CN105225964B - Rich layer gold silver-based wire manufacturing method containing solid phase reaction - Google Patents
Rich layer gold silver-based wire manufacturing method containing solid phase reaction Download PDFInfo
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Abstract
The present invention is related to a kind of rich layer gold silver-based wire manufacturing method containing solid phase reaction, first, prepares the aqueous solution of one of calcic, titanium or zirconium ion metal ion；Then, nano-gold powder is added in the aqueous solution, nano-gold powder forms more gold particles in the aqueous solution, using hydro-thermal method by adsorption of metal ions in gold particle surface, to form the compound gold particle of nano core-shell；Afterwards, filtering solution is to obtain the compound gold particle of solid phase nano core-shell；Then, the compound gold particle of solid phase nano core-shell is inserted into silver-colored liquation, stirred to form silver-based material, thereby, the compound gold particle of nano core-shell is uniformly distributed in silver-based material；Afterwards, two-stage vacuum heat is carried out, silver-colored substrate surface is formed Gold-rich alloys layer；Finally, silver-based material is carried out taking out Wiring technology to form the rich layer gold silver-based wire containing solid phase reaction.
Description
Technical field
The invention relates to a kind of rich layer gold silver-based wire manufacturing method containing solid phase reaction, refers in particular to a kind of different
In general coating technology and it is applied to the silver-based wire and its manufacture method of semiconductor packaging process or human body life doctor's level chip,
There is higher cell growth rate in the application field of raw doctor's level chip, can effectively reach excellent cell compatibility, be a kind of
Silver-based wire without the hot carbides gold alloy layer of coating surface.
Background technology
Generally, the cost of silver wire can reduce about 50%~70% compared to gold wire, thus with cost
Advantage, refers to Chinese patent, Publication No. CN101667566 " a kind of silver-based covers the manufacture method of the bonding silk thread of gold ",
It discloses a kind of bonding silk thread product that proof gold protection against oxidation layer is covered with using filamentary silver line as base material, surface, and gold accounts for weight percent
The 1.8%~10% of ratio, remaining is silver, and its material cost is bonded the 1/3 of silk thread less than proof gold；However, silver wire is soldered to
The problem of aluminium but there are reliability when padding, easily corrodes or occurs mainly due to the solder side of silver wire and aluminium pad
It is bonded incomplete phenomenon and seriously undermines the boundary strength of welding, in addition, silver metal and the sulfur dioxide reaction tool in air is special
There is the qualification rate that sulfation also has a strong impact on product；Furthermore silver-based material acellular compatibility only with bacteria resistance function,
The application aspect of raw doctor's product is limited to；Because alloy wire can lift containing metal the corrosion resistance of alloy wire, calcic metal is then
It can make alloy wire that there is bioaffinity, and can effectively lift the reliability that silver-colored billon engages in routing；Therefore, the golden calcium of silver closes
Golden wire is developed to solve the problems, such as that the raw doctor's application platform of above-mentioned semiconductor packaging process and lifting is met with then.
Refer to china taiwan invention patent publication number the 201001652nd " semiconductor packages is led containing silver alloy
Line ", it discloses a kind of argentiferous alloy lead wire, its gold, the calcium of 3ppm~5% of composition formed for 0.05%~5%, and
Remaining silver, but above-mentioned patent does not address the preparation method of any alloy wire, not only has no way of learning how metal is formed
In silver-based wire rod (silver wire surface gold-plating is considered as a kind of technique of high pollution at present), how it can not also state clearly in detail by calcium
Metal is formed on silver-colored gold alloy layer；Furthermore prior art is existed calcium metal-plated using the technology of coating (coating) at present
On the gold metal layer for covering silver metal layer, wire fracture risk is reduced with improving tensile strength to reach；However, because silver-colored calcium closes
Gold thread Composition Control is not easy, and calcium can not also engage with gold, therefore calcium metal is plated on to the golden metal of argentiferous with the technology of coating
Technology on layer can not effectively be reached, and cause the conjugation grade extreme difference of calcium metal and gold metal layer, the possibility for having stripping in technique, because
This, calcium metal with the technology of coating be plated on gold metal layer and can not reached；Accordingly, in order to effectively ensure leading for silver-colored golden calcium alloy
Line possesses good cell compatibility and structural stability when being used as raw doctor's level chip wire, and in semiconductor packages work
Wire fracture risk can be effectively reduced in skill and improves tensile strength, is still that this conductor packaging technology or raw doctor's level chip are used now
Silver-based wire manufacturer or researcher need ongoing effort overcome with solve important topic.
The content of the invention
Main purpose of the present invention refers in particular to one to provide a kind of rich layer gold silver-based wire manufacturing method containing solid phase reaction
Kind is different from general coating technology and suitable for the silver-based wire and its manufacture of semiconductor packaging process or human body life doctor's level chip
Method, there is higher cell growth rate in the application field of raw doctor's level chip, can effectively reach excellent cell compatibility,
It is a kind of silver-based wire of the hot carbides gold alloy layer of no coating surface.
In order to reach above-mentioned implementation purpose, the present inventor proposes a kind of rich layer gold silver-based wire manufacturer containing solid phase reaction
Method, its step include：
Step 1：Prepare the aqueous solution containing one of calcium ion, titanium ion or zirconium ion metal ion；
Step 2：Nano-gold powder is added in the above-mentioned aqueous solution, nano-gold powder forms more gold particles in the aqueous solution, profit
With hydro-thermal method by adsorption of metal ions in gold particle surface, to form the compound gold particle of nano core-shell；
Step 3：Filtering solution is to obtain the compound gold particle of the nano core-shell of solid phase；
Step 4：The compound gold particle of the nano core-shell of solid phase is inserted in silver-colored liquation, stirring and standing room temperature cools down
To form silver-based material, thereby, the compound gold particle of nano core-shell is uniformly distributed in silver-based material；
Step 5：Two-stage vacuum heat is carried out, silver-colored substrate surface is formed Gold-rich alloys layer；And
Step 6：Silver-based material is carried out taking out Wiring technology to form the rich layer gold silver-based wire containing solid phase reaction.
Rich layer gold silver-based wire manufacturing method containing solid phase reaction as described above, when wherein metal ion is calcium ion,
The aqueous solution is the aqueous solution of one of them such as addition calcium nitrate, calcium acetate, calcium phosphate or calcium carbonate.
Rich layer gold silver-based wire manufacturing method containing solid phase reaction as described above, wherein hydro-thermal method is to heat the aqueous solution
To boiling, make adsorption of metal ions in gold particle surface, to form the compound gold particle of nano core-shell.
Rich layer gold silver-based wire manufacturing method containing solid phase reaction as described above, wherein two-stage vacuum heat be in
First carried out under vacuum environment after 700 DEG C~800 DEG C of temperature is heat-treated 30~90 minutes, then with 425 DEG C~520 DEG C of temperature heat
Processing 30~60 minutes.
Rich layer gold silver-based wire manufacturing method containing solid phase reaction as described above, wherein Gold-rich alloys layer be for
AgAu7Ca2With AgAu9Ca2, or AgAuTi and AgAuTi2, or AgAuZr and AgAuZr2Etc. one kind therein.
In addition, the present invention a kind of rich layer gold silver-based wire containing solid phase reaction is separately provided, its be method described above prepare and
Into.
Rich layer gold silver-based wire containing solid phase reaction as described above, wherein the tool of the rich layer gold silver-based wire containing solid phase reaction
There is at least 90% cell growth rate.
Rich layer gold silver-based wire containing solid phase reaction as described above, wherein the rich layer gold silver-based wire containing solid phase reaction with
Blood plasma reaction does not generate layers of calcium salts.
Brief description of the drawings
Fig. 1：The step flow chart of rich layer gold silver-based wire manufacturing method of the invention containing solid phase reaction, wherein S1 represent step
Rapid one, S2 is represented Step 2: S3 is represented Step 3: S4 is represented Step 4: S5 is represented Step 5: S6 represents step 6.
Fig. 2：The not thermally treated silver-based wire of rich layer gold silver-based wire manufacturing method of the invention containing solid phase reaction shows
Micro mirror photo electronic chart.
Fig. 3：The rich layer gold silver-based wire manufacturing method one preferred embodiment containing solid phase reaction of the invention it is thermally treated
Silver-colored golden calcium wire microphotograph electronic chart.
Embodiment
First, refer to shown in Fig. 1, flowed for the step of rich layer gold silver-based wire manufacturing method of the present invention containing solid phase reaction
Cheng Tu, its manufacture method mainly include following steps：
Step 1 S1：Prepare the aqueous solution containing a metal ion species therein such as calcium ion, titanium ion or zirconium ion；
In one preferred embodiment of the present invention, when metal ion is calcium ion, the aqueous solution is addition calcium nitrate [Ca (NO3)2], acetic acid
Calcium [Ca (C2H3O2)2], calcium phosphate [Ca3(PO4)2] or calcium carbonate (CaCO3) etc. a kind of compound therein；In addition, titanium and zirconium etc.
Metal ion also can be via by Titanium Nitrate, acetic acid titanium, titanium phosphate, titanium carbonate or zirconium nitrate, acetic acid zirconium, basic zirconium phosphate, zirconium carbonate etc.
A kind of compound therein makes an addition to aqueous solution acquisition；
Step 2 S2：Nano-gold powder is added in the aqueous solution, nano-gold powder forms more gold particles in the aqueous solution, utilizes
Hydro-thermal method by adsorption of metal ions in gold particle surface, to form the compound gold particle of nano core-shell；It is preferably real in one of the present invention
Apply in example, hydro-thermal method is also known as vapour method, is the temperature that the aqueous solution is heated to 100 DEG C of boiling, then metal ion can adsorb
In gold particle surface, to form the compound gold particle of nano core-shell；
Step 3 S3：Filtering solution is to obtain the compound gold particle of the nano core-shell of solid phase；It is preferably real in one of the present invention
Apply in example, the compound gold particle of nano core-shell of solid-state is cladded with the nano particle of golden calcium material for a kind of proof gold；
Step 4 S4：The compound gold particle of the nano core-shell of solid phase is inserted in silver-colored liquation, stirs and to stand room temperature cold
But to form silver-based material, thereby, the compound gold particle of nano core-shell is uniformly distributed in silver-based material；In one preferred embodiment of the present invention
In, the temperature of silver-colored liquation is 1100 DEG C；
Step 5 S5：Two-stage vacuum heat is carried out, silver-colored substrate surface is formed Gold-rich alloys layer；Vacuum heat bar
Part is to insert the silver-colored liquation of the compound gold particle containing nano core-shell in vacuum continuous furnace, first carried out under vacuum environment 700 DEG C~
After 800 DEG C of temperature is heat-treated 30~90 minutes, then it is heat-treated 30~60 minutes with 425 DEG C~520 DEG C of temperature and completes silver-based
Material；In one preferred embodiment of the present invention, argentiferous, the Gold-rich alloys layer of calcium pass through the vacuum heat condition of first stage
730 DEG C, 60 minutes after 425 DEG C, 30 minutes of the vacuum heat condition of second stage with completing；In addition, Gold-rich alloys layer is
AgAu7Ca2With AgAu9Ca2, or AgAuTi and AgAuTi2, or AgAuZr and AgAuZr2Etc. one kind therein；And
Step 6 S6：Silver-based material is carried out taking out Wiring technology to form the rich layer gold silver-based wire containing solid phase reaction；In this hair
In bright one preferred embodiment, silver-based material take out can obtain about 20 microns of diameter (μm) after Wiring technology can be applied to raw doctor's level
The silver-colored golden calcium fine lines of chip and semiconductor packaging process.
In addition, the present invention separately provides a kind of rich layer gold silver-based wire containing solid phase reaction, it is the side with above-described embodiment
Method is prepared, that is, the rich layer gold silver-based wire containing solid phase reaction that method described above is prepared is 20 μm of diameter and had
The silver-based wire of Gold-rich alloys layer；Furthermore the rich layer gold silver-based wire of the invention containing solid phase reaction with least 90% it is thin
Born of the same parents' growth rate (cell relative growth rate, abbreviation RGR), that is, the silver of the rich layer gold containing solid phase reaction of the present invention
Base wire has excellent cell compatibility；In the experiment reacted with blood plasma, there is the characteristics of not generating layers of calcium salts, wherein originally
The rich layer gold silver-based wire containing solid phase reaction of invention is with artificial body fluid simulating blood plasma, by the present invention's with blood plasma reaction test
Containing solid phase reaction rich layer gold silver-based wire leaching be placed in the artificial body fluid of 37 DEG C of simulated humanbody temperature continue 96 hours after without
Layers of calcium salts is generated, that is, is suitable for the application of raw doctor's level chip wire.
Furthermore the present invention be by multiple experimental examples listed by following several forms to confirm the present invention the effect of；First,
One preferred embodiment of the present invention is to prepare one added with one kindization therein such as calcium nitrate, calcium acetate, calcium phosphate or calcium carbonate
The aqueous solution containing calcium ion of compound；Then, nano-gold powder is added in the aqueous solution containing calcium ion, and with 100 DEG C
The hydro-thermal method heating aqueous solution makes calcium adsorption of metal ions in gold particle surface, to form the compound gold particle of nano core-shell；Furthermore mistake
Drainage solution is to obtain the compound gold particle of the nano core-shell of solid phase；Afterwards, the compound gold particle of the nano core-shell of solid phase is inserted one
In silver-colored liquation, stir and stand room temperature cooling to form a silver-based material, thereby, the compound gold particle of nano core-shell is uniformly distributed
In silver-based material；Then, vacuum heat is carried out, silver-colored substrate surface is formed an argentiferous, the Gold-rich alloys layer (AgAu of calcium7Ca2With
AgAu9Ca2)；Simultaneously, the present inventor attempts a variety of heat treatment modes to find suitable vacuum heat condition
And obtain optimal parameter value；Finally, then by the silver-based material of argentiferous, the Gold-rich alloys layer of calcium carry out taking out Wiring technology to form 20 μm
The rich layer gold silver-based wire containing solid phase reaction；Experimental result as shown in the table, it is without any vacuum heat condition institute
Obtain each item data, wherein, though the percentage by weight (wt.%) of calcium content why, no vacuum heat step is not given birth to
Into nano surface gold calcium alloy layer, and seven days cell growth rate (RGR) empirical value be between 82%~87%, as a result
The compatible low of silver-based wire without vacuum heat and cell is shown, is unable to reach more than the 90% of standard value, this contains solid phase
The outward appearance of the rich layer gold silver-based wire of reaction is referred to shown in Fig. 2, for the rich layer gold silver-based wire system of the invention containing solid phase reaction
Make the not thermally treated silver-based wire microphotograph electronic chart of method.
In addition, when the temperature parameter of second stage vacuum heat be promoted to 290 DEG C, heat treatment time be 30 minutes when,
Following table is the experimental data for the rich layer gold silver-based wire containing solid phase reaction for representing one preferred embodiment of the present invention, wherein in
Be denoted as in " formed calcification silver golden thermal diffusion zone " field " NO " person be represent this golden calcium mixed proportion of silver containing solid phase reaction
Rich layer gold silver-based conductor structure is unstable, can not be effectively formed the available rich layer gold silver-based wire containing solid phase reaction；Furthermore this
Group experiment also adds the artificial body fluid leaching mixed with blood plasma and puts experiment, and the setting of experiment is used in artificial body fluid simulation human body
Blood plasma, the leaching of the rich layer gold silver-based wire containing solid phase reaction of the present invention is placed in 96 in the artificial body fluid of 37 DEG C of simulated humanbody body temperature
Hour, with the reaction condition of rich the layer gold silver-based wire and blood plasma containing solid phase reaction of the measurement present invention, wherein in " artificial body fluid
37 DEG C of -96hr of experiment are put in leaching " " NG " person is shown as in field is to represent that with blood plasma reaction the layers of calcium salts of insulator can be generated, and lead
Showing impedance when the rich layer gold silver-based wire containing solid phase reaction of the invention conducts as raw doctor's level chip in human body can improve,
And signal can not be effectively transmitted, raw doctor's level chip is in turn resulted in without effect；Shown by following table data, when calcium content is less than or equal to
0.32wt.%, the golden thermal diffusion zone of calcification silver can not be effectively formed and cause the structural instability of silver-based wire, and when calcium content is small
When 0.11wt.%, it can generate layers of calcium salts in artificial body fluid leaching is put and tested and make raw doctor's level chip of connection without work
With.
Furthermore when the temperature parameter of second stage vacuum heat be promoted to again 425 DEG C, heat treatment time be similarly 30 points
Zhong Shi, following table also represent the experimental data of the silver-colored golden calcium silver-based wire of one preferred embodiment of the present invention, wherein increasing in cell
The leaching of rate and artificial body fluid is put in experiment, though the percentage by weight of calcium content why, that is, when calcium content percentage by weight from
0.06wt.%~0.58wt.%, the cell growth rate of the rich layer gold silver-based wire of the invention containing solid phase reaction all can reach mark
More than the 90% of quasi- value, and layers of calcium salts will not be also generated with the reaction of blood plasma, it can effectively reach the application of raw doctor's level chip；Again
Person, the golden thermal diffusion zone of calcification silver that the condition of this vacuum heat can also be formed more than 13 nanometers (nm) completely, the display present invention
The rich layer gold silver-based wire containing solid phase reaction can be at stable configuration state.
In addition, following table represents same calcium, golden weight percent content under the conditions of same vacuum heat, it is different
Parameter characteristic, such as routing balling-up, routing splice density, blowout current density, and compound thickness etc. between interface metal,
Wherein routing balling-up is a kind of one of technique of integrated antenna package industry, is a kind of ball bond routing skill of electrion
Art, also known as discharge balling (electronic flame off, abbreviation EFO), by being shown in following table, no matter the weight of calcium content
Why is percentage, and its routing balling-up can all reach a standard；In addition, when calcium content is more than 0.46wt.%, its routing bond strength is
Downward trend is presented, this is represented in semiconductor packaging process, its intensity engaged deficiency, can not be effectively as integrated circuit
The wire of encapsulation uses；Furthermore also referring to shown in Fig. 3, manufactured for rich layer gold silver-based wire of the present invention containing solid phase reaction
The thermally treated silver-colored golden calcium wire microphotograph electronic chart of method one preferred embodiment, wherein being heat-treated in vacuum environment
After the lower temperature for first carrying out 730 DEG C is heat-treated 60 minutes, then is heat-treated 30 minutes and completed with 425 DEG C of temperature, with Fig. 2 without
The microphotograph electronic chart of heat treatment is relatively learnt, Gold-rich alloys layer can be generated through Overheating Treatment, after bracing wire technique, this
Gold-rich alloys layer can be coated on the outside of wire, and therefore, the outside of the rich layer gold silver-based wire containing solid phase reaction can be more smooth,
And the region of internal silver wire can also there are calcium metal ion.
Therefore, shown by the experimental data of the different vacuum heat conditions of aforementioned four form, if with total group of 100%
Percentage by weight into composition calculates, and the rich layer gold silver-based wire containing solid phase reaction of one preferred embodiment of the present invention is at least
Include 0.06wt.%~0.39wt.% calcium content, 3.2wt.% gold content, and the silver of residuals weight percentage contains
Amount, the rich layer gold silver-based wire containing solid phase reaction has at least 90% cell growth rate (RGR), and has with blood plasma reaction
Not the characteristics of not generating layers of calcium salts.
It is to prepare one added with Titanium Nitrate, acetic acid titanium, titanium phosphate first in addition, in the present invention secondly in preferred embodiment
A kind of or aqueous solution containing titanium ion of compound therein such as titanium carbonate；Then, bronze is added into the water containing titanium ion
In solution, titanium metal ions is adsorbed in gold particle surface with 100 DEG C of the hydro-thermal method heating aqueous solution, answered with forming nano core-shell
Alloy particle；Furthermore filtering solution is to obtain the compound gold particle of the nano core-shell of solid phase；Afterwards, by the nano core-shell of solid phase
Compound gold particle is inserted in silver-colored liquation, is stirred and is stood room temperature cooling to form a silver-based material, thereby, nano core-shell is compound
Goldc grains subsystem is uniformly distributed in silver-based material；Then, vacuum heat is carried out, silver-colored substrate surface is formed the richness gold of an argentiferous, titanium
Alloy-layer (AgAuTi and AgAuTi2)；Finally, then by the silver-based material of argentiferous, the Gold-rich alloys layer of titanium take out Wiring technology with shape
Into 20 μm of the rich layer gold silver-based wire containing solid phase reaction；Following table be represent two-stage vacuum heat condition be 730 DEG C, 60
Minute and the rich layer gold silver-based wire experimental result containing solid phase reaction under 465 DEG C, 30 minutes, are shown by data, anti-containing solid phase
The rich layer gold silver-based wire answered is to comprise at least the Ti content, the 2.8wt.% gold content that have 0.12wt.%~0.85wt.%,
And the silver content of residuals weight percentage, the rich layer gold silver-based wire containing solid phase reaction have more than 90% cell growth rate
(RGR), that is, possess excellent cell compatibility, and also possess with blood plasma reaction and have the characteristics of not generating titanium salt layer.
Furthermore it is to prepare one added with zirconium nitrate, acetic acid zirconium, basic zirconium phosphate first in the present invention thirdly in preferred embodiment
A kind of or aqueous solution containing zirconium ion of compound therein such as zirconium carbonate；Then, bronze is added into the water containing zirconium ion
In solution, zirconium adsorption of metal ions is set to be answered in gold particle surface to form nano core-shell with 100 DEG C of the hydro-thermal method heating aqueous solution
Alloy particle；Furthermore filtering solution is to obtain the compound gold particle of the nano core-shell of solid phase；Afterwards, by the nano core-shell of solid phase
Compound gold particle is inserted in silver-colored liquation, is stirred and is stood room temperature cooling to form a silver-based material, thereby, nano core-shell is compound
Goldc grains subsystem is uniformly distributed in silver-based material；Then, vacuum heat is carried out, silver-colored substrate surface is formed the richness gold of an argentiferous, zirconium
Alloy-layer (AgAuZr and AgAuZr2)；Finally, then by the silver-based material of argentiferous, the Gold-rich alloys layer of zirconium take out Wiring technology with shape
Into 20 μm of the rich layer gold silver-based wire containing solid phase reaction；Following table be represent vacuum heat condition be 730 DEG C, 60 minutes with
The rich layer gold silver-based wire experimental result containing solid phase reaction under 520 DEG C, 60 minutes, is shown, this is containing solid phase reaction by data
Rich layer gold silver-based wire is to comprise at least the zirconium content, the 4.1wt.% gold content that have 0.09wt.%~0.72wt.%, and
The silver content of residuals weight percentage, the rich layer gold silver-based wire containing solid phase reaction have more than 90% cell growth rate
(RGR), that is, possess excellent cell compatibility, and also possess with blood plasma reaction and have the characteristics of not generating zirconates layer.
Understood from above-mentioned implementation explanation, silver-based wire of the invention and its manufacture method and prior art in comparison,
The present invention has advantages below：
1. the present invention the rich layer gold silver-based wire manufacturing method containing solid phase reaction be by by the metals such as calcium, titanium or zirconium from
Son is adsorbed and crystallized in the compound gold particle of nano core-shell of bronze, and is melting into the silver-colored liquation of high temperature, is continued continuous with vacuum
Stove carries out effective two-stage vacuum heat-treating method, i.e., 700 DEG C~800 DEG C of temperature heat treatment is first carried out under vacuum environment
After 30~90 minutes, then it is heat-treated 30~60 minutes with 425 DEG C~520 DEG C of temperature, to prepare the silver with Gold-rich alloys layer
Baseline material, when the wire applied to raw doctor's level chip, has a higher cell growth rate, and the cell that can effectively reach excellent is simultaneous
Capacitive, it is a kind of silver-based wire of the hot carbides gold alloy layer of no coating surface.
2. the rich layer gold silver-based wire manufacturing method containing solid phase reaction of the present invention is by hydro-thermal method that calcium, titanium or zirconium is golden
Category ion is adsorbed in the compound gold particle of nano core-shell of bronze with mode of oxidizing, can effectively solve to be not easy using coating technique
By relevant metallization layer plate gold metal layer and it is in uneven thickness the shortcomings that, not only solve the problems, such as coating stripping, also can reach system
The target of the fine lines such as standby silver golden calcium, the golden titanium of silver or the golden zirconium of silver.
3. the rich layer gold silver-based wire manufacturing method containing solid phase reaction of the present invention is to simulate human body blood by artificial body fluid
The experiment of 96 hours is put in 37 DEG C of leachings of body temperature of slurry, the layers of calcium salts that effectively can be reacted with blood plasma without generating insulator, is effectively reached
When being conducted with the rich layer gold silver-based wire containing solid phase reaction of the present invention as raw doctor's level chip in human body, prevent layers of calcium salts from making
Into short circuit the shortcomings that can not effectively transmit signal.
Claims (8)
1. a kind of rich layer gold silver-based wire manufacturing method containing solid phase reaction, its step include：
Step 1：Prepare the aqueous solution containing one of calcium ion, titanium ion or zirconium ion metal ion；
Step 2：Nano-gold powder is added in the above-mentioned aqueous solution, nano-gold powder forms more gold particles in the aqueous solution, utilizes water
Hot method by adsorption of metal ions in gold particle surface, to form the compound gold particle of nano core-shell；
Step 3：Filtering solution is to obtain the compound gold particle of the nano core-shell of solid phase；
Step 4：The compound gold particle of the nano core-shell of solid phase is inserted in silver-colored liquation, stirs and stands room temperature cooling with shape
Into silver-based material, thereby, the compound gold particle of nano core-shell is uniformly distributed in silver-based material；
Step 5：Two-stage vacuum heat is carried out, silver-colored substrate surface is formed Gold-rich alloys layer；And
Step 6：Silver-based material is carried out taking out Wiring technology to form the rich layer gold silver-based wire containing solid phase reaction.
2. the rich layer gold silver-based wire manufacturing method according to claim 1 containing solid phase reaction, wherein the metal ion
For calcium ion when, the aqueous solution for one of addition calcium nitrate, calcium acetate, calcium phosphate or calcium carbonate the aqueous solution.
3. the rich layer gold silver-based wire manufacturing method according to claim 1 containing solid phase reaction, wherein the hydro-thermal method is
The aqueous solution is heated to seething with excitement, makes adsorption of metal ions in gold particle surface, to form the compound gold particle of nano core-shell.
4. the rich layer gold silver-based wire manufacturing method according to claim 1 containing solid phase reaction, wherein the two-stage is true
Sky heat treatment be first carried out under vacuum environment 700 DEG C~800 DEG C temperature be heat-treated 30~90 minutes after, then with 425 DEG C~
520 DEG C of temperature is heat-treated 30~60 minutes.
5. the rich layer gold silver-based wire manufacturing method according to claim 1 containing solid phase reaction, wherein the Gold-rich alloys
Layer is AgAu7Ca2With AgAu9Ca2, or Gold-rich alloys layer is AgAuTi and AgAuTi2, or Gold-rich alloys layer be AgAuZr with
AgAuZr2One of them.
A kind of 6. rich layer gold silver-based wire containing solid phase reaction prepared by method by any one of claim 1-5.
7. the rich layer gold silver-based wire according to claim 6 containing solid phase reaction, the wherein rich layer gold for containing solid phase reaction
Silver-based wire has at least 90% cell relative growth rate.
8. the rich layer gold silver-based wire according to claim 6 containing solid phase reaction, the wherein rich layer gold for containing solid phase reaction
Silver-based wire does not generate layers of calcium salts with blood plasma reaction.
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| CN101673789A (en) * | 2008-09-12 | 2010-03-17 | 台湾应解股份有限公司 | Light emitting diode package substrate structure, manufacturing method thereof and packaging structure thereof |
| CN101667566A (en) * | 2009-09-20 | 2010-03-10 | 宁波康强电子股份有限公司 | Gold-coated-sliver base bonding silk thread and manufacture method thereof |
| US20140054781A1 (en) * | 2012-08-24 | 2014-02-27 | Leo M. Higgins, III | Copper Ball Bond Features and Structure |
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