form in the operation at core, on the aluminium electrode, form the core that comprises nickel with electroless plating.At first, after use メ Le Network リ one Na, one SC7001 (メ Le テ Star Network ス company system) carries out degreasing, use メ Le プ レ one ト FZ-7350 (メ Le テ Star Network ス company system) to carry out the 1st zincate and process.Then, after use 30vol% nitric acid is peeled off zinc, use メ Le プ レ one ト FBZ (メ Le テ Star Network ス company system) to carry out the 2nd zincate and process, by aluminum and zinc is replaced zinc is separated out on the surface of aluminium electrode.And then use メ Le プ レ one ト NI869 (メ Le テ Star Network ス company system) to carry out 30 minutes electroless nickel platings, form the core of high 10 μ m.
Then, gold-plated to core enforcement in the coating operation, form projection.In embodiment 1 and comparative example 1～2, use the immersion gold plating liquid of the composition shown in the table 1 of lower note, implement 30 minutes gold-plated in pH6.5,55 ℃.
[table 1]
| Form | Embodiment 1 | Comparative example 1 | Comparative example 2 |
| Gold sodium sulfide (gold amount) | 1.5g/L | 1.5g/L | 1.5g/L |
| Disodium ethylene diamine tetraacetate | 30g/L | 30g/L | 30g/L |
| Ethylenediamine | 2g/L | 2g/L | 2g/L |
| Polymine | 2mg/L | 0 | 2mg/L |
| Potassium sulfite | 200mg/L | 200mg/L | 0 |
| pH | 6.5 | 6.5 | 6.5 |
In addition, in the coating operation, in the comparative example 3, use commercially available conduct without the プ レ シ ャ ス Off ァ Block IG-7903 (EEJA company system) of cyanogen immersion gold plating liquid, in pH6.0,60 ℃ implement 30 minutes gold-plated.In the comparative example 4, use プ レ シ ャ ス Off ァ Block IG-7903 (EEJA company system), after pH6.0,60 ℃ implement 5 minutes immersion gold platings, use commercially available conduct without the プ レ シ ャ ス Off ァ Block ACG3000 (EEJA company system) of cyanogen reduction gold plating liquid, reduced gold-plated in 30 minutes in pH7.5,65 ℃ of enforcements.It should be noted that in comparative example 3 and 4 use without cyanogen immersion gold plating liquid for not containing the immersion gold plating liquid of polymine and potassium sulfite.
Formed projection by above-mentioned each operation.Each operation is shown in following table 2.In embodiment 1 and the comparative example 1～4, the operation of implementing is represented with zero respectively.
[table 2]
For the golden film that forms on the projection that obtains, estimate thickness and outward appearance.In the mensuration of thickness, cut out the section of projection by focused ion beam (FIB:Focused Ion Beam), use scanning electron microscopy (SEN).The evaluation of outward appearance is carried out with visual, if be lemon yellow, metallic luster etc., is designated as " well ", redly or when being brown, is designated as " bad ".
For the projection that obtains, estimate engagement characteristics.The substrate that at first, will be formed with projection is installed as semiconductor device.Use to be fit to liquid crystal panel in the installation and to drive the method that the band with the encapsulation of semiconductor device carries encapsulation (Tape Carrier Package), TAB (Tape Automated Bonding, coil type engages automatically).Carry in the band that is formed with splice terminal (lead-in wire), load the substrate that is formed with projection, engage by heating and pressurization, install as semiconductor device.At this moment, put on zinc-plated (Sn) tunicle of lead-in wire and be formed at the golden film alloying of projection, lead-in wire and bump bond.The evaluation of engagement characteristics is that lead-in wire to the semiconductor device installed applies tension force and makes its fracture, if the position of its fracture is beyond the boundary of lead-in wire and projection then be designated as " well " if for the boundary of lead-in wire and projection then be designated as " bad ".
Evaluation result in embodiment shown in the table 31 and the comparative example 1～4.
[table 3]
| Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Thickness (μ m) | 0.30 | 0.34 | 0.09 | 0.04 | 0.30 |
| Outward appearance | Well | Bad | Well | Well | Well |
| Engagement characteristics | Well | Bad | Bad | Bad | Well |
(embodiment 1)
Among the embodiment 1, be formed as described above projection, in the coating operation, shown in the table 1 described above, use the immersion gold plating liquid that contains gold sodium sulfide (gold amount) 1.5g/L, disodium ethylene diamine tetraacetate 30g/L, ethylenediamine 2g/L, polymine 2mg/L and potassium sulfite 200mg/L.
The thickness of the golden film that forms on the projection that obtains shown in the table 3 described above, is 0.30 μ m, obtains fully thick golden film.The outward appearance of gold film is good, is lemon yellow.Engagement characteristics is good, fully possesses as the desired characteristic of electrode.
It should be noted that the golden film among the embodiment 1 is very fine and close, the homogeneity of thickness is high.Immersion gold plating liquid among the embodiment 1, the provable golden film that only can fully form the about 0.3 μ m of thickness by this plating solution.
(comparative example 1)
In the comparative example 1, do not contain polymine in the immersion gold plating liquid, except this point is different with embodiment 1, similarly to Example 1 enforcement.
The thickness of the golden film that forms on the projection that obtains as shown in Table 3 above, is 0.34 μ m, obtains fully thick golden film.But the outward appearance of golden film is general red, and the surface of golden film concavo-convex very coarse is the outward appearance that is not suitable for engaging, and is bad order therefore.Engagement characteristics is also bad.
(comparative example 2)
In the comparative example 2, do not contain potassium sulfite in the immersion gold plating liquid, except this point is different with embodiment 1, similarly to Example 1 enforcement.
The thickness of the golden film that forms on the projection that obtains as shown in Table 3 above, is 0.09 μ m, and outward appearance is good, but can't obtain fully thick golden film.As a result, engagement characteristics is bad.
(comparative example 3)
In the comparative example 3, be formed as described above projection, in the coating operation, use the immersion gold plating liquid that does not contain polymine and potassium sulfite.
The thickness of the golden film that forms on the projection that obtains as shown in Table 3 above, is 0.04 μ m, can't obtain fully thick golden film.The outward appearance of gold film is good, but thin thickness, so engagement characteristics is bad.
(comparative example 4)
In the comparative example 4, be formed as described above projection, in the coating operation, use the immersion gold plating liquid do not contain polymine and potassium sulfite to carry out immersion gold plating after, it is gold-plated to implement reduction again.
The thickness of the golden film that forms on the projection that obtains as shown in Table 3 above, is 0.30 μ m, has obtained abundant thick golden film.Outward appearance and the engagement characteristics of gold film are good.
[industrial applicability]
The formation method of the projected electrode that the present invention relates to can be simplified manufacturing process, reduces cost, thereby applicable to the manufacturing of semiconductor device etc.
Claims (7)
1. the formation method of projected electrode is characterized in that, comprises: the surface of the jut of the conductivity that forms at electrode, form by the coating operation of overlay film with the immersion gold plating liquid that contains potassium sulfite and polymine,
In above-mentioned coating operation once, form on the surface of above-mentioned jut more than the thickness 0.1 μ m below the 0.5 μ m by overlay film,
Above-mentioned immersion gold plating liquid contains below the above 500mg/L of above-mentioned potassium sulfite 50mg/L.
2. the formation method of projected electrode as claimed in claim 1 is characterized in that, above-mentioned immersion gold plating liquid contains below the above 10mg/L of above-mentioned polymine 0.01mg/L.
3. the formation method of projected electrode as claimed in claim 1, it is characterized in that above-mentioned immersion gold plating liquid further contains as the gold amount and is equivalent to sulphite and the edetate below the above 50g/L of 10g/L beyond the potassium sulfite below the above 70g/L of golden salt, 10g/L below the above 5.0g/L of 0.1g/L.
4. the formation method of projected electrode as claimed in claim 1 is characterized in that, above-mentioned immersion gold plating liquid be the above pH8 of pH6 following, more than 45 ℃ below 70 ℃.
5. immersion gold plating liquid, for the surface of the jut of the conductivity that forms at electrode, in coating operation once, be used to form the above 0.5 μ m of thickness 0.1 μ m following by the immersion gold plating liquid of overlay film, it is characterized in that,
Contain potassium sulfite and polymine,
Contain below the above 500mg/L of above-mentioned potassium sulfite 50mg/L.
6. immersion gold plating liquid as claimed in claim 5 is characterized in that, contains below the above 10mg/L of above-mentioned polymine 0.01mg/L.
7. immersion gold plating liquid as claimed in claim 5, it is characterized in that, further contain as the gold amount and be equivalent to sulphite and the edetate below the above 50g/L of 10g/L beyond the potassium sulfite below the above 70g/L of golden salt, 10g/L below the above 5.0g/L of 0.1g/L.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008322851A JP4758470B2 (en) | 2008-12-18 | 2008-12-18 | Method for forming protruding electrode and displacement gold plating solution |
| JP2008-322851 | 2008-12-18 |
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| CN101800180A CN101800180A (en) | 2010-08-11 |
| CN101800180B true CN101800180B (en) | 2013-01-02 |
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| JP (1) | JP4758470B2 (en) |
| KR (1) | KR101137757B1 (en) |
| CN (1) | CN101800180B (en) |
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| JP6940739B2 (en) * | 2016-03-17 | 2021-09-29 | 日亜化学工業株式会社 | Light emitting element and manufacturing method of light emitting element |
| CN110114507A (en) | 2016-12-27 | 2019-08-09 | 关东化学株式会社 | Without cyanogen immersion gold plating liquid composition |
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| JPH08239768A (en) * | 1995-03-01 | 1996-09-17 | Electroplating Eng Of Japan Co | Electroless gold plating bath |
| JP4147359B2 (en) * | 1998-12-24 | 2008-09-10 | 石原薬品株式会社 | Displacement gold plating bath and gold plating method using the bath |
| TWI239798B (en) * | 1999-05-28 | 2005-09-11 | Toppan Printing Co Ltd | Photo electric wiring substrate, mounted substrate, and the manufacture method of the photo electric wiring substrate |
| JP3831287B2 (en) * | 2002-04-08 | 2006-10-11 | 株式会社日立製作所 | Manufacturing method of semiconductor device |
| JP2004149824A (en) * | 2002-10-29 | 2004-05-27 | Murata Mfg Co Ltd | Gold plating liquid, plating method using the gold plating liquid, method of producing electronic component, and electronic component |
| JP4387175B2 (en) * | 2003-07-07 | 2009-12-16 | 積水化学工業株式会社 | Coated conductive particles, anisotropic conductive material, and conductive connection structure |
| JP2006322037A (en) * | 2005-05-18 | 2006-11-30 | Electroplating Eng Of Japan Co | Gold-plating solution |
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2008
- 2008-12-18 JP JP2008322851A patent/JP4758470B2/en not_active Expired - Fee Related
-
2009
- 2009-12-16 TW TW098143173A patent/TWI400356B/en not_active IP Right Cessation
- 2009-12-16 KR KR1020090125322A patent/KR101137757B1/en not_active IP Right Cessation
- 2009-12-17 CN CN2009102606104A patent/CN101800180B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5364460A (en) * | 1993-03-26 | 1994-11-15 | C. Uyemura & Co., Ltd. | Electroless gold plating bath |
| CN1407132A (en) * | 2001-07-02 | 2003-04-02 | 希普雷公司 | Nonelectrolytic gold plating liquid and method thereof |
| CN1506494A (en) * | 2002-12-10 | 2004-06-23 | �ض���ѧ��ʽ���� | Non-electrolytic goldplating liquid |
| CN1535103A (en) * | 2003-03-18 | 2004-10-06 | 日本特殊陶业株式会社 | Wiring board |
| CN1940147A (en) * | 2005-09-30 | 2007-04-04 | 恩伊凯慕凯特股份有限公司 | Formation method of gold bump or gold wiring |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101800180A (en) | 2010-08-11 |
| KR101137757B1 (en) | 2012-04-24 |
| TWI400356B (en) | 2013-07-01 |
| JP4758470B2 (en) | 2011-08-31 |
| JP2010144220A (en) | 2010-07-01 |
| KR20100070998A (en) | 2010-06-28 |
| TW201033404A (en) | 2010-09-16 |
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