CN1832073B - Solid electrolytic capacitor, its manufacturing method and couplant used by it - Google Patents
Solid electrolytic capacitor, its manufacturing method and couplant used by it Download PDFInfo
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- CN1832073B CN1832073B CN2005100513643A CN200510051364A CN1832073B CN 1832073 B CN1832073 B CN 1832073B CN 2005100513643 A CN2005100513643 A CN 2005100513643A CN 200510051364 A CN200510051364 A CN 200510051364A CN 1832073 B CN1832073 B CN 1832073B
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Abstract
This invention relates to a solid electrolyte condenser, its preparation method and its couplant, in which, said solid electrolyte condenser includes: a valve metal layer, an oxide dielectric layer on it to cover part of the surface of the layer, a coupled layer, the first end of its molecular chain is bonded to the dielectric layer with convalent bond, the second end includes a functional base of conductive high molecular monomers and a conductive high molecular layer on said coupled layer having a convalent bond bonding to said conductive high molecule monomers, which uses the invented couplant as a coupled layer and generates convalent bond bonding with the conductive high molecular layer to increase the bonding between the high molecular layer and the dielectric layer to avoid generating gaps.
Description
Technical field
The present invention relates to a kind of passive device and manufacture method thereof, particularly a kind of solid electrolytic capacitor, its manufacture method and employed coupling agent thereof.
Background technology
For a long time, a major subjects of electrolytic capacitor development is and improves electrolytical electrical conductivity, to reduce the equivalent series resistance of capacitor, reaches the characteristic of low impedance at high frequency and tool high-reliability.Because electroconductive polymer liquid electrolyte or the solid-state organic semiconductor complex salt used than the traditional electrical electrolysis condenser is as tcnq complex salt and inorganic semiconductor MnO
2, higher electrical conductivity is arranged, and have the high-temperature insulation characteristic of appropriateness, so electroconductive polymer becomes the exploitation trend of the employed solid electrolyte of electrolytic capacitor now.
Please refer to Fig. 1, is a profile, shows the local structure for amplifying of a solid electrolytic capacitor internal microstructure.Wherein, valve metal 100 is a fine porous material (meso-porous material) as positive electrode; Dielectric layer 110 is formed on the valve metal 100; Electroconductive polymer layer 120 is formed on the dielectric layer 110 as negative electrode.Wherein, electroconductive polymer layer 120 only is attached on the dielectric layer 110 with Van der Waals force, its bond power is faint, be easy to generate space 121 between dielectric layer 110 and the electroconductive polymer layer 120 and make, and to solid electrolytic capacitor 1 electrically cause harmful effect, for example capacity reduces, equivalent series resistance (equivalent series resistance; ESR) rising, the dissipation factor (dissipation factor; Df) rise or the like; Also can cause harmful effect to the reliability of solid electrolytic capacitor 1.
For addressing the above problem, people such as Sato are in No. 9246106, Japanese patent laid-open, be disclosed in and carry out the silane coupling agent pre-treatment on the formed aluminum foil, then form electroconductive polymer layer again, its used coupling agent is γ-glycide base propyl trimethoxy silicane (gamma-glycidoxypropyltrimethoxysilane) or octadecane-triethoxysilane (octadecyl-triethoxysilane).Yet the coupling agent that it provided contains the functional group of the electrical conductivity that is an impediment to electroconductive polymer, and can cause the equivalent series resistance of capacitor and the dissipation factor to rise.
People such as Sakata are in No. 5729428, United States Patent (USP), be disclosed in the pre-treatment of carrying out organic compound on the anodic oxide coating and then form electroconductive polymer layer, to improve the electric leakage problem that high temperature uses, its used organic compound comprises organic acid, phenol, silicon coupling agent, titanium coupling agent and aluminium coupling agent or the like; People such as Hahn are open in No. 6072694, United States Patent (USP), add silane coupling agent in the electroconductive polymer formula solution, to improve electric leakage and dielectric absorption.Yet, the above-mentioned two preceding employed coupling agents of case, the function that can't provide while and electroconductive polymer layer and dielectric layer to form bond, limited for the effect that helps electroconductive polymer layer and dielectric layer combination.
Summary of the invention
In view of this, main purpose of the present invention provides a kind of solid electrolytic capacitor and manufacture method thereof, in the above-mentioned solid electrolytic capacitor, between electroconductive polymer layer and dielectric layer, has a coupled layer, simultaneously with electroconductive polymer layer and dielectric layer generation covalency bond, to promote the associativity between electroconductive polymer layer and the dielectric layer, avoid the generation in space, show with the reliability that electrically reaches that promotes solid electrolytic capacitor.
Another object of the present invention provides a kind of coupling agent, be applicable to mode and monoxide and macromolecular material generation covalency bond with self assembly (Self-Assembly), to promote the associativity of above-mentioned oxide and macromolecular material, when being applied in solid electrolytic capacitor, can promote the associativity between its electroconductive polymer layer and the dielectric layer, avoid the generation in space, show with the reliability that electrically reaches that promotes solid electrolytic capacitor.
For reaching above-mentioned purpose of the present invention, the invention provides a kind of solid electrolytic capacitor, comprise: a valve metal layer; The monoxide dielectric layer on above-mentioned valve metal layer, the surface of the above-mentioned valve metal layer in cover part; One coupled layer, first end of its strand is binding on above-mentioned oxide dielectric layer with covalent bond, and second end has the functional group of an electroconductive polymer monomer; And an electroconductive polymer layer, on above-mentioned coupled layer, have covalent bond and be binding on above-mentioned electroconductive polymer monomer.
Solid electrolytic capacitor of the present invention, wherein this valve metal layer is aluminium, tantalum, titanium, niobium, niobium oxide or above-mentioned combination.
Solid electrolytic capacitor of the present invention, wherein this oxide dielectric layer is the oxide of this valve metal layer.
Solid electrolytic capacitor of the present invention, wherein the bond between this coupled layer and this oxide dielectric layer is silicon oxygen bond, phosphorus oxygen key, carbon-oxygen bond, sulphur oxygen key or boron oxygen key.
Solid electrolytic capacitor of the present invention, wherein the functional group of this electroconductive polymer monomer is anilino-, thienyl, pyrrole radicals or above-mentioned derivative.
Solid electrolytic capacitor of the present invention, wherein the functional group of this electroconductive polymer monomer is an anilino-.
Solid electrolytic capacitor of the present invention wherein also comprises C between first end of the strand of this coupled layer and second end
1To C
12Alkyl.
Solid electrolytic capacitor of the present invention, wherein this electroconductive polymer layer is polyaniline, polythiophene, polypyrrole or above-mentioned derivative.
Solid electrolytic capacitor of the present invention, wherein this electroconductive polymer layer is a polyaniline.
The present invention provides a kind of manufacture method of solid electrolytic capacitor again, comprises: a valve metal layer is provided; Form the monoxide dielectric layer on above-mentioned valve metal layer, the surface of the above-mentioned valve metal layer in cover part; Mode with self assembly forms a coupled layer on above-mentioned oxide dielectric layer, and first end of the strand of above-mentioned coupled layer is binding on above-mentioned oxide dielectric layer with covalent bond, and second end has the functional group of an electroconductive polymer monomer; And form an electroconductive polymer layer on above-mentioned coupled layer, have covalent bond and be binding on above-mentioned electroconductive polymer monomer.
The manufacture method of solid electrolytic capacitor of the present invention, wherein this valve metal layer is aluminium, tantalum, titanium, niobium, niobium oxide or above-mentioned combination.
The manufacture method of solid electrolytic capacitor of the present invention, wherein this oxide dielectric layer is the oxide of this valve metal layer.
The manufacture method of solid electrolytic capacitor of the present invention wherein forms this coupled layer and more comprises this oxide dielectric layer is immersed in the solution of a coupling agent, wherein the molecular formula of this following formula of coupling agent layer tool (1):
R
1-R
3 (1)
R wherein
1Select from silylation, phosphate, carboxyl, sulfonic group, boronate or above-mentioned derivative, R
3Select from anilino-, thienyl, pyrrole radicals or above-mentioned derivative.
The manufacture method of solid electrolytic capacitor of the present invention wherein forms this coupled layer and more comprises this oxide dielectric layer is immersed in the solution of a coupling agent, wherein the molecular formula of this following formula of coupling agent layer tool (2):
R
1-R
2-R
3 (2)
R wherein
1Select from silylation, phosphate, carboxyl, sulfonic group, boronate or above-mentioned derivative, R
3Be C
1To C
12Alkyl, R
3Select from anilino-, thienyl, pyrrole radicals or above-mentioned derivative.
The manufacture method of solid electrolytic capacitor of the present invention, wherein the bond between this coupled layer and this oxide dielectric layer is silicon oxygen bond, phosphorus oxygen key, carbon-oxygen bond, sulphur oxygen key or boron oxygen key.
The manufacture method of solid electrolytic capacitor of the present invention, wherein the functional group of this electroconductive polymer monomer is anilino-, thienyl, pyrrole radicals or above-mentioned derivative.
The manufacture method of solid electrolytic capacitor of the present invention, wherein the functional group of this electroconductive polymer monomer is an anilino-.
The manufacture method of solid electrolytic capacitor of the present invention wherein also comprises C between first end of the strand of this coupled layer and second end
1To C
12Alkyl.
The manufacture method of solid electrolytic capacitor of the present invention, wherein this electroconductive polymer layer is polyaniline, polythiophene, polypyrrole or above-mentioned derivative.
The manufacture method of solid electrolytic capacitor of the present invention, wherein this electroconductive polymer layer is a polyaniline.
The present invention provides a kind of coupling agent again, is applicable to mode and monoxide and macromolecular material generation covalency bond with self assembly, the molecular formula of the following formula of tool (1):
R
1-R
3 (1)
R wherein
1Select from silylation (silyl), phosphate (phosphono), carboxyl (carboxy), sulfonic group (sulfo), boronate (boric acid group) or above-mentioned derivative, R
3Be one of polymerization single polymerization monomer of above-mentioned macromolecular material.
Coupling agent of the present invention, wherein R
3Select from anilino-, thienyl, pyrrole radicals or above-mentioned derivative.
The present invention provides a kind of coupling agent again, is applicable to mode and monoxide and macromolecular material generation covalency bond with self assembly, the molecular formula of the following formula of tool (2):
R
1-R
2-R
3 (2)
R wherein
1Select from silylation (silyl), phosphate (phosphono), carboxyl (carboxy), sulfonic group (sulfo), boronate (boric acid group) or above-mentioned derivative, R
2Be C
1To C
12Alkyl, R
3Be one of polymerization single polymerization monomer of above-mentioned macromolecular material.
Coupling agent of the present invention, wherein R
3Select from anilino-, thienyl, pyrrole radicals or above-mentioned derivative.
Solid electrolytic capacitor of the present invention, use coupling agent of the present invention as coupled layer, simultaneously with electroconductive polymer layer and dielectric layer generation covalency bond, to promote the associativity between electroconductive polymer layer and the dielectric layer, avoid the generation in space, promote the electrical performance of solid electrolytic capacitor, can promote its reliability performance simultaneously.
Description of drawings
Fig. 1 is a profile, shows the local structure for amplifying of solid electrolytic capacitor 1.
Fig. 2 A to 2D is a series of profile, shows the manufacturing process of solid electrolytic capacitor 2 of the present invention.
Fig. 3 A to 3C is a series of schematic diagram, shows coupling agent of the present invention in solid electrolytic capacitor 2, with the reaction mechanism of oxide dielectric layer 210 and electroconductive polymer layer 230 generation covalency bond.
Embodiment
Please refer to Fig. 2 A to 2D, be a series of profile, show the flow process of the manufacture method of solid electrolytic capacitor 2 of the present invention.
In Fig. 2 A, at first, provide a valve metal layer 200, be generally fine porous material (meso-porous material), its material for example is aluminium, tantalum, titanium, niobium, niobium oxide or above-mentioned combination.Then, directly form monoxide dielectric layer 210 in valve metal layer 200, the surface of cover part valve metal layer 200, so that its part of exposing can be electrically connected to other electrical components, and with the positive electrode of valve metal layer 200 as capacitor.The material of oxide dielectric layer 210 is preferably the oxide of valve metal layer 200.
Next, provide the solution of coupling agent of the present invention, wherein, coupling agent of the present invention is applicable to the mode of self assembly and monoxide oxide dielectric layer 210 for example of the present invention and macromolecular material generation covalency bond, the molecular formula of the following formula of tool (2):
R
1-R
2-R
3 (2)
R wherein
1Be preferably silylation (silyl), phosphate (phosphono), carboxyl (carboxy), sulfonic group (sulfo), boronate (boric acid group) or above-mentioned derivative, because silicon, phosphorus, carbon, sulphur, boron atom can form stronger covalent bond with the oxygen atom of above-mentioned oxide surface, and more effectively promote the associativity between above-mentioned oxide and the macromolecular material; R
2Be preferably C
0To C
12Alkyl; R
3Be preferably one of polymerization single polymerization monomer of above-mentioned macromolecular material.Aforementioned C
0Situation promptly represent R
2There is not R
1With R
3Direct bond.And in the present invention, the polymer that is used as the electroconductive polymer layer for example is polyaniline (polyaniline), polythiophene (polythiophene), polypyrrole (polypyrrole) or above-mentioned derivative, therefore better R
3Be anilino-(anilino), thienyl (thiopheno), pyrrole radicals (pyrrole) or above-mentioned derivative.
Please refer to Fig. 2 B, form coupled layer 220 on oxide dielectric layer 210 in the mode of self assembly, the formation of coupled layer 220 is the R by the strand of the coupling agent of the invention described above
1End is binding on oxide dielectric layer 210 with covalent bond, and its reaction mechanism can Fig. 3 A, 3B be that example explains.In Fig. 3 A to 3C in order to illustrative coupling agent, R
1Derivative trimethoxy silane base (Si (MeO) for silylation
3), R
2Be propyl group, R
3Be anilino-, name is called 3-anilino-propyl trimethoxy silicane (3-(phenylamino) propyltrimethoxysilane), the various combinations that listed with formula (2) can both be reached reaction mechanism as shown in Fig. 3 A to 3C as coupling agent of the present invention, only being to enumerate one of them example with convenient explanation among Fig. 3 A to 3C, can not be restriction of the present invention according to this.
Please refer to Fig. 3 A, oxide dielectric layer 210 surfaces have hydroxy (hydroxylgroup), oxide dielectric layer 210 is immersed in the methanol solution of 3-anilino-propyl trimethoxy silicanes, above-mentioned hydroxy can with trimethoxy silane generation self-assembling reaction.
Please refer to Fig. 3 B, the oxygen atom generation self-assembling reaction on 3-anilino-propyl trimethoxy silicane and oxide dielectric layer 210 surfaces, in the 3-anilino-propyl trimethoxy silicane, the oxygen atom on silicon atom and oxide dielectric layer 210 surfaces forms silicon oxygen bond, trimethoxy silane base (R
1) methoxyl group then form methyl alcohol and slough with the hydrogen atom on oxide dielectric layer 210 surfaces, the oxygen atom that makes silicon atom and dielectric layer 210 surfaces in the coupling agent of the present invention with the covalent bond bond together, the coupled layer 220 among formation Fig. 2 B.
Next, please refer to Fig. 2 C, form electroconductive polymer layer 230 on coupled layer 220, have covalent bond and be binding on R in coupled layer 220 molecules
3End.Electroconductive polymer layer 230 is preferably to have and R
3Hold identical monomer, its material for example is polyaniline (polyaniline), polythiophene (polythiophene), polypyrrole (polypyrrole) or above-mentioned derivative.
Please refer to Fig. 3 C, hookup 3B, among the displayed map 2C, when forming electroconductive polymer layer 230, an example of the reaction mechanism of the polymerization reaction of going.Since among Fig. 3 A, the 3B with the example of 3-anilino-propyl trimethoxy silicane as coupling agent of the present invention, therefore, among Fig. 3 C, coupled layer 220 immersions are contained in the polymer fluid (not illustrating) of anilino-monomer, thereby formation polyaniline, the covalency bond also is connected in polyaniline in the 3-anilino-propyl trimethoxy silicane, and forms electroconductive polymer layer 230 of the present invention.So, constituted solid electrolytic capacitor 2 of the present invention shown in Fig. 2 C.
At last, please refer to Fig. 2 D, visual processing procedure needs, and forms carbon paste 240 and elargol 250 conducting resinls such as grade on electroconductive polymer layer 230 in regular turn, with protection electroconductive polymer layer 230, and as the leadout electrode of negative pole.
Next, enumerate four embodiment and a comparative example, further specifically describe effect of the present invention.
(formation voltage 36V, area 0.6cm * 2.0cm) are soaked in the methanol solution of 3-anilino-propyl trimethoxy silicane of concentration 0.1-50wt%, then are heated to 105 ℃ with its oven dry will to have the anodal aluminium foil of aluminum oxide dielectric layer.Then be soaked in aniline polymerization liquid (aqueous solution that contains the ammonium persulfate (ammonium persulfate) of the aniline of 0.5M, the pyrovinic acid of 0.5M (methanesulfonicacid), 0.5M) about 30 minutes, and cleaned with clear water again and dried about 10 minutes in 105 ℃.Repeat that above-mentioned aniline polymerization liquid soaks and steps 10 such as cleaning, drying time after, on the polyaniline layer, coat carbon paste and in 105 ℃ the oven dry about 1 hour, coat again afterwards elargol and in 105 ℃ the oven dry about 1 hour, promptly finish the making of solid electrolytic capacitor 2 of the present invention shown in Fig. 2 D, and measure its electrical performance as shown in Table 1.
(formation voltage 36V, area 0.6cm * 2.0cm) are soaked in the methanol solution of 4-(4-aminophenyl) butyric acid (4-(4-aminophneyl) butyric acid) of concentration 0.1-50wt%, then are heated to 105 ℃ with its oven dry will to have the anodal aluminium foil of aluminum oxide dielectric layer.Then be soaked in aniline polymerization liquid (aqueous solution of ammonium persulfate that contains pyrovinic acid, the 0.5M of aniline, the 0.5M of 0.5M) about 30 minutes, and cleaned with clear water again and in about 10 minutes of 105 ℃ of oven dry.Repeat that above-mentioned aniline polymerization liquid soaks and steps 10 such as cleaning, drying time after, on the polyaniline layer, coat carbon paste and in 105 ℃ the oven dry about 1 hour, coat again afterwards elargol and in 105 ℃ the oven dry about 1 hour, promptly finish the making of solid electrolytic capacitor 2 of the present invention shown in Fig. 2 D, and measure its electrical performance as shown in Table 1.
Embodiment 3
(formation voltage 36V, area 0.6cm * 2.0cm) are soaked in the methanol solution of aniline-2-sulfonic acid (aniline-2-sulfonic acid) of concentration 0.1-50wt%, then are heated to 105 ℃ with its oven dry will to have the anodal aluminium foil of aluminum oxide dielectric layer.Then be soaked in aniline polymerization liquid (aqueous solution of ammonium persulfate that contains pyrovinic acid, the 0.5M of aniline, the 0.5M of 0.5M) about 30 minutes, and cleaned with clear water again and in about 10 minutes of 105 ℃ of oven dry.Repeat that above-mentioned aniline polymerization liquid soaks and steps 10 such as cleaning, drying time after, on the polyaniline layer, coat carbon paste and in 105 ℃ the oven dry about 1 hour, coat again afterwards elargol and in 105 ℃ the oven dry about 1 hour, promptly finish the making of solid electrolytic capacitor 2 of the present invention shown in Fig. 2 D, and measure its electrical performance as shown in Table 1.
Embodiment 4
(formation voltage 36V, area 0.6cm * 2.0cm) are soaked in the methanol solution of 3-aminophenyl boric acid (3-aminophenylboronic acid) of concentration 0.1-50wt%, then are heated to 105 ℃ with its oven dry will to have the anodal aluminium foil of aluminum oxide dielectric layer.Then be soaked in aniline polymerization liquid (aqueous solution of ammonium persulfate that contains pyrovinic acid, the 0.5M of aniline, the 0.5M of 0.5M) about 30 minutes, and cleaned with clear water again and in about 10 minutes of 105 ℃ of oven dry.Repeat that above-mentioned aniline polymerization liquid soaks and steps 10 such as cleaning, drying time after, on the polyaniline layer, coat carbon paste and in 105 ℃ the oven dry about 1 hour, coat again afterwards elargol and in 105 ℃ the oven dry about 1 hour, promptly finish the making of solid electrolytic capacitor 2 of the present invention shown in Fig. 2 D, and measure its electrical performance as shown in Table 1.
Comparative example 1
(formation voltage 36V, area 0.6cm * 2.0cm) were soaked in aniline polymerization liquid (aqueous solution of ammonium persulfate that contains pyrovinic acid, the 0.5M of aniline, the 0.5M of 0.5M) about 30 minutes, cleaned with clear water and in about 10 minutes of 105 ℃ of oven dry again will to have the anodal aluminium foil of aluminum oxide dielectric layer.Repeat that above-mentioned aniline polymerization liquid soaks and steps 10 such as cleaning, drying time after, on the polyaniline layer, coat carbon paste and in 105 ℃ the oven dry about 1 hour, coat again afterwards elargol and in 105 ℃ the oven dry about 1 hour, promptly finish the making of the solid electrolytic capacitor of comparative example 1, and measure its electrical performance as shown in Table 1.Wherein, the electroconductive polymer layer of the solid electrolytic capacitor of comparative example 1 (polyaniline layer) only with Fan Dewali, is attached on the aluminum oxide dielectric layer.
Table one
The effect embodiment 1-4 as shown in table 1 of invention and the result of the test of comparative example 1, the capacitance of solid electrolytic capacitor 2 of the present invention is higher than the conventional conductive macromolecule layer and only is attached to capacitor on the aluminum oxide dielectric layer with Fan Dewali, and its equivalent series resistance and the dissipation factor also are lower than traditional capacitor.Therefore, solid electrolytic capacitor 2 of the present invention, use coupling agent of the present invention as coupled layer, simultaneously with electroconductive polymer layer and dielectric layer generation covalency bond, to promote the associativity between electroconductive polymer layer and the dielectric layer, avoid the generation in space, promoted the electrical performance of solid electrolytic capacitor, can promote simultaneously its reliability performance, reach the purpose of the invention described above.
Though the present invention with preferred embodiment openly as above; right its is not in order to limiting the present invention, anyly is familiar with this skill person, without departing from the spirit and scope of the present invention; when can being used for a variety of modifications and variations, so protection scope of the present invention is as the criterion when looking the scope that claims define.
Being simply described as follows of symbol in the accompanying drawing:
1: capacitor 2: solid electrolytic capacitor
100: valve metal 110: dielectric layer
120: electroconductive polymer layer 121: space
200: valve metal 210: oxide dielectric layer
220: coupled layer 230: the electroconductive polymer layer
240: carbon paste 250: elargol
Claims (22)
1. solid electrolytic capacitor is characterized in that comprising:
One valve metal layer;
The monoxide dielectric layer on this valve metal layer, the surface of this valve metal layer of cover part;
One coupled layer, it has (R
1-R
2-R
3) molecular formula, R wherein
1For first end of the strand of this coupled layer is binding on this oxide dielectric layer, R with covalent bond
3For second end of the strand of this coupled layer has the functional group of an electroconductive polymer monomer, wherein R
1Select from silylation, phosphate, carboxyl, sulfonic group, boronate or their derivative, R
2Be C
0～C
12Alkyl, R
3Select from anilino-, thienyl, pyrrole radicals or their derivatives; And
One electroconductive polymer layer on this coupled layer, has covalent bond and is binding on this electroconductive polymer monomer.
2. solid electrolytic capacitor according to claim 1 is characterized in that this valve metal layer is aluminium, tantalum, titanium, niobium, niobium oxide or above-mentioned combination.
3. solid electrolytic capacitor according to claim 1 is characterized in that the oxide of this oxide dielectric layer for this valve metal layer.
4. solid electrolytic capacitor according to claim 1 is characterized in that the bond between this coupled layer and this oxide dielectric layer is silicon oxygen bond, phosphorus oxygen key, carbon-oxygen bond, sulphur oxygen key or boron oxygen key.
5. solid electrolytic capacitor according to claim 1 is characterized in that the functional group of this electroconductive polymer monomer is anilino-, thienyl, pyrrole radicals or above-mentioned derivative.
6. solid electrolytic capacitor according to claim 1 is characterized in that the functional group of this electroconductive polymer monomer is anilino-.
7. solid electrolytic capacitor according to claim 1 is characterized in that this electroconductive polymer layer is polyaniline, polythiophene, polypyrrole or above-mentioned derivative.
8. solid electrolytic capacitor according to claim 1 is characterized in that this electroconductive polymer layer is a polyaniline.
9. the manufacture method of a solid electrolytic capacitor is characterized in that comprising:
One valve metal layer is provided;
Form the monoxide dielectric layer on this valve metal layer, the surface of this valve metal layer of cover part;
Mode with self assembly forms a coupled layer on this oxide dielectric layer, and this coupled layer has (R
1-R
2-R
3) molecular formula, R wherein
1For first end of the strand of this coupled layer is binding on this oxide dielectric layer, R with covalent bond
3For second end of the strand of this coupled layer has the functional group of an electroconductive polymer monomer, wherein R
1Select from silylation, phosphate, carboxyl, sulfonic group, boronate or their derivative, R
2Be C
0～C
12Alkyl, R
3Select from anilino-, thienyl, pyrrole radicals or their derivatives; And
Form an electroconductive polymer layer on this coupled layer, have covalent bond and be binding on this electroconductive polymer monomer.
10. the manufacture method of solid electrolytic capacitor according to claim 9 is characterized in that this valve metal layer is aluminium, tantalum, titanium, niobium, niobium oxide or above-mentioned combination.
11. the manufacture method of solid electrolytic capacitor according to claim 9 is characterized in that the oxide of this oxide dielectric layer for this valve metal layer.
12. the manufacture method of solid electrolytic capacitor according to claim 9 is characterized in that forming this coupled layer and more comprises this oxide dielectric layer is immersed in the solution of a coupling agent, wherein the molecular formula of this following formula of coupling agent layer tool (1):
R
1-R
3 (1)
R wherein
1Select from silylation, phosphate, carboxyl, sulfonic group, boronate or above-mentioned derivative, R
3Select from anilino-, thienyl, pyrrole radicals or above-mentioned derivative.
13. the manufacture method of solid electrolytic capacitor according to claim 9 is characterized in that the bond between this coupled layer and this oxide dielectric layer is silicon oxygen bond, phosphorus oxygen key, carbon-oxygen bond, sulphur oxygen key or boron oxygen key.
14. the manufacture method of solid electrolytic capacitor according to claim 9 is characterized in that the functional group of this electroconductive polymer monomer is anilino-, thienyl, pyrrole radicals or above-mentioned derivative.
15. the manufacture method of solid electrolytic capacitor according to claim 9 is characterized in that the functional group of this electroconductive polymer monomer is anilino-.
16. the manufacture method of solid electrolytic capacitor according to claim 9 is characterized in that also comprising C between first end of strand of this coupled layer and second end
1～C
12Alkyl.
17. the manufacture method of solid electrolytic capacitor according to claim 9 is characterized in that this electroconductive polymer layer is polyaniline, polythiophene, polypyrrole or above-mentioned derivative.
18. the manufacture method of solid electrolytic capacitor according to claim 9 is characterized in that this electroconductive polymer layer is a polyaniline.
19. a coupling agent is characterized in that being applicable to mode and a dielectric layer oxide and macromolecular material generation covalency bond with self assembly, the molecular formula of the following formula of tool (1):
R
1-R
3 (1)
R wherein
1Select from silylation, phosphate, carboxyl, sulfonic group, boronate or above-mentioned derivative, R
3Be one of polymerization single polymerization monomer of this macromolecular material.
20. coupling agent according to claim 19 is characterized in that R
3Select from anilino-, thienyl, pyrrole radicals or above-mentioned derivative.
21. a solid electrolytic capacitor is characterized in that comprising:
One valve metal layer;
The monoxide dielectric layer on this valve metal layer, the surface of this valve metal layer of cover part;
One coupled layer, it has (R
1-R
3) molecular formula, R wherein
1For first end of the strand of this coupled layer is binding on this oxide dielectric layer, R with covalent bond
3For second end of the strand of this coupled layer has the functional group of an electroconductive polymer monomer, wherein R
1Select from silylation, phosphate, carboxyl, sulfonic group, boronate or their derivative, R
3Select from anilino-, thienyl, pyrrole radicals or their derivative; And
One electroconductive polymer layer on this coupled layer, has covalent bond and is binding on this electroconductive polymer monomer.
22. the manufacture method of a solid electrolytic capacitor is characterized in that comprising:
One valve metal layer is provided;
Form the monoxide dielectric layer on this valve metal layer, the surface of this valve metal layer of cover part;
Mode with self assembly forms a coupled layer on this oxide dielectric layer, and this coupled layer has (R
1-R
3) molecular formula, R wherein
1For first end of the strand of this coupled layer is binding on this oxide dielectric layer, R with covalent bond
3For second end of the strand of this coupled layer has the functional group of an electroconductive polymer monomer, wherein R
1Select from silylation, phosphate, carboxyl, sulfonic group, boronate or their derivative, R
3Select from anilino-, thienyl, pyrrole radicals or their derivative; And
Form an electroconductive polymer layer on this coupled layer, have covalent bond and be binding on this electroconductive polymer monomer.
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| CN101819889A (en) * | 2010-03-30 | 2010-09-01 | 福建国光电子科技股份有限公司 | Surface treatment solution for manufacturing solid electrolytic capacitor |
| CN101819887A (en) * | 2010-03-30 | 2010-09-01 | 福建国光电子科技股份有限公司 | Surface processing solution for manufacturing solid electrolytic capacitor |
| CN103500659B (en) * | 2013-10-16 | 2016-06-22 | 中国振华（集团）新云电子元器件有限责任公司 | Macromolecular polymerization tantalum capacitor cathode preparation method |
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|---|---|---|---|---|
| US5729428A (en) * | 1995-04-25 | 1998-03-17 | Nec Corporation | Solid electrolytic capacitor with conductive polymer as solid electrolyte and method for fabricating the same |
| US6191013B1 (en) * | 1998-09-30 | 2001-02-20 | Kemet Electronics Corporation | Process for improving leakage and dissipation factor of solid electrolytic capacitors employing conductive polymer cathodes |
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2005
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5729428A (en) * | 1995-04-25 | 1998-03-17 | Nec Corporation | Solid electrolytic capacitor with conductive polymer as solid electrolyte and method for fabricating the same |
| US6191013B1 (en) * | 1998-09-30 | 2001-02-20 | Kemet Electronics Corporation | Process for improving leakage and dissipation factor of solid electrolytic capacitors employing conductive polymer cathodes |
Non-Patent Citations (1)
| Title |
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| JP平9-246106A 1997.09.19 |
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