CN101534603A - Conductor used in flexible substrate, method for producing conductor, and flexible substrate - Google Patents
Conductor used in flexible substrate, method for producing conductor, and flexible substrate Download PDFInfo
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- CN101534603A CN101534603A CN200810081793A CN200810081793A CN101534603A CN 101534603 A CN101534603 A CN 101534603A CN 200810081793 A CN200810081793 A CN 200810081793A CN 200810081793 A CN200810081793 A CN 200810081793A CN 101534603 A CN101534603 A CN 101534603A
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Abstract
The invention provides a conductor used in a flexible substrate, a method for producing the conductor, and the flexible substrate, and the conductor used in the flexible substrate has small or almost no possibility of generating crystal whiskers from an Sn coating surface or soldering tins around the conductor, and does not increase contact resistance even when being placed in the high-temperature environment. On the conductor which is arranged inside a flexible flat cable or a flexible printed circuit board, an Sn or Sn alloy coated film (15) is formed on the surface of the conductor which is composed of Cu or Cu alloys, and superficial oxidize films (16a) and (16b) of the coating film (15) are composed of an oxide of Sn-excluded elements or a mixed oxide of an Sn oxide and an oxide of Sn-excluded elements.
Description
Technical field
The present invention relates to a kind of related Wiring conductor and terminal connection part, particularly relate to conductor and manufacture method and the flexible substrate that uses on the flexible substrate of the flexible flat cable (FFC) that uses on the electronic equipment, flexible printing distributing board (FPC) etc.
Background technology
In order to prevent the oxidation of wiring material, particularly to apply the coating of Sn, Ag, Au or Ni at wiring material on the surface of copper or copper alloy in the past.
For example, as shown in Figure 2,, apply coating on the surface of the conductor 14 of plug (metal terminal) 12 of connector (link) 11 and FFC13 etc. at connector 11 terminal connection part with flexible flat cable (to call FFC in the following text) 13.Particularly because Sn with low cost since soft and under chimeric pressure easy deformation, contact area increases, contact resistance can be reduced to very low, so the surface that generally is widely used in wiring material has applied the material of Sn coating.
As this Sn coating alloy, used the good Sn-Pb alloy of whisker resistance in the past, but in recent years, viewpoint from the countermeasure that cooperates the environment aspect, pursue and use no Pb material (non-lead material), non-halogen material, the various materials that use on the wiring material are also pursued no Pbization, non-halogenization.
Patent documentation 1: the spy opens the 2006-111898 communique
Patent documentation 2: the spy opens the 2005-216749 communique
Patent documentation 3: the spy opens the 2005-206869 communique
Patent documentation 4: the spy opens the 2006-45665 communique
Non-patent literature 1:JEITA finishes unleaded urgent motion public lecture data (2005.2.17)
Non-patent literature 2:JEITA does not have lead welding practical research achievement report (2005.6) in 2005
Summary of the invention
But, along with the no Pbization of Sn coating, be on the alloy layer particularly at Sn or Sn, as shown in Figure 3, the problem of generation is that the acicular crystal that can be on coating produces Sn be whisker 21, owing to short circuit accident in abutting connection with wiring closet takes place whisker 21.
For the stress in the Sn coating that relaxes one of occurrence cause of being considered to whisker, can carry out reflow treatment by the Sn that will electroplate, reduce the generation of whisker.But, know the mechanism that this whisker suppresses with being inaccurate.In addition, when having applied the new external stress of chimeric grade with connector, even if implement reflow treatment, generation that can not inhibition of whiskers.And report, though alloy plated layer by Bi or Ag etc. or alloy coating can inhibition of whiskers,, produce more polycrystalline palpus in the time of on the contrary can be than pure Sn by reflow treatment.
On electronic component, must carry out reflow treatment for the part installation, problem is also arranged on these alloy layers.
At present, disclose the method that applies the following thin Sn coating of 1 μ m, but particularly when high temperature is placed, contact resistance has been arranged than the problem of increase in the past as effective countermeasure.
Situation more than the present invention has considered is released, it is its manufacture method and flexible substrate that its purpose is to provide a kind of used in flexible substrate conductor, particularly under the environment that has applied with the big external stress of the chimeric grade of connector, produce the little or generation hardly of possibility of whisker on Sn coating film surface around conductor or the scolding tin, place under the environment at high temperature, also can not come in contact resistance and increase.
To achieve these goals, the invention of technical scheme 1 relates to a kind of used in flexible substrate conductor, this conductor is provided in flexible flat cable or flexible print wiring board inside, it is characterized in that: form Sn or Sn alloy coating in the surface of conductors that is made of Cu or Cu alloy, the surface film oxide of this plated film is constituted or is made of the mixed oxide of Sn oxide with the oxide of Sn element in addition by the oxide of the element beyond the Sn.
The invention of technical scheme 2 is according to technical scheme 1 described used in flexible substrate conductor, and the element beyond the above-mentioned Sn is the element that oxidation tendency is higher than Sn.At this, the element that oxidation tendency is high is the element of the value of this oxide standard free energy of formation of expression less than Sn (absolute value is big on negative value), for example Zn, P, Al, Ti etc.
The invention of technical scheme 3 is according to technical scheme 1 or 2 described used in flexible substrate conductors, and the element beyond the above-mentioned Sn is at least a above element that is selected among Zn, P, Al, the Ti.
The invention of technical scheme 4 is according to technical scheme 1 to 3 described used in flexible substrate conductor, above-mentioned by the element beyond the Sn oxide or the surface oxidation film thickness that mixed oxide produced of Sn oxide and the oxide of Sn element in addition be below the 5nm.
The invention of technical scheme 5 relates to a kind of manufacture method of used in flexible substrate conductor, this conductor is provided in flexible flat cable or flexible print wiring board inside, it is characterized in that: form Sn or Sn alloy coating in the surface of conductors that constitutes by Cu or Cu alloy, and form the plated film be selected from the element more than Zn, P at least a on its surface, thereafter, by reflow treatment, make surface film oxide constitute or constitute by the mixed oxide of the oxide of the element of Sn oxide and these selections by the oxide of the element of these selections.
The invention of technical scheme 6 relates to a kind of manufacture method of used in flexible substrate conductor, this conductor is provided in flexible flat cable or flexible print wiring board inside, it is characterized in that: form in the surface of conductors that constitutes by Cu or Cu alloy and comprise Sn or the Sn alloy coating that is selected from the element more than Zn, P at least a, by reflow treatment, make surface film oxide constitute or constitute by the mixed oxide of the oxide of the element of Sn oxide and these selections by the oxide of the element of these selections thereafter.
The invention of technical scheme 7 relates to a kind of flexible substrate, it is characterized in that: have conductor group's the two sides of each described used in flexible substrate conductor of many technical schemes 1～4 that insulating barrier is set in parallel arranged.
The invention of technical scheme 8 is that the resin molding material that is had tack coat by single face constitutes above-mentioned insulating barrier according to technical scheme 7 described flexible substrates.
According to the present invention, on flexible flat cable or flexible print wiring board, even if in the occasion that has applied just as the external stress of fitting portion, the acicular crystal that also can suppress Sn is whisker, can solve bad as in abutting connection with the short circuit of wiring closet.In addition, even if under hot environment, can not make the contact reliability loss yet.
Description of drawings
Fig. 1 is the ideograph that shows an embodiment of the invention.
Fig. 2 is the stereogram that shows the chimeric example of connector and FFC.
Fig. 3 be explanation connector and FFC chimeric down, the generation whisker is in abutting connection with the amplification stereogram of the appearance of wiring closet short circuit.
Fig. 4 is XPS analysis result's the figure that shows the surface film oxide of the Sn be used to identify embodiments of the invention and conventional example.
Fig. 5 is XPS analysis result's the figure that shows the surface film oxide of the Zn be used to identify embodiments of the invention and conventional example.
Fig. 6 is the figure of analysis result of the AES depth direction of the surface film oxide that shows embodiments of the invention and conventional example, Sn plated film.
Fig. 7 is the figure of analysis result of the AES depth direction of the surface film oxide of conductor after heat treatment in 150 ℃, 24 hours that show embodiments of the invention and conventional example, Sn plated film.
Among the figure,
11-connector; 12-plug; 13-FFC; 14-conductor; 15-Sn plated film; 16a, 16b-surface film oxide; 21-whisker
Embodiment
Below based on accompanying drawing in detail a preferred forms of the present invention is described in detail.
The oxide-film of Sn plated conductor only is made of the oxide of Sn usually, but to achieve these goals, the conductor that the present invention relates to is that surface film oxide is made the oxide of Sn element in addition or the hopcalite beyond Sn oxide and the Sn.Element as beyond the Sn has Zn, P, Al, Ti.
For example, shown in Fig. 1 (a), the surface of the conductor (not shown) that constitutes at Cu or Cu alloy or form Sn or Sn alloy coating 15 on every side forms the surface film oxide 16a of Zn oxide or Sn oxide and Zn oxide formation on its surface.
In addition, shown in Fig. 1 (b), form the surface film oxide 16b that P oxide or Sn oxide and P oxide constitute on the surface of Sn or Sn alloy coating 15.
This surface film oxide 16a, 16b can be after the surface of Sn or Sn alloy coating 15 forms the coating of Zn, P, Al and Ti, with it as oxide, perhaps also can in Sn or Sn alloy, add Zn or P element, with its coating on conductor, form Sn or Sn alloy coating 15, with its surface oxidation, form the surface film oxide 16a, the 16b that comprise Zn, P, Al or Ti.
Usually, when Sn coating has applied stress, the defective of surface film oxide becomes the core that whisker produces, and is called as growth.(list of references: the explanation of growth of tin crystal whisker process and countermeasure R﹠amp; D plans society)
In patent documentation 1, disclosed method is by the Sn plated film being carried out oxidation processes, form thick and fine and close Sn oxide or hydroxide film, reducing the defective on surface, inhibition of whiskers.
But the occasion in the big large deformation of Sn plated film such as fitting portion of connector can not prevent the generation of the defective of surface film oxide.In addition, the surface forms thick oxide-film can make contact resistance increase, and is unfavorable.
Present inventors study with great concentration, found that, by form at least a oxide among Zn, P, Al, the Ti on the surface, can change the proterties of the existing oxide-film that only is made of the oxide of Sn, can reduce the probability that whisker produces.Learn in addition, if these oxide thickenings, on the contrary then the chimeric whisker that causes of connector produces the probability change greatly.
Therefore, by fusion coating on the Cu flat wire, apply Zn, the P, Al or the Ti that have added various concentration, thickness is the Sn plated film of 8～10 μ m, by XPS analysis (X linear light electronics optical spectroscopy), studied the kind of oxide on surface, analyzed the thickness that (auger electrons optical spectroscopy) studied oxide-film according to the AES depth direction.In addition, each sample and connector is chimeric, after the room temperature of carrying out for 2 weeks is placed, unload from connector, fitting portion is carried out SEM observe, the whisker that has measured the above whisker of 10 μ m produces probability.
Each data are presented in the table 1.
Table 1
| Sample No. | Add metal | Surface film oxide constitutes (according to XPS analysis) | Surface oxidation film thickness (analyzing) according to AES | Whisker produces |
|
| 1 | Do not have | The Sn oxide | 2.5nm | 47％ | |
| 2 | Zn | The Zn oxide | 2.5nm | 29％ | |
| 3 | Zn | The | 3nm | 40％ | |
| 4 | Zn | The Zn oxide | 4nm | 44％ | |
| 5 | Zn | The Zn oxide | 6nm | 55％ | |
| 6 | P | Sn oxide, P oxide | 2.5 |
21％ | |
| 7 | Al | The | 3nm | 40％ | |
| 8 | Ti | The | 3nm | 40％ |
Only compared by the sample No.1 that the Sn oxide constitutes with surface film oxide, the sample No.8 that the sample No.7 that the sample No.6 that the mixing of sample No.2～4, Sn oxide and P oxide that the Zn oxide constitutes constitutes, Al oxide constitute, Ti oxide constitute can make whisker generation probability reduce.
Like this, confirmed to compare with the occasion that only constitutes the surface by the Sn oxide, the mixed oxide of the oxide of the element beyond oxide by the element beyond the Sn or Sn oxide and the Sn can inhibition of whiskers generation frequency.
In addition, can learn,,, can not obtain whisker and suppress effect in the thick occasion of its thickness even if surface film oxide is made the oxide of the element beyond the Sn from the result of sample 5.Therefore, surface film oxide is preferably below the 5nm, more preferably below the 3nm.
Zn, P, Al, Ti have the tendency than the easy oxidation of Sn, by these elements being added in Sn coating and heat-treating, these oxides are formed naturally, and the proterties of Sn coating surface oxide-film is changed.
As the method that Zn adds, disclosed as patent documentation 2, have around Sn coating to apply Zn coating, and carry out heat-treating methods.When the time comes, can make the varied in thickness of surface film oxide by making the varied in thickness of Zn coating.
Embodiment
By electroplating the Sn coating that around the Cu of φ 0.6mm line, applies thickness 5 μ m, around it, apply 0.5 μ m thickness Z n by flash plating then.Through cold-drawn, pressure rolling operation, made the flat wire of 0.05mm thickness, 0.3mm width thereafter.Implemented reflow treatment with energising annealing then.
At last, these conductors are pressed 50 of 0.5mm spacing parallel arranged, having polyester with single face is that the polyester film of adhesive layer carries out lamination with its two sides, has made FFC.
Conventional example
By electroplating the Sn coating that around the Cu of φ 0.6mm line, applies thickness 5 μ m.Through cold-drawn, pressure rolling operation, made the flat wire of 0.05mm thickness, 0.3mm width thereafter.Thereafter operation be with the identical condition of embodiment under made FFC.
Be implemented in the XPS of the Sn plated conductor on the FFC portion of terminal of making in embodiment and the conventional example, in Fig. 4, Fig. 5, show its surface film oxide analysis result.
Fig. 4 shows the XPS analysis of Sn, and embodiment and conventional example all are that bond energy (Binding Energy) is 486,487eV, and the peak value of visible X line strength (kCPS) can confirm to have formed SnO, SnO
2
In addition, about Zn, as shown in Figure 5, in an embodiment, be bond energy 262eV, the peak value of visible X line strength can confirm that ZnO forms, but can not confirm the peak value of Zn in the prior embodiment.
Therefore learning that in the prior embodiment, surface film oxide only is made of the Sn oxide, in an embodiment, is to be made of Sn oxide and mixing of Zn oxide.
Below, in Fig. 6 (a), Fig. 6 (b), be presented at the AES depth direction analysis result of the Sn plated conductor of the FFC portion of terminal of making in embodiment and the conventional example.
With the conventional example of the embodiment of Fig. 6 (a) and Fig. 6 (b) relatively, can confirm that the distribution of depth direction of Sn, Cu, O, C is roughly the same, but in an embodiment, the peak value of Zn concentration is until degree of depth 5nm.
Then, the FFC and the connector of embodiment and conventional example is chimeric, carry out the room temperature of 250hr and place., FFC from connector unloaded, observe, measure the above whisker of 1 μ m and produce probability by fitting portion being carried out SEM thereafter.Be displayed in Table 2 the oxide thickness and the whisker generation frequency frequency that from XPS analysis result and the analysis of AES depth direction, obtain.
Table 2
| Surface film oxide constitutes | Oxide thickness | Whisker produces frequency | |
| Embodiment | Sn oxide, Zn oxide | 2.7nm | 7.6％ |
| Conventional example | The Sn oxide | 2.5nm | 22％ |
Like this, confirmed embodiments of the invention and conventional example relatively, whisker produces frequency and is reduced to 7.6% from 22%, has reduced by 1/3 approximately.
And then, handle the progress of the conductive surface oxidation cause for comparative heat, the FFC that makes in embodiment and the conventional example has been implemented the heat treatment of 24hr under 150 ℃.Implemented the AES depth direction analysis of the Sn coating of FFC portion of terminal thereafter.Its result is presented among Fig. 7 (a), Fig. 7 (b).
In the conventional example of Fig. 7 (b), with Fig. 6 (b) comparison of A-stage, under the state, the O atom is that peak value is arranged below 5nm in the early stage, but by heat treatment, the O atom enters into the above inside of 10nm, and oxide-film very heavy back has been grown.Different therewith, in the embodiments of the invention of Fig. 7 (a), under the state, the O atom also roughly becomes in heat treatment at the peak value below the 5nm in the early stage, and the degree of depth that enters of O atom is compared with A-stage, and it is very big poor not see.
Can confirm that thus in an embodiment of the present invention, using under the environment of FFC usually, surface film oxide is grown hardly, can keep good whisker characteristic, contact resistance behavior.
Claims (8)
1. used in flexible substrate conductor, it is provided in flexible flat cable or flexible print wiring board inside, it is characterized in that: the surface of conductors that constitutes at Cu or Cu alloy forms Sn or Sn alloy coating, and the surface film oxide of this plated film is made of the mixed oxide that the oxide of the oxide of the element beyond the Sn or Sn oxide and Sn element in addition mixes.
2. used in flexible substrate conductor according to claim 1 is characterized in that: the element beyond the above-mentioned Sn is the element that oxidation tendency is higher than Sn.
3. used in flexible substrate conductor according to claim 1 and 2 is characterized in that: the element beyond the above-mentioned Sn is at least a above element that is selected from Zn, P, Al, Ti.
4. according to the described used in flexible substrate conductor of claim 1 to 3, it is characterized in that: the surface oxidation film thickness that mixed oxide constituted that is mixed by the oxide of the oxide of the element beyond the above-mentioned Sn or Sn oxide and Sn element in addition is below the 5nm.
5. the manufacture method of a used in flexible substrate conductor, this conductor is provided in flexible flat cable or flexible print wiring board inside, it is characterized in that: the surface of conductors in Cu or Cu alloy formation forms Sn or Sn alloy coating, and form the plated film of at least a above element that is selected from Zn, P on this surface, by reflow treatment, make surface film oxide constitute or constitute by the mixed oxide of the oxide of the element of Sn oxide and these selections by the oxide of the element of these selections thereafter.
6. the manufacture method of a used in flexible substrate conductor, this conductor is provided in flexible flat cable or flexible print wiring board inside, it is characterized in that: the surface of conductors in Cu or Cu alloy formation forms Sn or the Sn alloy coating that comprises at least a above element that is selected from Zn or P, by reflow treatment, make surface film oxide by the oxide of the element of these selections constitute or by Sn oxide mix mixed oxide with the oxide of the element of these selections constitute thereafter.
7. flexible substrate is characterized in that: have conductor group's the two sides of each described used in flexible substrate conductor of many claims 1～4 to be provided with insulating barrier in parallel arranged.
8. flexible substrate according to claim 7 is characterized in that: the resin molding material that is had tack coat by single face constitutes above-mentioned insulating barrier.
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| CN2008100817939A CN101534603B (en) | 2008-03-13 | 2008-03-13 | Conductor used in flexible substrate, method for producing conductor, and flexible substrate |
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| CN101534603B CN101534603B (en) | 2012-05-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106676598A (en) * | 2016-12-13 | 2017-05-17 | 上海交通大学 | A method for restraining tin whisker growing based on micro-nano cone structure |
| CN109509731A (en) * | 2017-09-14 | 2019-03-22 | 屏东科技大学 | The tin silver connected structure and its manufacturing method of semiconductor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4367149B2 (en) * | 2004-01-30 | 2009-11-18 | 日立電線株式会社 | Flat cable conductor, method of manufacturing the same, and flat cable |
| JP5376553B2 (en) * | 2006-06-26 | 2013-12-25 | 日立金属株式会社 | Wiring conductor and terminal connection |
-
2008
- 2008-03-13 CN CN2008100817939A patent/CN101534603B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106676598A (en) * | 2016-12-13 | 2017-05-17 | 上海交通大学 | A method for restraining tin whisker growing based on micro-nano cone structure |
| CN106676598B (en) * | 2016-12-13 | 2019-08-23 | 上海交通大学 | A method of growth of tin crystal whisker is inhibited based on micro-nano needle wimble structure |
| CN109509731A (en) * | 2017-09-14 | 2019-03-22 | 屏东科技大学 | The tin silver connected structure and its manufacturing method of semiconductor |
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| Publication number | Publication date |
|---|---|
| CN101534603B (en) | 2012-05-09 |
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