CN104778992B - Wear-resisting erosion resistance is without coating copper cash and manufacture method thereof - Google Patents
Wear-resisting erosion resistance is without coating copper cash and manufacture method thereof Download PDFInfo
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- CN104778992B CN104778992B CN201410010037.2A CN201410010037A CN104778992B CN 104778992 B CN104778992 B CN 104778992B CN 201410010037 A CN201410010037 A CN 201410010037A CN 104778992 B CN104778992 B CN 104778992B
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- 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
- H01L24/42—Wire connectors; Manufacturing methods related thereto
- H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L24/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
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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
- H01L24/42—Wire connectors; Manufacturing methods related thereto
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- 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
- H01L2224/02—Bonding areas; Manufacturing methods related thereto
- H01L2224/04—Structure, shape, material or disposition of the bonding areas prior to the connecting process
- H01L2224/05—Structure, shape, material or disposition of the bonding areas prior to the connecting process of an individual bonding area
- H01L2224/0554—External layer
- H01L2224/05599—Material
- H01L2224/056—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
- H01L2224/05617—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 400°C and less than 950°C
- H01L2224/05624—Aluminium [Al] as principal constituent
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/43—Manufacturing methods
- H01L2224/438—Post-treatment of the connector
- H01L2224/43848—Thermal treatments, e.g. annealing, controlled cooling
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- 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
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
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- H—ELECTRICITY
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- 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
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45147—Copper (Cu) as principal constituent
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/4554—Coating
- H01L2224/45565—Single coating layer
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- H01L2924/00011—Not relevant to the scope of the group, the symbol of which is combined with the symbol of this group
Abstract
The invention provides a kind of wear-resisting erosion resistance without coating copper cash and manufacture method thereof.This manufacture method is to form the thickness plating carbon-coating less than 30nm prior to the surface of a copper core, the chromium coating that a thickness is 30nm 100nm is formed then at the surface of plating carbon-coating, finally carry out vacuum heat, plating carbon-coating and chromium coating is made to diffuse in the Al-Qaeda terrorist organization of copper core completely, and form a carbonization chromium-copper phase infiltrating tissues having wear-resisting erosion resistance characteristic in the Al-Qaeda terrorist organization surface of copper core, wherein carbonization chromium-copper includes (CrCu) mutually3C7With (CrCu)3C2.Thus, the manufacture method of the present invention not only can increase case hardness and the top layer nano hardness of copper core, also can promote non-oxidizability and the corrosion resistance of wire rod.
Description
Technical field
The present invention is related to a kind of wear-resisting erosion resistance without coating copper cash and manufacture method thereof, refers in particular to one and is applicable to partly lead
The wear-resisting erosion resistance of body encapsulation, IC encapsulation or LED package is without coating copper cash and manufacture method thereof.
Background technology
Semiconductor package is contained in routing and engages in (Wire-Bonding, WB) technique, often higher because of the hardness of copper cash and easy oxygen
The problem changed causes the defect in packaging technology；And for this defect, existing dealer changes for the joint copper cash of encapsulation
Good, refer to TaiWan, China patent of invention disclose No. 201207129 disclosed " the joint copper cash of encapsulation use and
Manufacture method ", wherein disclose a kind of joint copper cash encapsulated, composition includes silver (Ag), additive, Yi Jitong
(Cu)；Wherein, silver content is 0.1-3wt%；Additive at least one select free nickel (Ni), platinum (Pt), palladium (Pd), stannum (Sn),
And gold (Au) group that formed, and the content of additive is 0.1-3wt%；Furthermore, copper accounts for silver eutectic phase volume fraction
Entire volume of 0.1-8%, and joint copper cash tensile strength is at more than 250MPa, conductivity is at more than 70%IACS；
Thus, not only make impedance and tradition gold thread quite or even lower (> 70%IACS), can reach more preferably conductivity,
And hardness is moderate and is prone to welding, more can carry out ball-type welding, also can use under the critical conditions of resistance to thermal cycle.
But, though the above-mentioned copper cash that engages can meet cost and the requirement welded, but have wearability oxidizable, low and
Low defect against corrosion, for solving the defect of above-mentioned copper conductor, has dealer to be formed with a chrome plating in wire substrate surface,
Utilize the characteristic that chromium metal tool itself is wear-resisting and anti-corrosion, reach good wear-resisting and corrosion stability；For example, refer to
TaiWan, China patent of invention announce No. I411373, No. I378533, No. I347655, No. I255528,
No. 169454 etc.；And owing to hexavalent chromium is tool high toxicity, human body is had carcinogenesis and environment is had sternly
Heavily threatening, the most above-mentioned chrome plating, when reality is implemented, is based on trivalent chromium, but trivalent chromic ion particle diameter is excessive,
It is difficult to diffuse in the Al-Qaeda terrorist organization of copper core, causes electroplating deposition efficiency the best and cause copper core surface blistering or interior
The defect that portion peels off produces.
Additionally, also there is dealer further by a face coat, it can be integrated antenna package, it is provided that more preferably go between
Joint Properties；Refer to TaiWan, China patent of invention announce No. 480292 and disclosed " being applicable to what lead-in wire engaged
Palladium face coat and the method forming palladium face coat ", its face coat is formed on a substrate, comprises a palladium layers
With one or more material layers；These one or more material layers are clipped between substrate and palladium layers；When at least one material
When hardness is less than 250 (KHN50), the hardness of this palladium layers is less than about 500 (KHN50)；The wherein thickness of this palladium layers
More preferably greater than 0.075 micron, to avoid oxide to be formed on its lower material layer；Above-mentioned baseplate material can include
Copper or copper alloy, replace gold thread by plating palladium copper cash, not only can save the material cost of about seventy percent, and plate palladium
Reliability (such as high temperature resistant, high humidity ability) when copper cash is used also can meet the requirements；Additionally, also see also new
Tie new high-tech material limited company and Tie Wei Metallgesellschaft AG are applied for that a series of relevant quasiconductor fills
Put the TaiWan, China patent of invention with splice grafting line, announce No. I342809, No. I364806, No. I364806,
No. 201107499, No. 20114071 and No. 201230903 etc.；The bond wire configuration of above-mentioned case is big
Many be all be provided with in a core (can be constituted by the metal such as copper, gold, silver) surface an epidermal area (can be palladium, ruthenium, rhodium,
Platinum, and silver constituted), cause above-mentioned closing line to implement to use in reality and often produce following defect: (a) is because plating
The surface of palladium copper cash (core) has a palladium layers (epidermal area) so that hardness is higher, and process current controls to be difficult to, often
Cause plating palladium layers uneven thickness, cause encapsulation process entirety output rate variance, yield is on the low side；B () copper or copper alloy plate
Palladium layers is in time burning ball forming (electric frame off, EFO), because the palladium layers on surface makes balling-up (free air ball, FAB)
Centre of sphere hardness really up to the mark, the intensity causing soldered ball neck above is not enough, after routing (wire bonding, WB), often
There is cervical region breakage problem, and then the problem causing joint interface to be peeled off occurs；The surface formed on (c) copper or copper alloy
The food preservation test of coating at high temperature (160 DEG C, 24 hours) is the best, is easily caused the phenomenon of surface blistering, causes joint
Intensity reduces, and from the viewpoint of reliability, has problem；D, after () balling-up, palladium element is almost inclined in neck area
Analysis, grows up the most evident to compound (Intermetallic Compound, IMC) between suppression interface metal；And (e) does not has
Having antioxidation, effect of chlorine-resistant impedance, wire rod easily reduces its electric conductivity, even because of the corrosion etc. of high temperature, chloride ion
Cause broken string situation.
Summary of the invention
For solving above-mentioned technical problem, main purpose of the present invention is for providing a kind of wear-resisting erosion resistance without coating copper cash and manufacture thereof
Method.The manufacture method of the present invention not only can increase case hardness and the top layer nano hardness of copper core, also can increase line
The non-oxidizability of material and corrosion resistance.
In order to achieve the above object, the present invention provides a kind of wear-resisting erosion resistance without coating copper cash manufacture method, and it includes following
Step:
Step one: prepare a copper core；
Step 2: a plating carbon-coating is formed at the surface of this copper core, and the thickness of this plating carbon-coating is less than 30nm；
Step 3: form a chromium coating in the surface of this plating carbon-coating, the thickness of this chromium coating is 30nm-100nm；With
And
Step 4: carry out vacuum heat, makes this plating carbon-coating and this chromium coating diffuse to the base of this copper core completely
In tissue, the surface noresidue coating of this copper core, and form a tool in the Al-Qaeda terrorist organization surface of this copper core wear-resisting anti-
The carbonization chromium-copper phase infiltrating tissues of erosion characteristic, wherein, this carbonization chromium-copper includes (CrCu) mutually3C7With (CrCu)3C2。
At above-mentioned wear-resisting erosion resistance without in coating copper cash manufacture method, it is preferable that the thickness of described plating carbon-coating is
3nm-28nm。
At above-mentioned wear-resisting erosion resistance without in coating copper cash manufacture method, it is preferable that described plating carbon-coating divides with described chromium coating
Not by sputter, be deposited with or deposit in the way of formed.
At above-mentioned wear-resisting erosion resistance without in coating copper cash manufacture method, it is preferable that the temperature of described vacuum heat is
400 DEG C-600 DEG C, and the process time be 30-90 minute.
At above-mentioned wear-resisting erosion resistance without in coating copper cash manufacture method, it is preferable that described vacuum heat is with temperature
520 DEG C, the mode of 60 minutes time processes.
At above-mentioned wear-resisting erosion resistance without in coating copper cash manufacture method, it is preferable that described chromium coating is trivalent chromium chrome plating layer.
The manufacture method of the present invention is to be initially formed a thickness in the surface of a copper core less than 30nm (preferably
Plating carbon-coating 3nm-28nm), wherein chromium coating is trivalent chromium chrome plating layer；Then, the surface in plating carbon-coating forms one again
Chromium coating, and the thickness of chromium coating can be 30nm-100nm；Finally, carry out vacuum heat, make plating carbon-coating and
Chromium coating diffuses in the Al-Qaeda terrorist organization of copper core completely, that is the surface noresidue coating of copper core, and in copper core
The Al-Qaeda terrorist organization surface form the chrome carbide copper phase infiltrating tissues of a tool wear-resisting erosion resistance characteristic, wherein carbonization chromium-copper wraps mutually
Include (CrCu)3C7With (CrCu)3C2；Thus, in the carbonization chromium-copper phase surface layer that copper core the Al-Qaeda terrorist organization surface is formed,
Not only can increase case hardness and the top layer nano hardness of copper core, also can promote the non-oxidizability of wire rod with corrosion-resistant
Property, solve traditional in semiconductor packages and encapsulation process of light-emitting diode, wire rod is because of environmental oxidation, chloride ion corrosion
Problem is reduced by produced reliabilitys such as porcelain mouth abrasion broken strings with routing.
In one embodiment of the invention, wherein the temperature range of vacuum heat is preferably 400 DEG C-600 DEG C, and
The process time is 30-90 minute；More preferably with temperature 520 DEG C, the mode of 60 minutes time processes.
The present invention also provide for a kind of by above-mentioned wear-resisting erosion resistance without coating copper cash manufacture method prepare wear-resisting anti-
Erosion is without coating copper cash.
Detailed description of the invention according to the present invention, it is preferable that above-mentioned wear-resisting erosion resistance without coating copper cash in routing technique with
When aluminum pad combines, forming the aluminium carbide phase of compound thickness between suppression Cu/Al interface metal, this aluminium carbide includes mutually
Al4C and Al4C3。
Detailed description of the invention according to the present invention, it is preferable that between described Cu/Al interface metal, compound thickness is
0.45μm-0.75μm。
With the wear-resisting erosion resistance prepared by manufacture method of the present invention without coating copper cash, when routing technique is combined with aluminum pad, can
Forming the aluminium carbide phase of compound thickness between suppression Cu/Al interface metal, wherein aluminium carbide includes Al mutually4C with
Al4C3, and between Cu/Al interface metal, compound thickness is 0.45 μm-0.75 μm, reaches to promote faying face intensity, with
And there is the effect that can maintain loop low resistance characteristic.
The manufacture method of the present invention sequentially forms plating carbon-coating and the chromium coating of suitable thickness in copper core surface, then at suitable
When heat treatment under the conditions of so that the plating carbon ion that disengages of carbon-coating can spread up and down and form the carbon of tool wear-resisting erosion resistance characteristic
Change chromium-copper phase, and then the chromium ion solving known chromium coating is difficult to diffuse in the Al-Qaeda terrorist organization of copper core, causes copper core
Outside line surface blistering or the internal defect peeled off, and the carbonization chromium-copper phase surface that the present invention is formed in the Al-Qaeda terrorist organization surface
Layer, not only can increase case hardness and the top layer nano hardness of copper core, also can promote non-oxidizability and the corrosion resistant of wire rod
Erosion property.
Accompanying drawing explanation
Fig. 1 is the wear-resisting erosion resistance of the present invention manufacture method flow chart of steps without coating copper cash.
Fig. 2 is before wear-resisting erosion resistance of the present invention does not carries out vacuum heat without coating copper cash, and its copper core surface has plating carbon
Layer and the electron micrograph of chromium coating.
Fig. 3 is wear-resisting erosion resistance of the present invention diffuses to heart yearn base group completely without the coating on the copper core surface of coating copper cash
Electron micrograph in knitting.
Primary clustering symbol description:
Step one S1 step 2 S2
Step 3 S3 step 4 S4
Detailed description of the invention
First, the wear-resisting erosion resistance made by manufacture method of the present invention can such as be applicable to printed circuit board (PCB) without coating copper cash
The terminal of the electronics industry part of circuit, IC encapsulation, ito substrate, IC-card etc. or circuit surface, or need to be in evil
The packaging technology of (such as chloride ion, sulfidation corrosion) under bad environment；Refer to shown in Fig. 1, for wear-resisting erosion resistance of the present invention
The manufacture method flow chart of steps of copper cash without coating, it includes following step:
Step one S1: prepare a copper core；Wherein copper core can be fine copper heart yearn or copper alloy heart yearn, at this not
Limit, be in the present embodiment as a example by fine copper heart yearn；
Step 2 S2: again by a plating carbon-coating by sputter, be deposited with or deposit in the way of be formed at the surface of copper core, its
The thickness of middle plating carbon-coating be less than 30nm, preferably 3nm-28nm, and plate carbon-coating can such as but be not limited to a stone
Layer of ink or the oil reservoir etc. of Hydrocarbon；
Step 3 S3: then, in plating carbon-coating surface by sputter, be deposited with or deposit in the way of form a chromium coating again,
And chromium coating is preferably trivalent chromium chrome plating layer, its thickness can be 30nm-100nm；Refer to shown in Fig. 2, for this
Before bright copper core does not carries out vacuum heat, there is in its surface the electron micrograph of plating carbon-coating and chromium coating；With
And
Step 4 S4: the copper core of above-mentioned surface tool plating carbon-coating with chromium coating is carried out vacuum heat, makes plating carbon-coating
And chromium coating diffuses in the Al-Qaeda terrorist organization of copper core completely, the wherein surface noresidue coating of copper core, and in copper
The Al-Qaeda terrorist organization surface of heart yearn forms the carbonization chromium-copper phase infiltrating tissues of a tool wear-resisting erosion resistance characteristic, and carbonization chromium-copper wraps mutually
Include (CrCu)3C7With (CrCu)3C2；Wherein, the temperature of vacuum heat is 400 DEG C-600 DEG C, and the process time is
30-90 minute；Preferably with temperature 520 DEG C, the mode of 60 minutes time processes, in order to plating carbon-coating and chromium coating
Can diffuse to completely, in the Al-Qaeda terrorist organization of copper core (carbon ribbon chromium and run in copper), form a wear-resisting erosion resistance without coating copper
Line, refers to shown in Fig. 3, for wear-resisting erosion resistance of the present invention without the plating carbon-coating on the copper core surface of coating copper cash and chromium plating
Layer diffuses to the electron micrograph in heart yearn the Al-Qaeda terrorist organization completely.
Then, by further appreciating that the purpose of the present invention, feature and the effect reached, institute of the present invention is the most hereby lifted
The wear-resisting erosion resistance prepared is without some specific embodiments of coating copper cash, and proves that the manufacture method of the present invention can further
The scope of actual application, but it is not intended to limit in any form the scope of the present invention.First, preparing a line footpath (φ) is
The fine copper heart yearn (4N) of 20 μm；On copper core plated surface, a thickness is the plating carbon-coating of 0-36 nanometer, then at plating carbon-coating
Plate the chromium coating that a thickness is 62 nanometers, under not carrying out heat treatment, copper core is carried out surface hardness analysis,
Top layer nano hardness analysis, blowout current density, hot strength and ductility analysis；Its experimental result such as table 1
Shown in, should be clear from, after the thickness of plating carbon-coating is more than 28 nanometers, its blowout current density significantly reduces；Therefore,
It is preferred that the plating carbon layers having thicknesses of the present invention is defined to 3-28 nanometer.
Table 1
Then, on copper core plated surface, a thickness is respectively the plating carbon-coating of 3,12 and 28 nanometers, above-mentioned plating carbon
Layer plates a thickness the most respectively and is respectively the chromium coating of 38,62 and 95 nanometers, is formed with 9 groups accordingly and plates with difference
The embodiment that carbon-coating and chromium coating thickness are formed, i.e. sample A-I, by 9 groups of embodiments with temperature 460 DEG C, time
Within 60 minutes, carry out vacuum heat, and carry out oxidation test, surface hardness analysis, top layer nano hardness analyze and
Salt spray test；Wherein oxidation test has atmospheric oxidn test and the high temperature of 160 DEG C of-24hr of 20 DEG C of-196hr respectively
Oxidation test, salt spray test then with 100%, the NaCl of pH value 7-8 at 35 DEG C, carry out 96 hours, and table
Layer nano hardness analysis is by Nano-indentation system&Nano-mechanical microscopy company,
Model is the nano hardness tester (Nano Hardness Tester) of MTS Nano Indenter XP, to bear a heavy burden
The hardness that 20-30 μ N is measured；Its experimental result is as shown in table 2, should be clear from, the plating carbon-coating on copper core surface
Or chromium coating thickness is the thickest, under identical heat treatment time, the biggest in the probability of copper core remained on surface coating；Lift
For example, sample F is to be respectively provided with plating carbon-coating and the chromium coating of 95 nano thickness of 12 nano thickness, in 460
DEG C, under the vacuum heat of 60 minutes, still remain the chromium coating of 24 nanometers, as known core surfaces has table
The defect of cortex so that sample F cannot pass through high-temperature oxidation test and salt spray test；In like manner, sample H Yu I also because of
Copper core surface has residual layer (plating carbon-coating or chromium coating) cannot pass through high-temperature oxidation test or salt spray test；On the contrary
Ground, when copper core surface is without the residual of plating carbon-coating or chromium coating (such as sample A, B, D and E), all can be by big
Gas oxidation test, high-temperature oxidation test and salt spray test；At this it is noted that work as plating carbon-coating or the thickness of chromium coating
When spending the thinnest (such as plating carbon layers having thicknesses is less than 30 nanometers less than 3 nanometers and chromium coating thickness), in vacuum heat
Though rear two coating can diffuse to, in the Al-Qaeda terrorist organization of copper core, so cannot reach with the surface hardness of Durometer measurements completely
More than Knoop hardness HK=50 of general industrywide standard, and top layer nano hardness is also unable to reach more than 2.2GPa's
Standard, reflects plating carbon-coating and the important technology feature that chromium coating thickness range is the present invention.
Table 2
Referring to shown in table 3 again, it is with temperature 520 DEG C, time by 9 groups of embodiments of the sample A-I in table 2
Within 60 minutes, carry out vacuum heat, it will be evident that when copper core surface is without the residual of plating carbon-coating or chromium coating,
All samples all can be by atmospheric oxidn test, high-temperature oxidation test and salt spray test；Furthermore, ask for an interview sample in table 2
Product A is plating carbon-coating and the chromium coating of 38 nano thickness being respectively provided with 3 nano thickness, in not carrying out at Vacuum Heat
Before reason, its surface hardness and top layer nano hardness are divided into 41HK and 1.16GPa, in 460 DEG C, and the vacuum of 60 minutes
After heat treatment, copper core surface is without plating carbon-coating or the residual of chromium coating, and its surface hardness increases respectively with top layer nano hardness
Adding to 54HK and 2.35GPa, the most same sample A is in 520 DEG C, after the vacuum heat of 60 minutes, and its top layer
Hardness and top layer nano hardness can be significantly increased to 72HK and 3.21GPa, reflect that choosing of vacuum heat condition is same
An important technology feature for the present invention；Furthermore, from experimental data, surface hardness is big with top layer nano hardness
The little thickness tool positive correlation with plating carbon-coating or chromium coating, its reason is that carbon atom has minimum radius (about 70pm),
Therefore in the plating carbon-coating in the middle of copper core and chromium coating, under thermal environment, carbon ion can spread up and down and to form tool resistance to
Grind carbonization chromium-copper phase infiltrating tissues (such as (CrCu) of characteristic against corrosion3C7With (CrCu)3C2)；And when plating carbon-coating or chromium plating
When the thickness of layer is the thickest, copper core surface to be reached without plating carbon-coating or the residual of chromium coating, the temperature of vacuum heat with
Time all must increase, and right this measure certainly will be significantly increased manufacturing cost；Accordingly, it is known that plating carbon-coating or the thickness of chromium coating,
And the condition of vacuum heat is necessary for choosing of an optimal tradeoff (trade-off), this must obtain via excessively experiment side
To implement, and its result the most quite has effectiveness, and these experiment parameters operate the successfully required non-ability of factor considered
Territory those skilled in the art be readily apparent that；At this it is noted that according to the creation spirit of chromium coating of the present invention be can make many
Kind change or modify embodiment, such as chromium coating in addition to containing chromium metal, also can include palladium, nickel, gold, silver,
In the metal such as aluminum, zinc one or both above combinations, without affecting the enforcement of the present invention, as long as copper core can be reached
The surface noresidue coating of line, and the carbonization chromium-copper of a tool wear-resisting erosion resistance characteristic is formed in the Al-Qaeda terrorist organization surface of copper core
Effect of phase infiltrating tissues, therefore in chromium coating, in addition to chromium metal, the selection of added metal is to regard in fact
The demand of border application product and determine, do not limit at this.
Additionally, with temperature 520 DEG C, the sample A-I embodiment of 60 minutes time vacuum heat, carrying out routing
After balling-up, to routing balling-up (EFO), routing bond strength (gf), and compound (IMC) thickness between interface metal
Testing, the experimental data of measurement is as shown in table 3；Can substantially learn, the copper cash made in the process of the present invention, its
Routing bond strength is all more than 7gf, far above general pure copper wire 4-5gf, and general copper alloy wire 5-6gf, therefore
Balling-up (out of roundness) and routing bond strength all can comply fully with the packaging conductive wire prescription of electronics industry part；Again
Person, when the wear-resisting erosion resistance of the present invention is combined with aluminum pad in routing technique without coating copper cash, plating carbon-coating in carbon ion with
Aluminum forms aluminium carbide phase (such as Al4C and Al4C3) so that when the thickness plating carbon-coating or chromium coating is the thickest, generate more
Many aluminium carbides can suppress compound between Cu/Al interface metal to generate thickness, experimental result display Cu/Al interface gold mutually
Between genus, compound thickness is 0.45 μm-0.75 μm, far below general pure copper wire about 1.5 μm, and general copper alloy wire
About 1.0 μm, reach to promote faying face intensity, and have the effect that can maintain loop low resistance characteristic.
Table 3
From above-mentioned enforcement explanation, the wear-resisting erosion resistance of the present invention is without coating copper cash and manufacture method thereof and prior art
In comparison, the invention have the advantages that
1, the present invention is by the plating carbon-coating in the middle of copper core and chromium coating, under thermal environment, the carbon ion meeting disengaged
Diffuseing to form the carbonization chromium-copper phase of tool wear-resisting erosion resistance characteristic up and down, the chromium ion solving known chromium coating is difficult to diffuse to copper
In the Al-Qaeda terrorist organization of heart yearn, it is to avoid because electroplating deposition efficiency is the best, cause copper core surface blistering or internal peel off lack
Fall into and produce.
2, the present invention diffuses to copper core completely because of overlay coating, and is formed with (CrCu) in the Al-Qaeda terrorist organization surface3C7With
(CrCu)3C2Carbonization chromium-copper phase infiltrating tissues, not only can increase the case hardness of copper core and top layer nano hardness,
Also can promote non-oxidizability and the corrosion resistance of wire rod, solve tradition in semiconductor packages and encapsulation process of light-emitting diode
In, wire rod is reduced problem with routing by produced reliabilitys such as porcelain mouth abrasion broken strings because of environmental oxidation, chloride ion corrosion.
3, the present invention is by the plating carbon-coating in the middle of copper core and chromium coating so that copper core is tied with aluminum pad in routing technique
During conjunction, the carbon ion in plating carbon-coating forms aluminium carbide phase with aluminum, can effectively suppress compound between Cu/Al interface metal raw
Become thickness, reach to promote faying face intensity, and there is the effect that can maintain loop low resistance characteristic.
Claims (9)
1. wear-resisting erosion resistance is without a coating copper cash manufacture method, and it comprises the following steps:
Step one: prepare a copper core；
Step 2: a plating carbon-coating is formed at the surface of this copper core, and the thickness of this plating carbon-coating is less than 30nm；
Step 3: form a chromium coating in the surface of this plating carbon-coating, the thickness of this chromium coating is 30nm-100nm；With
And
Step 4: carry out vacuum heat, makes this plating carbon-coating and this chromium coating diffuse to the substrate of this copper core completely
In tissue, the surface noresidue coating of this copper core, and form a tool in the substrate microstructure surface of this copper core wear-resisting anti-
The carbonization chromium-copper phase infiltrating tissues of erosion characteristic, wherein, this carbonization chromium-copper includes (CrCu) mutually3C7With (CrCu)3C2。
2. wear-resisting erosion resistance as claimed in claim 1 is without coating copper cash manufacture method, wherein, and the thickness of described plating carbon-coating
Degree is 3nm-28nm.
3. wear-resisting erosion resistance as claimed in claim 1 is without coating copper cash manufacture method, and wherein, described plating carbon-coating is to spatter
Plating mode formed, described chromium coating by sputter, be deposited with or deposit in the way of formed.
4. wear-resisting erosion resistance as claimed in claim 1 is without coating copper cash manufacture method, wherein, described vacuum heat
Temperature be 400 DEG C-600 DEG C, and the process time is 30-90 minute.
5. wear-resisting erosion resistance as claimed in claim 4 is without coating copper cash manufacture method, wherein, described vacuum heat
Being with temperature 520 DEG C, the mode of 60 minutes time processes.
6. wear-resisting erosion resistance as claimed in claim 1 is without coating copper cash manufacture method, and wherein, described chromium coating is three
Valency chromium chromium coating.
7. one kind by the wear-resisting erosion resistance described in claim 1 without coating copper cash manufacture method prepare wear-resisting anti-
Erosion is without coating copper cash.
8. wear-resisting erosion resistance as claimed in claim 7 is without coating copper cash, wherein, without coating copper cash by routing technique
When aluminum pad is combined, forming the aluminium carbide phase of compound thickness between suppression Cu/Al interface metal, this aluminium carbide includes mutually
Al4C and Al4C3。
9. wear-resisting erosion resistance as claimed in claim 8 is without coating copper cash, wherein, changes between described Cu/Al interface metal
Compound thickness is 0.45 μm-0.75 μm.
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| TW201326435A (en) * | 2013-02-19 | 2013-07-01 | Truan-Sheng Lui | Copper-palladium alloy wire formed by solid phase diffusion reaction and the manufacturing method thereof |
| CN103903669A (en) * | 2014-03-24 | 2014-07-02 | 大连理工常州研究院有限公司 | Copper-based electrical connector and manufacturing method thereof |
| DE102013200308A1 (en) * | 2013-01-11 | 2014-07-17 | Infineon Technologies Ag | Bonding wire for use in power-electronic module and electrical component, has filament whose melting temperature at specific pressure is higher than melting temperature of matrix at specific pressure |
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| CN1643675A (en) * | 2002-03-26 | 2005-07-20 | 住友电工运泰克株式会社 | Bonding wire and an integrated circuit device using the same |
| EP2413351A1 (en) * | 2009-03-23 | 2012-02-01 | Tanaka Denshi Kogyo K.K. | Coated copper wire for ball bonding |
| CN101887942A (en) * | 2010-06-07 | 2010-11-17 | 江苏鑫钻新材料科技有限公司 | Metal baseplate provided with LED and manufacturing method thereof |
| DE102013200308A1 (en) * | 2013-01-11 | 2014-07-17 | Infineon Technologies Ag | Bonding wire for use in power-electronic module and electrical component, has filament whose melting temperature at specific pressure is higher than melting temperature of matrix at specific pressure |
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