US2016234947A1PendingUtilityA1
Adhesion Promotion in Printed Circuit Boards
Est. expiryJul 25, 2032(~6 yrs left)· nominal 20-yr term from priority
C23C 22/63C23C 22/52C23C 22/73B05D 3/10B05D 5/10C23C 22/78C23F 1/18C23G 1/20H05K 3/383H05K 3/385
56
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Claims
Abstract
Compositions and methods for enhancing adhesion between a copper conducting layer and a dielectric material during manufacture of a printed circuit board. Conditioning compositions contain a functional organic compound and preferably a transition metal ion. The functional organic compound, e.g., a purine derivative, is capable of forming a self-assembled monolayer. Adhesion promoting compositions contain an acid, preferably an inorganic acid, and an oxidant. The latter compositions may also contain a corrosion inhibitor and/or a transition metal ion selected from among Zn, Ni, Co, Cu, Ag, Au, Pd or another Pt group metal. The corrosion inhibitor may comprise a nitrogen-containing aromatic heterocyclic compound.
Claims
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53 . An aqueous alkaline composition as set forth in claim 117 wherein the aqueous alkaline composition is substantially free of peroxide.
54 . An aqueous alkaline composition as set forth in claim 117 wherein said aqueous alkaline composition is substantially free of an oxidant.
55 . An aqueous alkaline composition as set forth in claim 117 wherein said aqueous alkaline composition has an oxidation potential not greater than about 1.02 volts or 0.8 volts or 0.2 volts or 0.1 volts.
56 . An aqueous alkaline composition as set forth in claim 117 wherein said aqueous alkaline conditioning composition comprises an alkaline component.
57 . An aqueous alkaline composition as set forth in claim 56 wherein said alkaline component is selected from the group consisting of an alkali metal hydroxide, an alkali metal carbonate, or an alkalyamine.
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117 . An aqueous alkaline composition comprising a functional organic compound and a transition metal ion, said functional organic compound being capable of forming a self-assembled monolayer on a copper surface and being selected from the group consisting of nitrogen-containing aromatic heterocyclic compounds, arylamines, aralkylamines, fatty amines, sulfur-bearing aromatic heterocyclic compounds, aryl thos, aralkyl thiols, and combinations thereof,
wherein the aqueous alkaline composition has a pH between about 10 and about 15.
118 . A composition as set forth in claim 117 wherein said transition metal is selected from the group consisting of zinc, nickel, cobalt, copper, silver, gold, palladium and other platinum group metals.
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120 . An aqueous alkaline composition as set forth in claim 117 having a pH between about 10 and about 14.
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122 . An aqueous alkaline composition as set forth in claim 117 wherein said transition metal ion is selected from the group consisting of Zn, Ni, Co, Ag, Au, Pd or other platinum group metal ion.
123 . An aqueous alkaline composition as set forth in claim 117 wherein said transition metal ion comprises a zinc cation or zincate anion.
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125 . An aqueous alkaline composition as set forth in claim 117 further comprising a surfactant.
126 . An aqueous alkaline solution as set forth in claim 125 comprising both an anionic and a nonionic surfactant.
127 . An aqueous alkaline solution as set forth in claim 117 further comprising iodide ion.
128 . An aqueous alkaline solution as set forth in claim 117 further comprising an alkanolamine.
129 . An aqueous alkaline solution as set forth in claim 117 comprising between about 0.1 and about 3 wt. % of the transition metal ion and between about 0.05 and about 2.5 wt. % of the functional organic compound.
130 . An aqueous alkaline solution as set forth in claim 129 comprising between about 0.1 and about 3 wt % of a transition metal ion selected from the group consisting of Zn, Ni, Co, Cu, Ag, Au, Pd and other platinum group metals.
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132 . An aqueous alkaline solution as set forth in claim 129 comprising between about 0.1 and about 3 wt. % zinc ion.
133 . An aqueous alkaline solution as set forth in claim 117 further comprising an anionic surfactant in a concentration between about about 0.001 and about 0.03 wt. % and/or a glycol ether in a concentration between about 0.5 and about 5 wt. %.
134 . An aqueous alkaline solution as set forth in claim 117 further comprising an alkanolamine in a concentration between about 0.5 and about 5 wt. %.
135 . An aqueous alkaline solution as set forth in claim 117 comprising purine or a purine derivative in a concentration between about 0.05 and about 2.5 wt. %.
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137 . An aqueous alkaline solution as set forth in claim 117 wherein said functional organic compound capable of forming a self assembled monolayer comprises both a ring
group and an amine substituent on the ring.
138 . An aqueous alkaline solution as set forth in claim 136 wherein the substituted hydrocarbyl comprises a substituent selected from the group consisting of amino, cyano, nitro, halo, hydroxy and suithydryl.
139 . An aqueous alkaline solution as set forth in claim 117 wherein said nitrogen-containing aromatic heterocyclic compound comprises a ring substituent selected from the group consisting of cyano, nitro, halo, hydroxy and sulfhydryl.
140 . An aqueous alkaline solution as set forth in claim 139 wherein said nitrogen containing aromatic heterocyclic compound comprises a compound selected from the group consisting of mercaptobenzamidazoles, mercaptobenzothiazoles, and mercaptobenzotriazoles.
141 . An aqueous alkaline solution as set forth in claim 136 wherein said conditioning composition comprises purine or a purine derivative.
142 . An aqueous alkaline solution as set forth in claim 141 wherein said functional organic compound corresponds to the formula:
wherein each of R 2 , R 6 , and R 8 is independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydroxycarbonyl, alkoxycarbonyl, alkoxy, alkenoxy, hydroxyl, hydroxyalkyl, hydroxyalkenyl, sulfhydryl, halo, nitro, cyano and NR 9 R 10 , R 7 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydroxyl, or a negative charge, and each of R 9 and R 10 is independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl.
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150 . An aqueous alkaline solution as set forth in claim 142 comprising 6-benzylaminopurine.
151 . An aqueous alkaline solution as set forth in claim 135 wherein said purine derivative is substituted with a functional group selected from the group consisting of substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or unsubstituted carboxylic acid, substituted or unsubstituted carboxylate, substituted or unsubstituted alcohol, substituted or unsubstituted silane or alkoxysilane.
152 . An aqueous alkaline solution as set forth in claim 117 wherein said functional organic compound has the structure (Ia) or structure (Ib):
wherein:
A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , and A 7 are carbon atoms or nitrogen atoms and the sum of nitrogen atoms from A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , and A 7 is 0, 1, 2, or 3;
A 11 , A 27 , A 33 , A 44 , A 55 , A 66 , and A 77 are selected from the group consisting of electron pair, hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or unsubstituted carboxylic acid, substituted or unsubstituted ester, substituted or unsubstituted alcohol, and substituted and unsubstituted silane or alkoxysilane; and
at least one of A 1I , A 22 , A 33 , A 44 , and A 55 is selected from the group consisting of substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or unsubstituted carboxylic acid, substituted or unsubstituted ester, substituted or unsubstituted alcohol, and substituted and unsubstituted silane or alkoxysilane.
153 . An aqueous alkaline solution as set forth in claim 152 wherein the functional organic compound corresponds to structure (II), structure (III), or structure (IV):
wherein A 22 , A 44 , A 55 , A 66 , and A 77 are as defined in connection with structures (Ia) and (Ib).
154 . An aqueous alkaline solution as set forth in claim 117 wherein said functional organic compound has the structure (V):
wherein:
A 2 , A 3 , A 4 and A 5 are carbon atoms or nitrogen atoms and the sum of nitrogen atoms from A 2 , A 3 , A 4 and A 5 is 0, 1 or 2;
A 22 , A 33 , A 44 , and A 55 are selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or unsubstituted carboxylic acid, substituted or unsubstituted ester, substituted or unsubstituted alcohol, and substituted and unsubstituted silane or alkoxysilane; and
at least one of A 22 , A 33 , A 44 , and A 55 is selected from the group consisting of substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or unsubstituted carboxylic acid, substituted or unsubstituted ester, substituted or unsubstituted alcohol, and substituted and unsubstituted silane or alkoxysilane.
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