CN1918326A - Electroplating in presence of co2 - Google Patents
Electroplating in presence of co2 Download PDFInfo
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- CN1918326A CN1918326A CN 200580004599 CN200580004599A CN1918326A CN 1918326 A CN1918326 A CN 1918326A CN 200580004599 CN200580004599 CN 200580004599 CN 200580004599 A CN200580004599 A CN 200580004599A CN 1918326 A CN1918326 A CN 1918326A
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Abstract
A method for performing electroplating in the co-presence of CO2 and an aqueous solution containing a metal salt is characterized in that CO2 is in a liquid, subcritical or supercritical state and a nonionic compound having a CO2 affinity portion is further added into the system where the aqueous solution and CO2 are co-present. By this method, the electrochemical reaction proceeds more efficiently and there can be formed a very good metal coating.
Description
Technical field
The present invention relates to CO
2Environment reply technology for replace solvents.More particularly, relate to CO
2For the efficient activity technology of the electrochemical reaction of solvent with used the electroplating technology of this technology.
Background technology
Because remarkableization of environmental problem utilized CO
2Receive publicity with the technology that substitutes the high organic solvent of toxicity as solvent.And, if can be at CO
2In handle compound, then wastewater treatment expense may be cut down significantly, receives publicity especially in the application of the high industrial field of cost for wastewater treatment such as dyeing, plating.Under such technical background, disclose and under agitation made aqueous metal salt and CO
2Outstanding turbid and carry out galvanized technology (patent documentation 1, non-patent literature 1 and 2).
According to disclosed information wherein, to compare with existing the plating, this technology can form high-quality plating pellicle, and plating pellicle free of pinholes, opacifying power are good, and can expect plating pellicle high rigidityization because the crystallization particle diameter that forms is little.
But, we at length supplementary test this technology, found that in order to form plating pellicle free of pinholes, good, containing the bigger restriction of existence on the plating operational condition of tensio-active agent.
In for example wherein disclosed technology, polyethylene oxide block copolymer or polyethylene oxide alkyl ethers have been used as hydrocarbon-surfactant as tensio-active agent.These tensio-active agents are at CO
2Surface active function in the-aqueous systems is low, therefore uses the nearly tensio-active agent (patent documentation 1 and non-patent literature 1,2) of 3 weight % (wt%)～6 weight % with respect to aqueous metal salt (being designated hereinafter simply as plating liquid).Thus, when practicality, require to solve tensio-active agent and the plating liquid and the exsiccant problem of removing attached to the plating pellicle.
And then the polyethylene oxide compound has quite a few dissolving owing to water-soluble also big in plating liquid as used herein.Thus, the CO in plating operation back plating is bathed
2Be not easy to separate with plating liquid, and then a large amount of bubbles that contain tensio-active agent and plating liquid that the produce during decompression in subsequent handling, these bubbles are invaded in pipe arrangements etc., produce the pipe arrangement blocking problem.The pipe arrangement blocking problem can cause serious efficient to reduce when technical application aspect throughput.
And then, require the chemical stability under the electrochemical conditions of these tensio-active agents in plating is bathed, but do not study fully so far.
So far at CO
2In the tensio-active agent very limited (patent documentation 2, non-patent literature 3) that plays a role.
And then, about this overcritical coating technology, also there is not the related information of plating overlay film of operability, the formation of employed tensio-active agent and plating so far.
Patent documentation 1:WO02/16673
Patent documentation 2: the spy opens flat 10-36680
Non-patent literature 1: Jitian etc., monthly magazine " MATERIAL STAGE ", Vol.1, No.9,2001,70 pages
Non-patent literature 2: Jitian etc., " Surface and Coatings Technology ", Vol.173,2003,285 pages
Non-patent literature 3: big bamboo etc., " surface ",, 40 volumes, 353 pages in 2002
Summary of the invention
The object of the present invention is to provide with CO
2For the efficient activity technology of the electrochemical reaction of solvent with use its electroplating technology.
From making immiscible in essence CO
2Consider that with aqueous metal salt emulsification or muddy angle of carrying out the mechanism of electrochemical reaction the inventor uses has CO
2The compound of affinity part is studied.Aniorfic surfactant forms insoluble salt in plating liquid, even can not carry out plating or can also can stop up pipe arrangement by plating.In addition, for cationic surfactant, can not form the plating pellicle.In contrast, for nonionic compound, can carry out good plating operation.And then, be applied at CO
2In plating the time, the plated film of having investigated in the plating groove forms mechanism, and is final so that finished following invention.
1. electro-plating method, it is at the aqueous solution that contains metal-salt and CO
2Coexistence under carry out electric plating method, it is characterized in that CO
2Exist with liquid, subcritical or supercritical state, further to the described aqueous solution and CO
2The coexistence system in add and to have CO
2The nonionic compound of affinity part, at this, so-called CO
2Affinity is partly represented to be selected from by (1) and is selected from least a homopolymer, 2 membered copolymers or 3 membered copolymers in the group of being made up of poly(propylene oxide), polybutylene oxide and polyethylene oxide, (2) part or all of hydrogen atom is contained fluoroalkyl by what fluorine replaced, (3) at least a in the group that the fluorochemical polyether base that replaced by fluorine of part or all of hydrogen atom, and (4) dialkyl group siloxy-is formed.
2. above-mentioned 1 described method, wherein, described nonionic compound is ether system or ester based compound.
3. above-mentioned 1 described method, wherein, described nonionic compound is pure based compound.
4. above-mentioned 1 described method, wherein, described nonionic compound is a hydrofluoric ether.
5. above-mentioned 1 described method, wherein, described nonionic compound is poly-alkylsiloxane.
6. above-mentioned 1 described method, wherein, described nonionic compound is a fluoropolymer.
7. plating is bathed, and it is to comprise the aqueous solution, the CO that contains metal-salt
2And have CO
2The plating of the nonionic compound of affinity part is bathed CO
2Exist with liquid, subcritical or supercritical state, at this, so-called CO
2Affinity is partly represented to be selected from by (1) and is selected from least a homopolymer, 2 membered copolymers or 3 membered copolymers in the group of being made up of poly(propylene oxide), polybutylene oxide and polyethylene oxide, (2) part or all of hydrogen atom is contained fluoroalkyl by what fluorine replaced, (3) at least a in the group that the fluorochemical polyether base that replaced by fluorine of part or all of hydrogen atom, and (4) dialkyl group siloxy-is formed.
8. electroplate and use additive, it comprises and has CO
2The nonionic compound of affinity part is the CO in liquid, subcritical or supercritical state
2Exist down and electroplate the additive of usefulness, at this, so-called CO
2Affinity is partly represented to be selected from by (1) and is selected from least a homopolymer, 2 membered copolymers or 3 membered copolymers in the group of being made up of poly(propylene oxide), polybutylene oxide and polyethylene oxide, (2) part or all of hydrogen atom is contained fluoroalkyl by what fluorine replaced, (3) at least a in the group that the fluorochemical polyether base that replaced by fluorine of part or all of hydrogen atom, and (4) dialkyl group siloxy-is formed.
9. the pre-treating process of plating, its use before the plating operation has CO
2The nonionic compound of affinity part is carried out the degreasing washing of clad substate, at this, and so-called CO
2Affinity is partly represented to be selected from by (1) and is selected from least a homopolymer, 2 membered copolymers or 3 membered copolymers in the group of being made up of poly(propylene oxide), polybutylene oxide and polyethylene oxide, (2) part or all of hydrogen atom is contained fluoroalkyl by what fluorine replaced, (3) at least a in the group that the fluorochemical polyether base that replaced by fluorine of part or all of hydrogen atom, and (4) dialkyl group siloxy-is formed.
10. the post-treating method of plating, it is to use in plating operation back to have CO
2The nonionic compound of affinity part is carried out the washing of plating pellicle, at this, and so-called CO
2Affinity is partly represented to be selected from by (1) and is selected from least a homopolymer, 2 membered copolymers or 3 membered copolymers in the group of being made up of poly(propylene oxide), polybutylene oxide and polyethylene oxide, (2) part or all of hydrogen atom is contained fluoroalkyl by what fluorine replaced, (3) at least a in the group that the fluorochemical polyether base that replaced by fluorine of part or all of hydrogen atom, and (4) dialkyl group siloxy-is formed.
11. the plating overlay film has following feature:
(1) diameter is every 1cm more than or equal to the pin hole of 1 μ m
2Smaller or equal to 1,
(2) thickness of overlay film is smaller or equal to 1 μ m, and
(3) surfaceness of overlay film is smaller or equal to 10nm.
Above-mentioned 1 described method of 12-wherein, used nonionic compound, (the CO of described nonionic compound
2The affinity part)-X-or X-(CO
2The affinity part)-X-is shown below 1) or 2):
1)F-(CF
2)
q-(OCF
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
p-X-
2)-X-(CH
2)
p-(CF
2O)
o-(C
2F
4O)
n-(C
3F
6O)
m-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
p-X-
At this, m, n, o, p, q are the integer more than or equal to 0, and m and n are 0～15 integer, and are not 0 simultaneously, n+m≤20, o=0～20, p=0～2, q=1～10; Regardless of the order of each repeating unit ,-(OC
3F
6)
m-expression-(OCF
2CF
2CF
2)
m-or-(OCF (CF
3) CF
2)
m-,-(OC
2F
4)
n-expression-(OCF
2CF
2)
n-or-(OCF (CF
3))
n-;
Here, X can be the same or different, expression singly-bound, O, S, NH, NR (R
a: alkyl), C=O, C (O) O, OC (O), C (O) S, SC (O), C (O) NH, C (O) NR
a(R
a: alkyl), NH (O) C, NR (O) C, CH
2, CHR
a, CR
a 2(R
a: alkyl), SO
2NH or NHSO
2
13. above-mentioned 1 described method wherein, uses shown below 1)～3) nonionic compound,
1)F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
pX-Rh
2)F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
pX-Rh-X-(CH
2)
p-(CF
2O)
o-(C
2F
4O)
n-(C
3F
6O)
m-(CF
2)
q-F
3)Rh-X(CH
2)
p-(CF
2O)
o-(C
2F
4O)
n-(C
3F
6O)
m-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
pX-Rh
At this, m, n, o, p, q are the integer more than or equal to 0, and m and n are 0～15 integer, and are not 0 simultaneously, n+m≤20, o=0～20, p=0～2, q=1～10; Regardless of the order of each repeating unit ,-(OC
3F
6)
m-expression-(OCF
2CF
2CF
2)
m-or-(OCF (CF
3) CF
2)
m-,-(OC
2F
4)
n-expression-(OCF
2CF
2)
n-or-(OCF (CF
3))
n-;
Here, X can be the same or different, expression singly-bound, O, S, NH, NR (R
aAlkyl), C=O, C (O) O, OC (O), C (O) S, SC (O), C (O) NH, C (O) NR
a(R
a: alkyl), NH (O) C, NR (O) C, CH
2, CHR
a, CR
a 2(R
aAlkyl), SO
2NH or NHSO
2
Rh is a hydrophilic parts, and it is for containing the alkyl of heteroatomic straight chain or side chain in molecule.
14. above-mentioned 13 described methods, wherein, Rh is a polyoxyalkylenes.
15. above-mentioned 13 described methods wherein, are used CO
2The carbonatoms of affinity part is identical with the carbonatoms of Rh base or than its nonionic compound of Duoing.
16. above-mentioned 1 described method wherein, used nonionic compound, (CO in the described nonionic compound
2The affinity part)-X-or X-(CO
2The affinity part)-X-is shown below 1) or 2):
1)Y-(CF
2)
m1-(CH
2)
n1-X
2)X-(CH
2)
n1-(CF
2)
m1-(CH
2)
n1-X
At this, Y is F or H, and X can be the same or different, and expression is selected from by COO, O, S, CONH, NHCO, SO
2NH, NHSO
2Combination base in the group of forming;
M1 is 3～20 integer, and n1 can be the same or different, and is 0～2 integer.
17. above-mentioned 16 described methods, wherein, nonionic compound has shown below 1)～3) any one structure,
1)Y-(CF
2)
m1-(CH
2)
n1-X-Rh
2)Y-(CF
2)
m1-(CH
2)
n1-X-Rh-X-(CH
2)
n1-(CF
2)
m1-Y
3)Rh-X-(CH
2)
n1-(CF
2)
m1-(CH
2)
n1-X-Rh
At this, Y is F or H, and X can be the same or different, and expression is selected from by COO, O, S, CONH, NHCO, SO
2NH, NHSO
2Combination base in the group of forming;
M1 can be the same or different, and is 3～20 integer, and n1 can be the same or different, and is 0～2 integer;
Rh is a hydrophilic parts, and it is for containing the alkyl of heteroatomic straight chain or side chain in molecule.
18. above-mentioned 17 described methods, wherein, Rh is a polyoxyalkylenes.
19. above-mentioned 17 described methods, wherein, CO
2The carbonatoms of affinity part is identical or more than it with the carbonatoms of Rh base.
Among the present invention, CO
2-plating liquid is the aqueous solution of ionogen (for example metal-salt), has CO simultaneously by using
2Disengaging antifoam performance and the matrix-plating liquid and the CO of the gas bubbles that produces when good emulsifying ability between-plating liquid, operation
2Between appropriateness wettability and have CO
2The nonionic compound of affinity part can make electroplating reaction efficient higher, can form very good metal pellicle simultaneously.And then the pre-treatment of plating and postprocessing working procedures also can easy, can also improve throughput significantly.
When using nonionic compound of the present invention, because the carbonic acid gas after stirring-metal water solution can sharp separation, the bubble of the metal water solution of problem and carbonic acid gas enters pipe arrangement inside, metal-salt stops up problems such as inside so can positively avoid becoming in the past.
And then nonionic compound of the present invention is owing to have a washing effect in supercritical co, so also be effective to degreasing washing in the operation before the plating and the washing of the pellicle behind the plating.Therefore, can make major contribution to the metal waste liquid that washing produced that reduces in alkali, acid waste liquid and the subsequent handling in the preceding operation that in plating technic, became big problem in the past.
Description of drawings
Fig. 1 is the device that uses in the embodiment of the invention.
Fig. 2 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 1.
Fig. 3 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 2.
Fig. 4 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 3.
Fig. 5 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 4.
Fig. 6 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 5.
Fig. 7 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 6.
Fig. 8 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 7.
Fig. 9 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 8.
Figure 10 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 9.
Figure 11 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 10.
Figure 12 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 11.
Figure 13 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 12.
Figure 14 is the scanning electron microscope photo of the plating overlay film that obtains among the embodiment 13.
Figure 15 is the scanning electron microscope photo (multiplying power: 500 times) of the plating overlay film that obtains among the embodiment 15.
Figure 16 is the SEM cross-section photograph (multiplying power: 30000 times, 10000 times) of the plating overlay film that obtains in the reference example.
Figure 17 is the scanning electron microscope photo of the plating overlay film that obtains in the comparative example 1.
Figure 18 is the scanning electron microscope photo of the plating overlay film that obtains in the comparative example 2.
Nomenclature
1 CO 2 high pressure bottle
2 valves
3 infusion pumps
4 thermostatic baths
5 agitators
6 rotors
7a electrode (anode)
7b electrode (negative electrode)
8 high pressure vessels
9 plating power supplys
10 pressure-regulators
Embodiment
At CO
2In electrochemical reaction preferably utilize and have CO
2The nonionic compound of affinity part makes unmixed in fact CO
2-plating liquid only forms emulsified state (O/W type micella) or cloudy state when stirring, and when stopping to stir CO
2-plating liquid separates with suitable speed.And then in plating operation, the ability that the bubble of the gases such as hydrogen that produce on the matrix is broken away from apace froth breaking is very important for the needleless permeability of plating pellicle.Moreover, when forming pellicle, pass through control plating liquid and CO
2Separately with the wettability of matrix, can suppress the be full of cracks of the plating pellicle that causes by the formed micella of plating liquid.
In order to pursue aforesaid function, have CO
2Affinity and have the appropriateness wetting ability be important, can reach a conclusion thus: do not contain group (non-ionic type) and have CO with electric charge at intramolecularly
2The compound of affinity part is effective.
The research of carrying out the plating operation particularly as described below, the result determines that only the compound exhibits of non-ionic type goes out excellent function.In contrast, also determine to utilize anionic and cationic surfactant can not form the plating pellicle, perhaps in operation, had bigger problem (with reference to comparative example).
That is, think in the present technique that effectively nonionic compound is because to CO
2Have high solubleness and have the CO of making
2Dispersion effectively in plating liquid, muddiness or emulsive function; In electroplating operations easily with the function of the bubble disengagement froth breaking that produced on the matrix; And plating liquid and CO
2The wettability appropriate each other with matrix.
Show as the character of the above-claimed cpd that is derived from non-ionic type in this appropriate wettability, and then wherein selecting of optimizing compound can be judged by the various parameters corresponding with tensio-active agent as essential function.
In the preferred implementation of the present invention, has CO
2The nonionic compound of affinity part has CO
2Affinity part and hydrophilic parts are (to CO
2The part that affinity is low).In one embodiment, these two portions through in conjunction with basic X can in conjunction with.
About CO
2The affinity part, be selected from least a homopolymer, 2 membered copolymers or 3 membered copolymers in the group of forming by poly(propylene oxide), polybutylene oxide and polyethylene oxide as (1), can enumerate poly(propylene oxide), polybutylene oxide, polyethylene oxide, polyethylene oxide-poly(propylene oxide) multipolymer, polyethylene oxide-polybutylene oxide multipolymer, poly(propylene oxide)-polybutylene oxide multipolymer, polyethylene oxide-poly(propylene oxide)-polybutylene oxide multipolymer particularly.This multipolymer can be enumerated random copolymers, segmented copolymer, graft copolymer, is preferably segmented copolymer.
The nonionic compound of using among the present invention is to have CO at least
2The compound of affinity part (Rf) can be only by CO
2The compound that affinity part (Rf) forms also can be with linking CO in conjunction with base (X)
2The compound of affinity part (Rf) and hydrophilic parts (Rh).
In the preferred embodiment of the present invention, of the present invention have a CO
2The nonionic compound of affinity part has that (X represents singly-bound, O, S, NH, NR (R with suitable concatenating group (X)
a: alkyl), C=O, C (O) O, OC (O), C (O) S, SC (O), C (O) NH, C (O) NR
a(R
a: alkyl), NH (O) C, NR (O) C, CH
2, CHR
a, CR
a 2(R
a: alkyl), SO
2NH or NHSO
2) binding CO
2The structure of affinity part (Rf) and hydrophilic parts (Rh), between Rf and X or Rh and X, can also accompany by the fluorine replacement also can straight chain or have alkylidene group (A) ((CH for example of side chain
2)
m, (CF
2)
n, CF (CF
3), (CF
2)
n(CH
2) etc.).
Method of the present invention is at the aqueous solution that contains metal-salt and CO
2Coexistence under carry out electric plating method, it is characterized in that CO
2Exist with liquid, subcritical or supercritical state, further to the described aqueous solution and CO
2The coexistence system in add and to have CO
2The nonionic compound of affinity part.At this, so-called " further to the described aqueous solution and CO
2The coexistence system in add nonionic compound " be meant to use and comprise CO
2The plating liquid of (the 1st composition), the aqueous solution (the 2nd composition) that contains metal-salt and these three kinds of compositions of nonionic compound (the 3rd composition) is electroplated, with the interpolation sequence independence of three kinds of compositions.For example, can be to comprising CO
2Form the plating liquid of three composition systems with mixing nonionic compound in the plating liquid of the aqueous solution that contains metal-salt; Can be to CO
2Mix nonionic compound in advance, and then mix the plating liquid that contains the aqueous solution of metal-salt and form three composition systems; Can also mix the aqueous solution and nonionic compound that contains metal-salt and then mixed C O in advance
2And form the plating liquid of three composition systems.
As CO
2Affinity part (Rf), can enumerate to be selected from and be selected from least a homopolymer, 2 membered copolymers or 3 membered copolymers in the group of forming by poly(propylene oxide), polybutylene oxide and polyethylene oxide by (1), (2) part or all of hydrogen atom is contained fluoroalkyl by what fluorine replaced, (3) fluorochemical polyether, and at least a in the group formed of (4) dialkyl group siloxy-.CO particularly
2The affinity part is preferred by following structural formula 1)～4) expression.
1)F-(CF
2)
q-(OCF
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
p-
2)-(CH
2)
p-(CF
2O)
o-(C
2F
4O)
n-(C
3F
6O)
m-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
p-
(wherein, m, n, o, p, q with above-mentioned in definition identical.)
3)Y-(CF
2)
m-(CH
2)
n-
4)-(CH
2)
n-(CF
2)
m-(CH
2)
n-
(wherein, m, n, Y with above-mentioned in definition identical.)
As hydrophilic parts (Rh), can enumerate at intramolecularly and not contain group and contain alkyl and at least a group of (gathering) ether or hydroxyl (alcohol) with electric charge.Rh is the alkyl that contains heteroatoms (for example Sauerstoffatom, nitrogen-atoms, sulphur atom) or do not contain heteroatomic straight or branched in molecule.Preferred Rh base is a polyoxyalkylenes.As polyoxyalkylenes, can enumerate the polyether-based of polyoxy propylidene, polyoxy butylidene and polyoxyethylene etc.The long polyalkylene oxide groups of chain appropriateness also has close CO
2The function of property group.Thereby, preferably do not become close CO as the polyoxyalkylenes of Rh base
2The property chain length group, that possess possess hydrophilic property (for example Rf base is F-(CF (CF
3) CF
2O)
nCF (CF
3) time have 1～15 repeating unit) poly-alkane glycol.
As having CO
2The nonionic compound of affinity part (Rf) and hydrophilic parts (Rh), compound that can the following structure of illustration.
Rf-X-Rh、
Rf-A-X-Rh、
Rf-X-A-Rh、
Rh-X-Rf-X-Rh、
Rf-X-Rh-X-Rf。
(Rf, Rh, X with above-mentioned in definition identical, A is meant alkylidene group straight chain or that have side chain that can be replaced by fluorine.)
Compounds effective is for having CO in the present invention
2The nonionic compound of affinity part, and then in order to make H.D plating pellicle, importantly CO
2The balance of affinity part (Rf) and hydrophilic parts (Rh).This balance can be represented with the carbonatoms of each group, be preferably following ratio.Hydrophilic parts is the situation of hydrocarbon, and Rf: Rh is 20: 1 to 1: 2 (being preferably 10: 1 to 1: 1 especially).Hydrophilic parts is the situation that contains the group of ether, and Rf: Rh is 20: 1 to 1: 1 (being preferably 5: 1 to 2: 1 especially).
Here, when nonionic compound had 2 Rh or 2 Rf, each carbonatoms was meant the total of 2 Rh or 2 Rf.
In general, fluorochemical is compared at CO with hydrocarbon compound
2In the function excellence, can help to reduce emulsification CO significantly for this plating operation
2Addition with the necessary compound of plating liquid.And then has a CO
2The nonionic compound of affinity part is because water-soluble low, so the solubleness in plating liquid is low, and the plating liquid-CO after plating is handled
2Disengaging time also can shorten, confirmed to have CO
2It is effective additives that the nonionic compound of affinity part is compared with existing hydrocarbon-surfactant.
And then, consider from the hydrophilic angle of appropriateness, determine to have CO
2The nonionic compound of affinity part can demonstrate excellent function.In contrast, in the anionic, carboxylate salt in use can form insoluble salt with the metal of plating liquid (metal water solution), the processing after can not forming good plating pellicle and can not carrying out plating.And then, for Sulfonates in the anionic and since in subsequent handling micella can not be when using nonionic compound quick disappearance (separation of plating liquid is insufficient), so produce the pipe arrangement obstruction by the bubble that contains plating liquid.In addition, for the cationic surfactant as the ammonium salt, tensio-active agent can adsorb to negative electrode during energising, so can not form plating pellicle (with reference to comparative example).
In a preferred implementation of the present invention, as having CO
2The nonionic compound of affinity part can illustration ether system or ester based compound, pure based compound, poly-alkylsiloxane, hydrofluoric ether or fluoropolymer compounds, more preferably ether system or ester based compound.The fluorinated compound is excellent especially, illustration following 1)～6) compound.
1)F-(CF
2)
q-(OCF
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
p-X-Rh
2)F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
pX-Rh-X-(CH
2)
p-(CF
2O)
o-(C
2F
4O)
n-(C
3F
6O)
m-(CF
2)
q-F
3)Rh-X(CH
2)
p-(CF
2O)
q-(C
2F
4O)
n-(C
3F
6O)
m-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
pX-Rh
(wherein, m, n, o, p, q, X and Rh are identical with above-mentioned middle definition, regardless of the order of each repeating unit, and-(OC
3F
6)
m-expression-(OCF
2CF
2CF
2)
m-or-(OCF (CF
3) CF
2)
m-,-(OC
2F
4)
n-expression-(OCF
2CF
2)
n-or-(OCF (CF
3))
n-)
4)Y-(CF
2)
m1-(CH
2)
n1-X-Rh
5)Y-(CF
2)
m1-(CH
2)
n1-X-Rh-X-(CH
2)
n-(CF
2)
m-Y
6)Rh-X-(CH
2)
n-(CF
2)
m-(CH
2)
n-X-Rh
(wherein, m1 is 3～20 integer, and n1 can be identical, also can be different, be 0～2 integer, X, Y, Rh with above-mentioned in define identical)
As concrete example with above structural formula illustrative ether system or ester based compound, can enumerate compound shown below, but in addition as long as satisfy the CO that is derived from above-mentioned carbonatoms ratio
2Balance between affinity part-hydrophilic parts just can play a role effectively.These compounds are owing to can control matrix and plating liquid and CO most effectively
2The defoaming of hydrogen of wettability, generation, therefore can form good plating pellicle.
F-(CF(CF
3)CF
2O)
nCF(CF
3)COO(CH
2)
mCH
3(n＝1～15、m＝0～30)
F-(CF(CF
3)CF
2O)
nCF(CF
3)CH
2OOC(CH
2)
mCH
3(n＝1～15、m＝0～30)
F-(CF(CF
3)CF
2O)
nCF(CF
3)CH
2O(CH
2)
mCH
3(n＝1～15、m＝0～30)
F-(CF(CF
3)CF
2O)
nCF(CF
3)COO(CH
2CH
2O)
mCH
3(n＝1～15、m＝1～10)
F-(CF(CF
3)CF
2O)
nCF(CF
3)COO(CH(CH
3)CH
2O)
mCH
3(n＝1～15、m＝1～10)
F-(CF
2CF
2O)
nCF
2COO(CH
2)
mCH
3(n＝1～15、m＝0～30)
F-(CF
2CF
2O)
nCF
2CH
2OOC(CH
2)
mCH
3(n＝1～15、m＝0～30)
F-(CF
2CF
2O)
nCF
2CH
2O(CH
2)
mCH
3(n＝1～15、m＝0～30)
F-(CF
2CF
2O)
nCF
2COO(CH
2CH
2O)
mCH
3(n＝1～15、m＝1～10)
F-(CF
2CF
2O)
nCF
2COO(CH(CH
3)CH
2O)
mCH
3(n＝1～15、m＝1～10)
CF
3(CF
2)
n-(CF
2CF
2O)
mCF
2COO(CH
2)
pCH
3(n＝1～8、m＝1～15、p＝0～30)
CF
3(CF
2)
n-(CF
2CF
2O)
mCF
2COO(CH
2CH
2O)
pCH
3(n＝1～8、m＝1～15、p＝1～10)
CF
3(CF
2)
n-(CF
2CF
2O)
mCF
2COO(CH(CH
3)CH
2O)
pCH
3(n＝1～8、m＝1～15、p＝1～10)
F-(CF
2CF
2CF
2O)
nCF
2CF
2COO(CH
2)
mCH
3(n＝1～15、m＝0～30)
F-(CF
2CF
2CF
2O)
nCF
2CF
2CH
2OOC(CH
2)
mCH
3(n＝1～15、m＝0～30)
F-(CF
2CF
2CF
2O)
nCF
2CF
2CH
2O(CH
2)
mCH
3(n＝1～15、m＝0～30)
F-(CF
2CF
2CF
2O)
nCF
2CF
2COO(CH
2CH
2O)
mCH
3(n＝1～15、m＝1～10)
F-(CF
2CF
2CF
2O)
nCF
2CF
2COO(CH(CH
3)CH
2O)
mCH
3(n＝1～15、m＝1～10)
F-(CF
2CF
2CF
2O)
nCF
2CF
2CH
2O(CH
2CH
2O)
mCH
3(n＝1～15、m＝1～10)
F-(CF
2CF
2CF
2O)
nCF
2CF
2CH
2O(CH(CH
3)CH
2O)
mCH
3(n＝1～15、m＝1～10)
F-(CF(CF
3)CF
2O)
n(CF
2CF
2O)
mCF
2COO(CH
2)
pCH
3(n＝1～10、m＝1～10、p＝0～30)
F-(CF(CF
3)CF
2O)
n(CF
2CF
2O)
mCF
2COO(CH
2CH
2O)
pCH
3(n＝1～10、m＝1～10、p＝1～10)
F-(CF(CF
3)CF
2O)
n(CF
2CF
2O)
mCF
2COO(CH(CH
3)CH
2O)
pCH
3(n＝1～10、m＝1～10、p＝1～10)
F-(CF(CF
3)CF
2O)
nCF(CF
3)COO(CH
2CH
2O)
mOCO(CF
3)CF(OCF
2(CF
3)CF)
pF(n＝1～15、m＝1～20、p＝1～15)
F-(CF(CF
3)CF
2O)
nCF(CF
3)COO(CH
2)
mOCO(CF
3)CF(OCF
2(CF
3)CF)
pF(n＝1～15、m＝1～30、p＝1～15)
F-(CF(CF
3)CF
2O)
nCF(CF
3)COO(CH(CH
3)CH
2O)
mOCO(CF
3)CF(OCF
2(CF
3)CF)
pF(n＝1～15、m＝1～20、p＝1～15)
CH
3(CH
2)
nOCOCF(CF
3)(CF(CF
3)CF
2O)
mCF(CF
3)COO(CH
2)
pCH
3(n＝0～20、m＝1～20、p＝0～20)
CH
3(CH
2)
nOCOCF
2(OCF
2CF
2)
mOCF
2COO(CH
2)
pCH
3(n＝0～20、m＝1～20、p＝0～20)
CH
3(OCH
2CH
2)
nOCOCF(CF
3)(CF(CF
3)CF
2O)
mCF(CF
3)COO(CH
2CH
2O)
pCH
3(n＝1～10、m＝1～20、p＝1～10)
CH
3(OCH
2CH
2)
nOCOCF(CF
3)(OCF
2CF(CF
3))
m(CF
2)
n(CF(CF
3)CF
2O)
oCF(CF
3)COO(CH
2CH
2O)
pCH
3(n＝1～5、m+o＝2～20、p＝1～10)
CH
3(OCH
2CH
2)
nOCOCF
2(OCF
2CF
2)
mOCF
2COO(OCH
2CH
2)
pCH
3(n＝0～20、m＝1～20、p＝0～20)
CH
3(OCH
2CH(CH
3))
nOCOCF(CF
3)(CF(CF
3)CF
2O)
mCF(CF
3)COO(CH(CH
3)CH
2O)
pCH
3(n＝1～10、m＝1～20、p＝1～10)
F-(CF(CF
3)CF
2O)
nCF(CF
3)CH
2O(CH
2)
m(CF
2)
pCF
3(n＝1～15、m＝1～10、p＝1～20)
XCF
2(CF
2)
n(CH
2)
mO(CH
2)
pCH
3(X＝H、F，n＝3～20、m＝1～2、p＝1～20)
XCF
2(CF
2)
n(CH
2)
mO(CH
2CH
2O)
pCH
3(X＝H、F，n＝3～20、m＝1～2、p＝1～10)
XCF
2(CF
2)
n(CH
2)
mO(CH(CH
3)CH
2O)
pCH
3(X＝H、F，n＝3～20、m＝1～2、p＝1～10)
XCF
2(CF
2)
n(CH
2)
mOOC(CH
2)
pCH
3(X＝H、F，n＝3～20、m＝1～2、p＝0～20)
XCF
2(CF
2)
n(CH
2)
mCOO(CH
2)
pCH
3(X＝H、F，n＝3～20、m＝0～2、p＝0～20)
XCF
2(CF
2)
n(CH
2)
mCOO(CH
2CH
2O)
pCH
3(X＝H、F，n＝3～20、m＝0～2、p＝1～10)
XCF
2(CF
2)
n(CH
2)
mCOO(CH(CH
3)CH
2O)
pCH
3(X＝H、F，n＝3～20、m＝0～2、p＝1～10)
CH
3(CH
2)
mOOC(CF
2)
nCOO(CH
2)
pCH
3(m＝0～20、n＝1～20、p＝0～20)
CH
3(OCH
2CH
2)
mOOC(CF
2)
nCOO(CH
2CH
2O)
pCH
3(m＝1～10、n＝1～20、p＝1～10)
CH
3(OCH
2CH(CH
3))
mOOC(CF
2)
nCOO(CH(CH
3)CH
2O)
pCH
3(m＝1～10、n＝1～20、p＝1～10)
CH
3(CH
2)
mCOO(CH(CH
3)CH
2O)
nCH
3(m＝1～20、n＝1～30)
CH
3(CH
2)
mO(CH(CH
3)CH
2O)
nCH
3(m＝1～20、n＝1～30)
The part fluoric compound of below representing preferred ether system or ester system:
F-(CF(CF
3)CF
2O)
nCF(CF
3)COO(CH
2)
mCH
3(n＝1～15、m＝0～30)、
F-(CF(CF
3)CF
2O)
nCF(CF
3)COO(CH
2CH
2O)
mCH
3(n＝1～15、m＝1～10)、
XCF
2(CF
2)
n(CH
2)
mO (CH
2)
pCH
3(X=H, F, n=3～20, m=1～2, p=0～20) and XCF
2(CF
2)
n(CH
2)
mCOO (CH
2)
pCH
3(X=H, F, n=3～20, m=0～2, p=0～20).
As the pure based compound of one of embodiment of nonionic compound can be below the illustration compound.
XCF
2(CF
2)
n(CH
2)
mOH(X＝H、F，n＝3～20、m＝1～2)
HOCH
2(CH
2)
m(CF
2)
n(CH
2)
pCH
2OH(m＝1～20、n＝1～20、p＝1～20)
F-(CF(CF
3)CF
2O)
nCF(CF
3)CH
2OH(n＝1～15)
HOCH
2(CF(CF
3)CF
2O)
nCF(CF
3)CH
2OH(n＝1～15)
HOCH
2CF(CF
3)(CF(CF
3)CF
2O)
mCF(CF
3)CH
2OH(m＝1～20)
F-(CF
2CF
2O)
mCF
2CH
2OH(m＝1～20)
CF
3O-(CF
2CF
2O)
mCF
2CH
2OH(m＝1～20)
HOCH
2(CF
2CF
2O)
mCF
2CH
2OH(m＝1～20)
HOCH
2CF
2(OCF
2CF
2)
m(OCF
2)
nOCF
2CH
2OH(n+m＝1～20)
F-(CF
2CF
2CF
2O)
mCF
2CF
2CH
2OH(m＝1～20)
F-(CF(CF
3)CF
2O)
n(CF
2CF
2O)
mCF
2CH
2OH(n＝1～10、m＝1～10)
CF
3(CF
2)
n-(CF
2CF
2O)
mCF
2CH
2OH(n＝1～10、m＝1～10)
As the poly-alkylsiloxane of one of embodiment of nonionic compound can be below the illustration compound.
-(Si(CH
3)((CH
2)
3-(OCH
2CH
2)
p-OCH
3))
mO-(Si(CH
3)
2O)
n-(m＝10～100、n＝10～100、p＝1～10)
-(Si(CH
3)((CH
2)
3-(OC
3H
6)
p-OCH
3))
mO-(Si(CH
3)
2O)
n-(m＝10～100、n＝10～100、p＝1～10)
CH
3O-(Si(CH
3)-(O
2C(CH
2)
pCH
3))
mO-(Si(CH
3)
2O)
n-CH
3(m＝10～100、n＝10～100、p＝1～20)
CH
3O-(Si(CH
3)
2)
mO-(Si(CH
3)
2O)
n-CH
3(m＝10～100、n＝10～100)
R
3Si-O-(SiR
2O-)
n-(SiR (Rh) O-)
m-SiR
3(in the formula ,-(SiR
2O-)
n(SiR (Rh) O-)
mBe random or block body, R is the alkyl of C1～C4, and Rh is identical with above-mentioned middle definition, n: m=10: 1 to 1: 1, and n=10～500)
R
2RhSi-O-(SiR
2O-)
n-(SiR
2Rh) (in the formula, n: m=10: 1 to 1: 1, n=10～500, R is the alkyl of C1～C4, Rh is identical with above-mentioned middle definition)
R
3Si-O-(SiR
2O-)
n-Rh-(SiR
2O-)
m-SiR
3(in the formula, n: m=10: 1 to 1: 1, n=10～500, R is the alkyl of C1～C4, Rh is identical with above-mentioned middle definition)
As the hydrofluoric ether of one of embodiment of nonionic compound can be below the illustration compound.
X(CF
2)
m(CH
2)
nH(X＝H、F，n＝3～20、m＝1～20)
As the fluoropolymer of one of embodiment of nonionic compound can be below the illustration polymkeric substance.
-(CH
2CH(CO
2CH
2CH
2(CF
2)
mCF
3))
n-(m＝2～8、n＝5～100)
-(CH
2CH(OCH
2CH
2OCOCH
2CH
2(CF
2)
mCF
3))
n-(m＝2～8、n＝5～100)
-(CH
2CH(OCH
2CH
2OCOCF(CF
3)(OCF
2CF(CF
3))
mF)
n-(m＝1～15、n＝5～100)
-(CH
2CH(CH
2OCH
2CH
2(CF
2)
mCF
3)O)
n-(m＝2～8、n＝5～100)
-(CH
2CH(CH
2OCH
2CF(CF
3)(OCF
2CF(CF
3))
mF)
n-(m＝1～15、n＝5～100)
Carrying out galvanized situation, the CO that uses among the present invention
2(overcritical, subcritical or liquid) is plating liquid: CO with the volume ratio of plating liquid (aqueous solution that contains metal-salt)
2=5: 95 to 95: 5, be preferably 10: 90 to 80: 20, more preferably 20: 80 to 60: 40.
That uses among the present invention has a CO
2The nonionic compound of affinity part is a commercially available product, and perhaps those skilled in the art can easily make by known method.
With respect to the aqueous solution that contains metal-salt, has a CO among preferred the present invention
2The consumption of the nonionic compound of affinity part is 0.001wt%～10wt% degree, is preferably 0.01wt%～5wt% degree, more preferably 0.1wt%～1wt% degree.Particularly owing to have CO
2The high functionality of the nonionic compound of affinity part, its consumption about with 0.1wt% can play a role fully, therefore also is being better than hydrocarbon compound aspect this.
And then also can add organic solvent shown below (solubility promoter).Alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol for example, ketones such as acetone, acetonitrile, ester classes such as vinyl acetic monomer, ethers such as ether, fluorocarbon class, halogenide such as methylene dichloride, chloroform.Preferred especially low, the low-molecular-weight solvent of toxicity.
In addition, the CO that uses in the present invention
2With liquid, subcritical, supercritical state use.In addition, so owing to be that two phase systems must stir.At this, so-called stirring can be enumerated magnetic agitation, mechanical stirring or based on the stirring of ultrasonic irradiation etc.
About concrete revolution, according to having CO
2The kind of the nonionic compound of affinity part, the scale of device, stirring means and change, thus need be in actually operating optimizing.
In addition, tensio-active agent of the present invention has by making plating liquid and CO
2Mix and make the micella stable existence that forms this moment easily and form the function of good plating pellicle.Therefore, the effect of tensio-active agent of the present invention is not subjected to tensio-active agent, plating liquid, CO
2Order in the adding apparatus, the blending means that also has these compositions, the special qualification of whipped form.The embodiment that puts down in writing in this specification sheets is undertaken by small-scale experimental technique, has the mixing or the stirring means of the composition corresponding with its scale during still owing to extensiveization, so should design the introduction method of each optimized tensio-active agent.Such introduction method can easily be determined by those skilled in the art.But, no matter use which kind of mode mixed C O
2-plating liquid carries out plating, and tensio-active agent of the present invention can obtain better plating pellicle than other the hydro carbons or the tensio-active agent of ionic.
In this manual, galvanized notion also comprises electrode reactions such as electrolytic oxidation, electrolytic reduction, electrochemical analysis, corrosion of metal, protection against corrosion, passivation etc. except electroplating.
The temperature of electroplating reaction of the present invention is 10 ℃～100 ℃ a degree.
Pressure is the degree of 0.1MPa～30MPa, is preferably 1MPa～20MPa degree, more preferably 5MPa～15MPa degree.
As stirring, magnetic agitation or churned mechanically situation can illustration 100rpm～100000rpm, are preferably 400rpm～1000rpm; The situation of ultrasonic irradiation can illustration 20kHz～10MHz.
Carry out under the galvanized situation, make ionogen particularly contain the electrolyte dissolution of one or more metals at aqueous phase.As so electrolytical metal, can illustration Ni, Co, Cu, Zn, Cr, Sn, W, Fe, Ag, Cd, Ga, As, Cr, Se, Mn, In, Sb, Te, Ru, Rh, Pd, Au, Hg, Tl, Pb, Bi, Po, Re, Os, Ir, Pt etc.As ionogen, halogenide such as water miscible muriate that can these metals of illustration, bromide, iodide, nitrate, vitriol, sulfamate, organic acid salts such as acetate, prussiate, oxide compound, oxyhydroxide, complex compound etc.
In addition, handle, also can utilize present technique to make semi-conductors such as oxide compound pellicle, nitride pellicle as electrochemical surface in addition.
The plating of the application of the invention additive (nonionic compound), the carbonic acid gas after can electroplating apace and the froth breaking (separation) of the muddy liquid of metal water solution.
For example with 10MPa, 50 ℃, when 500r.p.m. stirs, use the foam time after plating of the present invention stops to stir with the situation of additive to be generally, be preferably smaller or equal to 5 minutes smaller or equal to 10 minutes.
The plating overlay film that the present invention obtains has feature as described below.
(1) diameter is every 1cm more than or equal to the pin hole of 1 μ m
2Smaller or equal to 1,
(2) thickness of overlay film is smaller or equal to 1 μ m, and
(3) surfaceness of overlay film is smaller or equal to 10nm.
And then the particle diameter ratio of the metallics of the plating pellicle that obtains among the present invention uses the supercritical CO of hydrocarbon-surfactant
2It is little to form film during plating, just compares with the situation of existing plating and has said nothing of.It is reported that the crystallization particle diameter is 1 μ m during common gloss plating, existing overcritical plating is (people's such as Jitian " Surface and Coatings Technology ", the 285th page of, 173 volumes in 2003) about 100nm.Yet, the additive of the application of the invention, the size of crystallization particle diameter is (with reference to a reference example) about 10nm.Thus, the metal pellicle that obtains among the present invention is very fine and close, can expect wear resistant.These can be low with productivity in the past, need high-octane electroless plating or the resulting metal pellicle of dry method suitable.Thereby, can become a technology, the metallic substance of provide this so far production rate variance very effectively, always making by dry method.
And then, owing to can carry out plating by low state with the surface tension that supercutical fluid was had, thus the plating that also can handle in the past can not form mother metal surface pellicle, that have micro concavo-convex.Specifically be the pattern width of sub-micro level, the structure of high-aspect-ratio, the material ranges of using among semi-conductor, the MEMS is suitable therewith.More specifically for instance, can to pattern width smaller or equal to 1 μ m, long-width ratio more than or equal to 3 concavo-convexly carry out plating with certain thickness.In addition, can the distribution plating to the inside of the through hole-groove structure of semiconductor wafer.
In addition, according to ratio, pressure, the current density of carbonic acid gas and plating liquid, can be with plating pellicle gauge control in number 10nm rank.Thus, as being unusual otherwise effective technique by the technology of sub-micro thickness, metal pellicle that surfaceness is very little, free of pinholes obtains erosion resistance is high.Specifically, these films are fuel cell with electronic material, member for internal combustion engine, compression pump parts such as the jet orifice part of parts, ink-jet printer, magnetic heads.
Need to prove that the surfaceness of plating overlay film can be measured by the scanning electron microscope photo.
Utilize overcritical plating to make this high-quality metallic film, as long as use tensio-active agent of the present invention.
And then therefore nonionic compound of the present invention also is effective to degreasing washing in the operation before the plating and the washing of the pellicle behind the plating owing to have washing effect in supercritical co.Specifically, even, also can contain this nonionic compound and (overcritical, subcritical or liquid) CO not in advance to carrying out the substrate degreasing washing of plating
2Mixture in after the degreasing washing, electroplate, in other words, by containing this nonionic compound, (overcritical, subcritical or liquid) CO all comprising
2With carry out degreasing washing and plating simultaneously in the plating liquid of the aqueous solution of metal-salt, can form high-quality plating pellicle of the present invention.And,, also can remove the degree of surperficial plating liquid that remain in until abundant practicality even the plating pellicle behind the plating does not use a large amount of water to remove plating liquid.That is, can utilize the washing of galvanized pellicle moulding and plating pellicle simultaneously.Under some situation, the plating pellicle behind the plating also can be by containing this nonionic compound and (overcritical, subcritical or liquid) CO
2Mixture in washing carry out aftertreatment.Thus, can make major contribution to the metal waste liquid that washing produced that reduces in alkali, acid waste liquid and the subsequent handling in the preceding operation that in plating technic, became big problem in the past.
Embodiment
By the following examples, reference example specifically describes the present invention, but the present invention is not limited to this.
Embodiment 1
Fig. 1 is the device that uses in the embodiment of the invention.
Internal volume be add 20cc nickel plating bath (watt is bathed: single nickel salt 280g/L, nickelous chloride 60g/L, boric acid 50g/L, gloss-imparting agent are an amount of) in the high pressure vessel 8 of 50cc, plating is bathed and is the F of 0.3wt% (CF (CF relatively
3) CF
2O)
3CF (CF
3) COO (CH
2CH
2O)
2CH
3, install on the negative electrode and the sheet brass of sealing degreasing, on anode, install and sealing pure nickel plate (each surface-area is 4cm
2), in thermostatic bath 4, be warming up to 50 ℃ after, utilize infusion pump 3 and pressure-regulator 10 to enclose CO
2Until 10MPa.By utilizing agitator 5 to make rotor 6 rotations, stir CO with 500r.p.m
2-plating liquid is again with 5A/dm
2Switched on 6 minutes, and carried out nickel plating.Energising is reduced pressure after finishing, and takes out negative plate then, washes fully, utilizes scanning electron microscope (SEM) to carry out surface observation.The scanning electron microscope photo that obtains is shown among Fig. 2.
As having CO
2The nonionic compound of affinity part is used H (CF
2)
6COOCH
2CH
3, utilize method similarly to Example 1 to carry out plating in addition.
The scanning electron microscope photo that obtains is shown among Fig. 3.
As having CO
2The nonionic compound of affinity part is used F (CF
2)
6(CH
2)
10H utilizes method similarly to Example 1 to carry out plating in addition.
The scanning electron microscope photo that obtains is shown among Fig. 4.
As having CO
2The nonionic compound of affinity part is used F (CF
2)
7COOCH
2CH
3, utilize method similarly to Example 1 to carry out plating in addition.
The scanning electron microscope photo that obtains is shown among Fig. 5.
As having CO
2The nonionic compound of affinity part is used F (CF (CF
3) CF
2O)
4CF (CF
3) COOCH
3, utilize method similarly to Example 1 to carry out plating in addition.
The scanning electron microscope photo that obtains is shown among Fig. 6.
As having CO
2The nonionic compound of affinity part is used F (CF
2)
7COO (CH
2)
5CH
3, utilize method similarly to Example 1 to carry out plating in addition.
The scanning electron microscope photo that obtains is shown among Fig. 7.
Embodiment 7
As having CO
2The nonionic compound of affinity part is used F (CF (CF
3) CF
2O)
2CF (CF
3) CH
2OH utilizes method similarly to Example 1 to carry out plating in addition.
The scanning electron microscope photo that obtains is shown among Fig. 8.
As having CO
2The nonionic compound of affinity part is used F (CF (CF
3) CF
2O)
3CF (CF
3) COOCH
2CH
2OCH
3, utilize method similarly to Example 1 to carry out plating in addition.The scanning electron microscope photo that obtains is shown among Fig. 9.
Embodiment 9
As having CO
2The nonionic compound of affinity part is used F (CF (CF
3) CF
2O)
3CF (CF
3) COOC
6H
13, utilize method similarly to Example 1 to carry out plating in addition.The scanning electron microscope photo that obtains is shown among Figure 10.
As having CO
2The nonionic compound of affinity part is used F (CF (CF
3) CF
2O)
3CF (CF
3) CO (OCH
2CH
2)
3OCOCF (CF
3) (OCF
2(CF
3) CF)
3F utilizes method similarly to Example 1 to carry out plating in addition.The scanning electron microscope photo that obtains is shown among Figure 11.
Embodiment 11
As having CO
2The nonionic compound of affinity part is used CH
3OCH
2CH
2OCCF
2(OCF
2CF
2)
6OCF
2COOCH
2CH
2OCH
3, utilize method similarly to Example 1 to carry out plating in addition.The scanning electron microscope photo that obtains is shown among Figure 12.
Embodiment 12
As having CO
2The nonionic compound of affinity part is used C
12H
25OCOCF (CF
3) O (CF
2(CF
3) CFO)
m-(CF
2)
5-(OCF (CF
3) CF
2)
m-OCF (CF
3) COOC
12H
25(m=3～5) utilize method similarly to Example 1 to carry out plating in addition.The scanning electron microscope photo that obtains is shown among Figure 13.
Embodiment 13
Internal volume be add the acid gold plating bath (potassium auric cyanide 10g/L, citric acid 90g/L) of 20cc in the high pressure vessel 8 of 50cc, plating is bathed and is the F of 0.3wt% (CF (CF relatively
3) CF
2O)
3CF (CF
3) COO (CH
2CH
2O)
2CH
3, install and sealing is coated with the sheet brass of nickel, install on anode and sealing is coated with the titanium plate of platinum (each surface-area is 4cm at negative electrode
2), in thermostatic bath 4, be warming up to 40 ℃ after, utilize infusion pump 3 and pressure-regulator 10 to enclose CO
2Until 10MPa.By utilizing agitator 5 to make rotor 6 rotations, stir CO with 500r.p.m
2Plating liquid is again with 2A/dm
2Switched on 2 minutes, and carried out gold-plated.Energising is reduced pressure after finishing, and takes out negative plate then, washes fully.Can obtain good gold-plated pellicle.The scanning electron microscope photo that obtains is shown in (multiplying power: 500 times) among Figure 14.
Embodiment 14
At internal volume is to add in the high pressure vessel 8 of 50cc that 20cc copper sulfate plating is bathed (copper sulfate five water and thing 200g/L, sulfuric acid 50g/L, hydrochloric acid an amount of), the bath of relative plating is the F of 0.3wt% (CF (CF
3) CF
2O)
3CF (CF
3) COO (CH
2CH
2O)
2CH
3, install on the negative electrode and the sealing sheet brass, on anode, install and the sealing copper coin (each surface-area is 4cm
2), in thermostatic bath 4, be warming up to 50 ℃ after, utilize infusion pump 3 and pressure-regulator 10 to enclose CO
2Until 10MPa.By utilizing agitator 5 to make rotor 6 rotations, stir CO with 500r.p.m
2Plating liquid is again with 5A/dm
2Switched on 5 minutes, and carried out copper facing.Energising is reduced pressure after finishing, and takes out negative plate then, washes fully.Can obtain good copper facing pellicle.
Embodiment 15
Internal volume be add the acid gold plating bath (Palladous chloride 0.10mol/L, Potassium Bromide 4.00mol/L, saltpetre 0.10mol/L, boric acid 0.49mol/L, glycine 0.10mol/L, citric acid 90g/L) of 20cc in the high pressure vessel 8 of 50cc, plating is bathed and is the F of 0.3wt% (CF (CF relatively
3) CF
2O)
3CF (CF
3) COO (CH
2CH
2O)
2CH
3, install on the negative electrode and gold-plated and then platinized silver plate was carried out in sealing, on anode, install and sealing platinum plate (each surface-area is 4cm as anode
2), in thermostatic bath 4, be warming up to 40 ℃ after, utilize infusion pump 3 and pressure-regulator 10 to enclose CO
2Until 12MPa.By utilizing agitator 5 to make rotor 6 rotations 1 hour, mix CO fully with 650r.p.m
2Plating liquid.With 1A/dm
2Switched on 15 minutes, and plated palladium.Energising is reduced pressure after finishing, and takes out negative plate then, washes fully.Can obtain good plating palladium pellicle.The scanning electron microscope photo that obtains is shown among Figure 15.
Embodiment 16
With condition similarly to Example 1, untreated sheet brass is installed on the negative electrode, the pure nickel plate is installed on anode, and (each surface-area is 4cm
2), carry out nickel plating.Reduce pressure after energising finishes, take out negative plate then, utilize visual and scanning electron microscope (SEM) carries out surface observation.Obtain the plating pellicle of equal extent roughly with embodiment.Can determine to simplify the preceding operation and the subsequent handling of plating from this result by supercritical co, using compound of the present invention.
Reference example
Carry out the SEM cross-section of the plating pellicle that obtains among the embodiment 8.SEM cross-section photograph with 10000 times and 30000 times as a result of is shown among Figure 16.Crystal grain body is 7nm～12nm, can determine that the surface is very smooth.The deviation of surface thickness is about 10nm.In addition, pellicle thickness is 1 μ m, has hinted the gauge control that can easily carry out about 100nm thus.
Comparative example 1
Substitute and have CO
2The nonionic compound of affinity part and use the CH of 3wt%
3(CH
2)
12(OCH
2CH
2)
8OH carries out plating with method similarly to Example 1 in addition.In subsequent handling, stop up owing to producing the bubble generation pipe arrangement.
The scanning electron microscope photo that obtains is shown among Figure 17.Though observe by SEM, there is not pin hole, have CO with use
2The situation of the nonionic compound of affinity part is compared, and the roughness of surface particle is obvious.
Comparative example 2
Use the plating liquid of forming similarly to Example 1, not apply CO
2Existing method carry out plating.
The scanning electron microscope photo that obtains is shown among Figure 18.Find to produce big pin hole.
Comparative example 3
Substitute and have CO
2The nonionic compound of affinity part and use F (CF (CF
3) CF
2O)
14CF (CF
3) COO
-NH
4 +, carry out plating with method similarly to Example 1 in addition.Electric current is circulation not, does not form the plating pellicle.In addition, in reacted device, form gelatinous solution.
Comparative example 4
Substitute and have CO
2The nonionic compound of affinity part and use following formula:
The compound of expression carries out plating with method similarly to Example 1 in addition.Current flowing can plating, overflows from device but the bubble that the emulsive plating liquid forms takes place during decompression in subsequent handling, also invades in the pipe arrangement simultaneously.
Comparative example 5
Substitute and have CO
2The nonionic compound of affinity part and use F (CF
2(CF
3) CF
2O)
3(CF
3) CFCONHCH
2CH
2N
+(CH
3)
3I
-, carry out plating with method similarly to Example 1 in addition.Electric current does not circulate, and finds that at cathode surface brown material adheres to.
When the surface observation photo of embodiment 1～16 and comparative example 1 (use hydrocarbon-surfactant) is compared, the plating face that can clearly determine embodiment 1～16 has formed the good plating pellicle that do not have pin hole and surfaceness little (observed by SEM, surfaceness is obviously little when using hydrocarbon compound).And then, even hydrocarbon-surfactant can be carried out plating, spend problems (comparative example 1) such as time when also having aftertreatment.
In addition, be tensio-active agent even adopt fluorine, utilize aniorfic surfactant can not carry out plating, spend problems such as time when perhaps having aftertreatment; Cationic compound can not carry out plating.Can determine that like this for present technique, owing to be derived from the different in kind of the additive structure of use, formed plating pellicle can produce big difference.Can determine from above, the application of the invention have a CO
2The nonionic compound of affinity part can form liquid, subcritical or supercritical CO
2The high-quality plating pellicle that the advantage of plating is brought.
Claims (19)
1. electro-plating method, it is at the aqueous solution that contains metal-salt and CO
2Coexistence under carry out electric plating method, it is characterized in that CO
2Exist with liquid, subcritical or supercritical state, to the described aqueous solution and CO
2The coexistence system in further add and have CO
2The nonionic compound of affinity part is at this so-called CO
2Affinity is partly represented to be selected from by (1) and is selected from least a homopolymer, 2 membered copolymers or 3 membered copolymers in the group of being made up of poly(propylene oxide), polybutylene oxide and polyethylene oxide, (2) part or all of hydrogen atom is contained fluoroalkyl by what fluorine replaced, (3) at least a in the group that the fluorochemical polyether base that replaced by fluorine of part or all of hydrogen atom, and (4) dialkyl group siloxy-is formed.
2. method according to claim 1, wherein, described nonionic compound is ether system or ester based compound.
3. method according to claim 1, wherein, described nonionic compound is pure based compound.
4. method according to claim 1, wherein, described nonionic compound is a hydrofluoric ether.
5. method according to claim 1, wherein, described nonionic compound is poly-alkylsiloxane.
6. method according to claim 1, wherein, described nonionic compound is a fluoropolymer.
7. plating is bathed, and it is to comprise the aqueous solution, the CO that contains metal-salt
2And have CO
2The plating of the nonionic compound of affinity part is bathed CO
2Exist with liquid, subcritical or supercritical state, at this so-called CO
2Affinity is partly represented to be selected from by (1) and is selected from least a homopolymer, 2 membered copolymers or 3 membered copolymers in the group of being made up of poly(propylene oxide), polybutylene oxide and polyethylene oxide, (2) part or all of hydrogen atom is contained fluoroalkyl by what fluorine replaced, (3) at least a in the group that the fluorochemical polyether base that replaced by fluorine of part or all of hydrogen atom, and (4) dialkyl group siloxy-is formed.
8. electroplate and use additive, it comprises and has CO
2The nonionic compound of affinity part is the CO in liquid, subcritical or supercritical state
2Exist down and electroplate the additive of usefulness, at this so-called CO
2Affinity is partly represented to be selected from by (1) and is selected from least a homopolymer, 2 membered copolymers or 3 membered copolymers in the group of being made up of poly(propylene oxide), polybutylene oxide and polyethylene oxide, (2) part or all of hydrogen atom is contained fluoroalkyl by what fluorine replaced, (3) at least a in the group that the fluorochemical polyether base that replaced by fluorine of part or all of hydrogen atom, and (4) dialkyl group siloxy-is formed.
9. the pre-treating process of plating, its use before the plating operation has CO
2The nonionic compound of affinity part is carried out the degreasing washing of clad substate, at this so-called CO
2Affinity is partly represented to be selected from by (1) and is selected from least a homopolymer, 2 membered copolymers or 3 membered copolymers in the group of being made up of poly(propylene oxide), polybutylene oxide and polyethylene oxide, (2) part or all of hydrogen atom is contained fluoroalkyl by what fluorine replaced, (3) at least a in the group that the fluorochemical polyether base that replaced by fluorine of part or all of hydrogen atom, and (4) dialkyl group siloxy-is formed.
10. the post-treating method of plating, it is to use in plating operation back to have CO
2The nonionic compound of affinity part is carried out the washing of plating pellicle, at this so-called CO
2Affinity is partly represented to be selected from by (1) and is selected from least a homopolymer, 2 membered copolymers or 3 membered copolymers in the group of being made up of poly(propylene oxide), polybutylene oxide and polyethylene oxide, (2) part or all of hydrogen atom is contained fluoroalkyl by what fluorine replaced, (3) at least a in the group that the fluorochemical polyether base that replaced by fluorine of part or all of hydrogen atom, and (4) dialkyl group siloxy-is formed.
11. the plating pellicle has following feature:
(1) diameter is every 1cm more than or equal to the pin hole of 1 μ m
2Smaller or equal to 1,
(2) thickness of pellicle is smaller or equal to 1 μ m, and
(3) surfaceness of pellicle is smaller or equal to 10nm.
12. method according to claim 1 wherein, is used nonionic compound, (the CO of described nonionic compound
2The affinity part)-X-or X-(CO
2The affinity part)-X-is shown below 1) or 2):
1)F-(CF
2)
q-(OCF
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
p-X-
2)-X-(CH
2)
p-(CF
2O)
o-(C
2F
4O)
n-(C
3F
6O
)m-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
p-X-
At this, m, n, o, p, q are the integer more than or equal to 0, and m and n are 0～15 integer, and are not 0 simultaneously, n+m≤20, o=0～20, p=0～2, q=1～10; Regardless of the order of each repeating unit ,-(OC
3F
6)
m-expression-(OCF
2CF
2CF
2)
m-or-(OCF (CF
3) CF
2)
m-,-(OC
2F
4)
n-expression-(OCF
2CF
2)
n-or-(OCF (CF
3))
n-;
Here, X is identical or different, expression singly-bound, O, S, NH, NR (R
a: alkyl), C=O, C (O) O, OC (O), C (O) S, SC (O), C (O) NH, C (O) NR
a(R
a: alkyl), NH (O) C, NR (O) C, CH
2, CHR
a, CR
a 2(R
a: alkyl), SO
2NH or NHSO
2
13. method according to claim 1 wherein, uses shown below 1)～3) nonionic compound,
1)F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
pX-Rh
2)F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
pX-Rh-X-(CH
2)
p-(CF
2O)
o-(C
2F
4O)
n-(C
3F
6O)
m-(CF
2)
q-F
3)Rh-X(CH
2)
p-(CF
2O)
o-(C
2F
4O)
n-(C
3F
6O)
m-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
pX-Rh
At this, m, n, o, p, q are the integer more than or equal to 0, and m and n are 0～15 integer, and are not 0 simultaneously, n+m≤20, o=0～20, p=0～2, q=1～10; No matter the order of each repeating unit is as ,-(OC
3F
6)
m-expression-(OCF
2CF
2CF
2)
m-or-(OCF (CF
3) CF
2)
m-,-(OC
2F
4)
n-expression-(OCF
2CF
2)
n-or-(OCF (CF
3))
n-;
Here, X is identical or different, expression singly-bound, O, S, NH, NR (R
a: alkyl), C=O, C (O) O, OC (O), C (O) S, SC (O), C (O) NH, C (O) NR
a(R
a: alkyl), NH (O) C, NR (O) C, CH
2, CHR
a, CR
a 2(R
a: alkyl), SO
2NH or NHSO
2
Rh is a hydrophilic parts, its alkyl for containing heteroatoms or do not have heteroatomic straight chain or side chain in molecule.
14. method according to claim 13, wherein, Rh is a polyoxyalkylenes.
15. method according to claim 13 wherein, is used CO
2The carbonatoms of affinity part is identical with the carbonatoms of Rh base or than its nonionic compound of Duoing.
16. method according to claim 1 wherein, is used nonionic compound, (the CO of described nonionic compound
2The affinity part)-X-or X-(CO
2The affinity part)-X-is shown below 1) or 2):
1)Y-(CF
2)
m1-(CH
2)
n1-X
2)X-(CH
2)
n1-(CF
2)
m1-(CH
2)
n1-X
At this, Y is F or H, and X is identical or different, and expression is selected from by COO, O, S, CONH, NHCO, SO
2NH, NHSO
2Combination base in the group of forming;
M1 is 3～20 integer, and n1 is identical or different, is 0～2 integer.
17. method according to claim 16, wherein, nonionic compound has shown below 1)～3) any one structure,
1)Y-(CF
2)
m1-(CH
2)
n1-X-Rh
2)Y-(CF
2)
m1-(CH
2)
n1-X-Rh-X-(CH
2)
n1-(CF
2)
m1-Y
3)Rh-X-(CH
2)
n1-(CF
2)
m1-(CH
2)
n1-X-Rh
At this, Y is F or H, and X is identical or different, and expression is selected from by COO, O, S, CONH, NHCO, SO
2NH, NHSO
2Combination base in the group of forming;
M1 is identical or different, is 3～20 integer, and n1 is identical or different, is 0～2 integer;
Rh is a hydrophilic parts, its alkyl for containing heteroatoms or do not have heteroatomic straight chain or side chain in molecule.
18. method according to claim 17, wherein, Rh is a polyoxyalkylenes.
19. method according to claim 17, wherein, CO
2The carbonatoms of affinity part is identical or more than it with the carbonatoms of Rh base.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP035281/2004 | 2004-02-12 | ||
| JP2004035281 | 2004-02-12 | ||
| JP349651/2004 | 2004-12-02 |
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| Publication Number | Publication Date |
|---|---|
| CN1918326A true CN1918326A (en) | 2007-02-21 |
Family
ID=37738683
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| CN103173795A (en) * | 2012-03-27 | 2013-06-26 | 上海域高环境技术有限公司 | Electroplating method |
| CN103319996A (en) * | 2013-05-27 | 2013-09-25 | 赛吉材料科技（上海）有限公司 | Surface treatment composition, preparation method and articles with treated surface |
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| CN103173795A (en) * | 2012-03-27 | 2013-06-26 | 上海域高环境技术有限公司 | Electroplating method |
| CN103173795B (en) * | 2012-03-27 | 2016-08-03 | 上海域高环境技术有限公司 | A kind of electric plating method |
| CN103319996A (en) * | 2013-05-27 | 2013-09-25 | 赛吉材料科技（上海）有限公司 | Surface treatment composition, preparation method and articles with treated surface |
| CN103319996B (en) * | 2013-05-27 | 2015-10-28 | 赛吉材料科技（上海）有限公司 | The article that surface treating composition and preparation method thereof is treated with surface |
| CN105986289A (en) * | 2015-03-18 | 2016-10-05 | 株式会社东芝 | Electroplating method and electroplating device |
| US10233557B2 (en) | 2015-03-18 | 2019-03-19 | Kabushiki Kaisha Toshiba | Electroplating method and electroplating device |
| CN105986289B (en) * | 2015-03-18 | 2020-08-11 | 株式会社东芝 | Electroplating method and electroplating device |
| CN106801235A (en) * | 2015-05-12 | 2017-06-06 | 江苏理工学院 | Supercritical composite electroforming system recycling device capable of reducing processing cost |
| CN106801235B (en) * | 2015-05-12 | 2018-06-08 | 江苏理工学院 | Supercritical composite electroforming system recycling device capable of reducing processing cost |
| CN106191943A (en) * | 2016-07-19 | 2016-12-07 | 佛山市零碳节能光电科技有限公司 | The supercritical electroplating preparation method of a kind of cobalt-nickel alloy light protective coating and preparation system thereof |
| CN106906501A (en) * | 2017-03-30 | 2017-06-30 | 江苏理工学院 | A kind of overcritical electric deposition device of ultrasonic wave added |
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