EP0374487A2
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EP
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Method for conditioning an organic polymeric material
Assignee: International Business Machines Corp
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Filing: 1989-11-17
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Granted: —
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Expires: 2009-11-17
Abstract
Abstract Certain organic polymeric materials are capable of reversibly accepting or donating electrons from a reducing entity. The redox sites in the polymer accept electrons and, as a result, a change in the properties of the polymer occurs. This change is useful in modifying or etching the polymeric material. The material can be modified by incorporation of metallic seeds into the material at a controlled depth. The seeds are incorporated by interaction of cations of the metals with the redox sites in the polymer, which cause the reduction of the cations to form the neutral metallic seeds. Subsequent exposure of the polymeric material containing the seeds to an electroless bath causes further deposition of metal having the desirable characteristic of good adhesion to the polymeric material. Etching of the polymeric material can be carried out as a result of an increase in solubility of the polymer in aprotic solvents when its redox sites have accepted electrons. The increased solubility allows openings to be etched in certain areas of the polymeric material that have been reduced, leaving other areas unchanged.
Inventors
- 👤 Alfred Viehbeck
- 👤 Stephen L. Buchwalter
- 👤 William A. Donson
- 👤 John J. Glenning
- 👤 Martin J. Goldberg
- 👤 Kurt R. Grebe
- 👤 Caroline A. Kovac
- 👤 Linda C. Matthew
- 👤 Walter P. Pawlowski
- 👤 Mark J. Schadt
- 👤 Michael R. Scheuermann
- 👤 Stephen L. Tisdale
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-05 19:35
CPC Classifications
C; C23; C23C; C23C18/00; C23C18/16; C23C18/1601; C23C18/1603; C23C18/1607; C23C18/1608; C23C18/1633; C23C18/1655; C23C18/166; C23C18/18; C23C18/20; C23C18/2006; C23C18/2046; C23C18/2073; C23C18/2086; C23C18/28; C23C18/30; H; H05; H05K; H05K3/00; H05K3/38; H05K3/381; Y; Y10; Y10S; Y10S525/00; Y10S525/903
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
105 words
Method for conditioning at least one surface of an organic polymeric material that is capable of transporting electrons in a reversible manner which comprises supplying electrons to redox sites of said polymeric material; then contacting said organic polymeric material with a solution that contains cations of a metal which will penetrate the said organic polymeric material and contact the redox sites, thereby transferring electrons to the cation that is energetically disposed to receiving electrons from said redox sites to thereby reduce the cation to metal atoms in the zero oxidation state; and then depositing a metal from an electroless bath onto the zero oxidation metal.
Claim 2
Dependent Claim
105 words
Method for conditioning at least one surface of an organic polymeric material that is capable of transporting electrons in a reversible manner which comprises supplying electrons to redox sites of said polymeric material; then contacting said organic polymeric material with a solution that contains cations of a metal which will penetrate the said organic polymeric material and contact the redox sites, thereby transferring electrons to the cation that is energetically disposed to receiving electrons from said redox sites to thereby reduce the cation to metal atoms in the zero oxidation state; and then depositing a metal from an electroless bath onto the zero oxidation metal.
Claim 3
Dependent Claim
59 words
Method of claim 1 wherein said electrons are supplied to said organic polymer material by contacting at least one surface of said organic material to a solution containing a chemical reducing agent that is energetically disposed to transferring electron(s) to said redox sites in said organic polymeric material without causing chemical reducing agent to remain with the polymeric material.
Claim 4
Dependent Claim
33 words
Method of claim 1 wherein said polymeric material is a polyimide whereby said polyimide is cured by any method by which imide ring cyclization can be obtained, including thermal and chemical dehydration curing.
Claim 5
Dependent Claim
40 words
Method of claim 3 wherein said polyimide material is a free-standing or supported film derived from a dianhydride selected from the group of pyromellitic dianhydride, 3,3′,4,4′-benzophe- nonetetracarboxylic dianhydride, 3,3′,4,4′biphenyltetracarboxylic dianhydride, naphthalene- tetracarboxylic dianhydride, perylenetetracarbox-ylic dianhydride, 4,4′-(hexafluoroisopropylidene)-bis-phthalic anhydride, and bis(3,4-dicarboxy-phenyl)sulfide dianhydride.
Claim 6
Dependent Claim
20 words
Method of claim 4 wherein the thickness of said polyimide material is about 10 nm to 0.127 mm (5 mil).
Claim 7
Dependent Claim
38 words
Method of claim 2 wherein said chemical reducing agent is a neutral organic compound whereby all or a portion of the said neutral organic compound has been electrochemically reduced in an aprotic solvent containing a supporting electrolyte salt.
Claim 8
Dependent Claim
52 words
Method of claim 6 wherein said neutral organic compound is at least one specie selected from the group of unsaturated aromatic hydrocarbons, aromatic carbonyl compounds, imides, diimides, carbodiimides, anhydrides, quinones, quaternary aromatic nitrogen compounds, aromatic heterocyclic nitrogen compounds, azomethines, immonium salts, azo compounds, amine oxides, nitro and nitroso compounds and organometallic compounds.
Claim 9
Dependent Claim
41 words
Method of claim 2 wherein said reducing agent is selected from the group of benzoin dianion, benzil anion, anthracene anion, dibenzoylmethane radical anion, benzophenone anion, anthraquinone anion, 9-fluorenone, N-n-butylphthalimide anion, N,N′-di-n-butyl-3,3′,4,4′-biphenyltetracarboxylic diimide anion, N,N′-di-n-butylpyromellitic diimide anion, acridine anion, and 1-azafluoranthene anion.
Claim 10
Dependent Claim
61 words
Method of claim 6 wherein said supporting electrolyte salt contains a cation which is at least one member of the group of tetraalkylammo-nium, tetraalkylphosphonium, alkali metal, mixed alkyl-aryl ammonium, mixed alkyl-aryl phosphonium, or chelated metal and said supporting electrolyte salt anion is at least one member selected from the group of tetrafluoroborate, hexafluorophosphate, perchlorate, halide, aryl sulfonate, and aromatic organic compounds.
Claim 11
Dependent Claim
36 words
Method of claim 9 wherein said supporting electrolyte salt contains at least one member selected from the group of tetrabutylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetraethylammonium bromide, lithium tetrafluoroborate, lithium perchlorate, benzyltributylammonium tetrafluoroborate, and sodium naphthalenide.
Claim 12
Dependent Claim
34 words
Method of claim 6 wherein said aprotic solvent is at least one member selected from the group of nitriles, nitro compounds, amides, cyclic amides, amines, esters, cyclic esters, ethers, carbonates, oxides, and sulfo compounds.
Claim 13
Dependent Claim
26 words
Method of claim 1 wherein said cation of said metal is selected from the group of palladium, platinum, ruthenium, silver, gold, copper, nickel, cobalt, and tin.
Claim 14
Dependent Claim
32 words
Method of claim 1 wherein said metals are at a depth no greater than 200 nm, preferably no greater than 80 or 20 nm respectively below the surface of said polymeric material.
Claim 15
Dependent Claim
69 words
Method of claim 2 wherein said organic polymeric material surface is patterned with a photoresist, metal, or non-electroactive coating to act as a mask, thereby exposing specific areas of the organic polymer surface to said reducing agent and depositing zero yalent metal only in the exposed areas, and wherein said photoresist or said metal mask is removed by dissolution, leaving a two-dimensional metal pattern remaining on the polymeric surface.
Claim 16
Dependent Claim
61 words
Method of claim 1 wherein said polymeric material is a polyimide and said electrons are supplied electrochemically by a cathode in contact with said polyimide in an electrochemical circuit using an aprotic solvent containing a supporting electrolyte salt, and wherein the electrochemical reduction of said polyimide is done by either control of the current supply or control of the applied potential.
Claim 17
Dependent Claim
45 words
Method of claim 1 for etching an organic polymeric material that is capable of accepting and donating electrons and ions in a reversible manner which comprises supplying electrons to redox sites of said polymeric material and then dissolving said polymeric material in an aprotic solvent.
Claim 18
Dependent Claim
38 words
Method of claim 11 wherein the said aprotic solvent is selected from at least one member of the group of acetonitrile, N,N-dimethylformamide, N-methylformamide, N,N-diethylformamide, N-ethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoramide propylene carbonate, ethylene carbonate, γ -butyrolactone, dimethylsulfoxide, acetone, and sulfolane.
Claim 19
Dependent Claim
60 words
Method of claim 16 wherein said organic polymeric material surface is patterned with a photoresist or metal to act as a mask, thereby exposing specific areas of the organic polymer surface to said reducing agent and dissolving polymeric material in the exposed areas, and wherein said photoresist or said metal mask is removed by dissolution, leaving a two-dimensional polymeric pattern.
Claim 20
Dependent Claim
57 words
Method of claim 1 for conditioning at least one surface of an organic polymeric material that is capable of transporting electrons in a reversible manner which comprises contacting said organic polymeric material with tetrakis(dimethylamino)ethylene to thereby reduce redox sites of said polymeric material to the radical anion form and to oxidize said tetrakis(dimethylamino)ethylene to a cation form.
Claim 21
Dependent Claim
22 words
Method of claims 1, 16, or 19 wherein said organic polymeric material is a cured polyimide from 3,3′,4,4′-biphenyltetracarboxylic dianhydride and a diamine.
Claim 22
Dependent Claim
18 words
Method of claims 1, 16, or 19 wherein said organic polymeric material is a polyester, preferably polyethylene terephthalate.
Claim 23
Dependent Claim
31 words
Method of claim 1 which further comprises, prior to said supplying electrons in a reversible manner, coating metal onto said organic polymeric material, resulting in pinholes and exposed organic polymeric material.
Claim 24
Dependent Claim
35 words
Method of claim 1 wherein said organic polymeric material includes a through-hole and/or blind via structure, and wherein only the polymeric material at the sidewalls of said through-holes have electrons supplied to redox sites thereof.
Claim 25
Dependent Claim
66 words
Method for bonding two surfaces together of organic polymeric material that is capable of transporting electrons in a reversible manner which comprises supplying electrons to redox sites of the polymeric material of both surfaces to create reduced regions therein; bringing together said surfaces whereby the reduced regions interpenetrate and form an interphase; and then reoxidizing the reduced interphase region to thereby bond the two surfaces together.
Claim 26
Dependent Claim
66 words
Method for bonding two surfaces together of organic polymeric material that is capable of transporting electrons in a reversible manner which comprises supplying electrons to redox sites of the polymeric material of both surfaces to create reduced regions therein; bringing together said surfaces whereby the reduced regions interpenetrate and form an interphase; and then reoxidizing the reduced interphase region to thereby bond the two surfaces together.
Claim 27
Dependent Claim
36 words
Method of claim 1 wherein said cations are supplied by an electroless plating bath for deposition of a zero oxidation metal and for further deposition of metal onto zero oxidation metal from said electroless plating bath.
References Cited (Backward Citations)
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