US3778357A - Electrolyte and method for electrodepositing copper - Google Patents
Electrolyte and method for electrodepositing copper Download PDFInfo
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- US3778357A US3778357A US00317720A US3778357DA US3778357A US 3778357 A US3778357 A US 3778357A US 00317720 A US00317720 A US 00317720A US 3778357D A US3778357D A US 3778357DA US 3778357 A US3778357 A US 3778357A
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- Prior art keywords
- alkyl
- copper
- electrolyte
- ions
- liter
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 22
- 229910052802 copper Inorganic materials 0.000 title abstract description 22
- 239000010949 copper Substances 0.000 title abstract description 22
- 239000003792 electrolyte Substances 0.000 title description 29
- 238000000034 method Methods 0.000 title description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 24
- -1 CYANOBENZYL Chemical class 0.000 abstract description 11
- 238000007747 plating Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical class [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical class [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 abstract 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical group C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229960003237 betaine Drugs 0.000 description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 239000002659 electrodeposit Substances 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000002946 cyanobenzyl group Chemical group 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 125000001326 naphthylalkyl group Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 150000003343 selenium compounds Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- RMLIMUXFHLUHGD-UHFFFAOYSA-N 2-[(2-sulfophenyl)disulfanyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1SSC1=CC=CC=C1S(O)(=O)=O RMLIMUXFHLUHGD-UHFFFAOYSA-N 0.000 description 1
- JJFSOYCVVILLEH-UHFFFAOYSA-N 3-(3-sulfopropyldiselanyl)propane-1-sulfonic acid Chemical compound S(=O)(=O)(O)CCC[Se][Se]CCCS(=O)(=O)O JJFSOYCVVILLEH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GMEHFXXZSWDEDB-UHFFFAOYSA-N N-ethylthiourea Chemical compound CCNC(N)=S GMEHFXXZSWDEDB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 101001041669 Oryctolagus cuniculus Corticostatin 1 Proteins 0.000 description 1
- 241001424397 Paralucia pyrodiscus Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Chemical group 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 241000272534 Struthio camelus Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XNYQDIFYWJLJBH-UHFFFAOYSA-M [Br-].OC[P+](CCCC)(CO)CO Chemical compound [Br-].OC[P+](CCCC)(CO)CO XNYQDIFYWJLJBH-UHFFFAOYSA-M 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WCHPXAFAEZGCMB-UHFFFAOYSA-M benzyl(tributyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC1=CC=CC=C1 WCHPXAFAEZGCMB-UHFFFAOYSA-M 0.000 description 1
- XXJSZTRBVJXLSH-UHFFFAOYSA-M benzyl(tricyclohexyl)phosphanium;bromide Chemical compound [Br-].C1CCCCC1[P+](C1CCCCC1)(C1CCCCC1)CC1=CC=CC=C1 XXJSZTRBVJXLSH-UHFFFAOYSA-M 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- SSXHYKKELBCVAF-UHFFFAOYSA-M methyl sulfate tetrabutylphosphanium Chemical compound COS(=O)(=O)[O-].C(CCC)[P+](CCCC)(CCCC)CCCC SSXHYKKELBCVAF-UHFFFAOYSA-M 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 150000005451 methyl sulfates Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000570 polyether Chemical group 0.000 description 1
- HYTYHTSMCRDHIM-UHFFFAOYSA-M potassium;2-sulfanylacetate Chemical compound [K+].[O-]C(=O)CS HYTYHTSMCRDHIM-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- KSMYREBPTSSZDR-UHFFFAOYSA-M tributyl(prop-2-enyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC=C KSMYREBPTSSZDR-UHFFFAOYSA-M 0.000 description 1
- AVMUXDOWIVNPJK-UHFFFAOYSA-M tributyl-(2-methoxy-2-oxoethyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC(=O)OC AVMUXDOWIVNPJK-UHFFFAOYSA-M 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- R to R may be lower alkyl, halo-, aminoor hydroxy derivatives thereof, benzyl, cyanobenzyl, carblower-alkoxy, carb-lower-alkoxy-lower-alkyl, naphthyllower alkyl, trialkyl phosphonium-alkyl-diphenylalkyl, phenyl, cycloalkyl having 5 to 8 carbon atoms, or lower alkenyl.
- R and R jointly with the P may constitute phosphindolinium, and R may also be wherein n is an integer between 1 and 4, and Y is S0 S04, P04, P03, or CO2.
- This invention relates to aqueous, acid copper plating electrolytes, and particularly to such electrolytes containing addition agents for improving the properties of the copper electrodeposit, and to the use of the electrolytes.
- Aqueous electrolytes containing only copper sulfate and sulfuric acid as solutes yield visibly crystalline and dull cathodic copper deposits. It is known to add small amounts of certain organic addition agents to the basic electrolyte for obtaining bright copper deposits.
- the addition agents proposed heretofore are organic, sulfur-bearing compounds which, in addition to divalent sulfur, may contain phosphorus, sulfonic acid radicals, and polyether moieties.
- the sulfur-bearing compounds have been found practically applicable only when employed in combination with an oxygen-bearing compound of high molecular weight.
- Such brightener compositions are limited in their use to a narrow range of cathodic current densities, and particularly to a maximum cathode current density of approximately 85 amps/sq. ft. At higher current densities, enough hydrogen is co-deposited to make the deposit powdery, and thus useless.
- the primary object of this invention is the provision of an addition agent for acid copper plating electrolytes which permits bright and ductile copper electrodeposits to be produced at higher current densities than were permissible heretofore, more specifically, at cathode current densities greater than 100 amps./sq. ft.
- R R R and K may be identical or dilferent.
- R R R are members of the group consisting of alkyl haloalkyl, aminoalkyl, hydroxyalkyl, benzyl, cyanobenzyl, carbalkoxy, carbalkoxyalkyl, naphthylalkyl, and trialkylphosphonium-alkyl-diphenyl, in all these compounds the alkyl groups having one to four carbon atoms, also phenyl, cycloalkyl having 5 to 8 carbon atoms, and alkenyl having 2 to 4 carbon atoms, or R and R jointly with the P constitute phosphindolinium, while R is a member of the afore-mentioned group or (CH wherein n is an integer between one and four, and Y is 80,, S0 P04, P03, 01' CO2.
- the addition agents are preferably hydroxides or salts of the phosphonium, and preferably sulfates, methylsulfates, chlorides, bromides, iodides, nitrates, or acetates.
- R is (CH ),,Y-, the addition agent is a betaine, and Y is the radical of sulfuric, sulfurous, phosphoric, phosphorous acid or of the radical of a carboxyl group.
- addition agents of the invention are known in part. They can be prepared by known methods in an obvious manner, as far as they are novel, as by reacting suitable tertiary phosphines with organic halides or sulfonic acid esters.
- Tetrabutylphosphonium chloride Tetraethylphosphonium sulfate Tributyl-benzylphosphonium chloride 4 9) a 2 s 5] C Tricyclohexyl-benzylphosphonium bromide s 11)s Z- B 5] Tris(hydroxymethyl) -butylphosphonium bromide (HOCH PC H Br Methyl-diethyl-carbomethoxyphosphonium iodide P-C O O CH3]I Triethyl-B-chloroethylphosphonium chloride z s 3 2) 2 C1 Triethyl-fi-aminoethylphosphonium chloride [(C H P(CH NHflCl Triphenyl-propylsulfophosphonium betaine a s)S TCHZu W Trimethyl-acetophosphonium betaine (CH P .CH COO 3 1,l-diethylphosphindolin
- Tributyl-cyanobenzylphosphonium chloride Tributyl-carbomethoxymethylphosphonium chloride (C H P-CH OOOCH Cl Tributyl-propylsulfophosphonium betaine 4 9)a 2)a 3 Tetrabutylphosphonium methylsulfate Tributyl-allylphosphonium chloride Among the compounds enumerated above, those having aromatic groups directly bound to the phosphorus atom are less effective than others.
- the addition agents of the invention produce beneficial effects in copper plating electrolytes which may contain 100-280 g./liter copper sulfate pentahydrate and 20-100 g./liter sulfuric acid, but they are equally effective in electrolytes, otherwise known, in which the sulfate ions are replaced partly or entirely by fluoroborate ions, pyrophosphate ions, or those of other acids, At this time, the sulfate electrolytes are of greatest economic significance.
- the electrolyte may be free from chloride ions, other than those introduced with an addition agent of the invention, or it may be mixed with alkali metal chlorides or hydrochloric acid in amounts of 0.001 to 0.5 g./liter for improved brightness and levelling effect.
- Addition agents of the invention used singly or jointly, in adequate amounts permit the average cathode current density to be increased substantially beyond 85 amps/sq. ft., and even to much more th'an 100 amps./sq. ft., without causing plating defects, more specifically, loosely adhering, powdery copper deposits in areas of highest current density. Simultaneously, throwing and covering power is greatly improved so that a satisfactory copper coating is obtained in areas of lowest actual current density which would not be covered in an electrolyte not containing the addition agent or agents of the invention. Electrolyte temperatures up to about 45 C. may safely be employed when using the addition agents.
- the concentration of addition agent in the electrolyte may be chosen between about 0.01 g./
- the addition agents of the invention when used jointly with other known brighteners and/or wetting agents, permit copper electrodeposits of high brightness and free from haze to be produced at very high cathode current densities.
- the increase in the permissible current densities is particularly striking when the addition agents of the invention are mixed with copper plating electrolytes containing organic thio and seleno compounds.
- Such solutions may also contain levelling agents, known in themselves, such as nitrogen-bearing thio compounds, polymeric phenazonium compounds, and the like.
- the thio or seleno compounds containing hydrophilic groups which make them water-soluble are employed jointly with addition agents of the invention in amounts of about 0.0005 to 0.2 g./liter, and preferably 0.01 to 0.1 g./liter, and the broad range of concentrations is the same for the nitrogen bearing thio compounds and phenazonium derivatives, although optimum concentrations are usually between 0.0005 and 0.02 g./liter.
- EXAMPLE 1 A copper plating electrolyte containing 200: g./liter copper sulfate pentahydrate and 55 g./liter concentrated sulfuric acid yielded dull copper deposits of unsatisfactory throwing power at all practical cathode current densities.
- An aqueous acidic electrolyte for the electrodeposition of copper comprising, as solutes, a source of copper ions, a source of hydrogen ions, and in an amount sufiicient to provide better throwing and covering power, a source of ions of a phosphonium of the formula wherein R R and R are members of the group consisting of alkyl, haloalkyl, aminoalkyl, hydroxyalkyl, benzyl, cyanobenzyl, carbalkoxy, carbalkoxyalkyl, naphthylalkyl, and trialkyl phosphonium-alkyl-diphenylalkyl, the alkyl of said members having one to four carbon atoms, phenyl, cycloalkyl having 5 to 8 carbon atoms, and alkenyl having 2 to 4 carbon atoms, or
- R and R jointly with said P constitute phosphindolinium
- R is a member of said group or (CH Y, wherein n is an integer between one and four, and Y is S0 80,, P0 P0 or C0 2.
- R is a member of said group and said source is a hydroxide, sulfate, methylsulfate, chloride, bromide, iodide, nitrate, or acetate of said phosphonium.
- a process of electrodepositing copper which comprises making a conductive object the cathode in an elec- 8 References Cited UNITED STATES PATENTS 2,893,932 7/1959 Haas et a1. 204-52 R X 3,084,111 4/1-963 Strauss et a1. 20452 R X 3,269,925 8/1966 Du Rose 204-52 Y X 3,309,293 3/1967 Ostrow et al 204-52 Y 3,475,293 10/1969 Haynes et al. 20452 R X FOREIGN PATENTS 6,807 3/1967 Japan 204-106 GERALD L. KAPLAN, Primary Examiner US. Cl. X.R.
- trolyte defined in claim 1 at a cathode current density 15 2 0 350 456 4 5 47 5 3 0 5 substantially greater than 100 amps. per square foot.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2204326A DE2204326C3 (de) | 1972-01-26 | 1972-01-26 | Wäßriges saures Bad zur galvanischen Abscheidung von glänzenden und duktilen Kupferüberzügen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3778357A true US3778357A (en) | 1973-12-11 |
Family
ID=5834477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00317720A Expired - Lifetime US3778357A (en) | 1972-01-26 | 1972-12-22 | Electrolyte and method for electrodepositing copper |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3778357A (enrdf_load_stackoverflow) |
| JP (1) | JPS5625517B2 (enrdf_load_stackoverflow) |
| DE (1) | DE2204326C3 (enrdf_load_stackoverflow) |
| FR (1) | FR2169222B1 (enrdf_load_stackoverflow) |
| GB (1) | GB1423530A (enrdf_load_stackoverflow) |
| IE (1) | IE37141B1 (enrdf_load_stackoverflow) |
| IT (1) | IT973212B (enrdf_load_stackoverflow) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5849171A (en) * | 1990-10-13 | 1998-12-15 | Atotech Deutschland Gmbh | Acid bath for copper plating and process with the use of this combination |
| US20030010646A1 (en) * | 1999-05-17 | 2003-01-16 | Barstad Leon R. | Electrolytic copper plating solutions |
| US20040045832A1 (en) * | 1999-10-14 | 2004-03-11 | Nicholas Martyak | Electrolytic copper plating solutions |
| DE10261852B3 (de) * | 2002-12-20 | 2004-06-03 | Atotech Deutschland Gmbh | Gemisch oligomerer Phenaziniumverbindungen und dessen Herstellungsverfahren, saures Bad zur elektrolytischen Abscheidung eines Kupferniederschlages, enthaltend die oligomeren Phenaziniumverbindungen, sowie Verfahren zum elektrolytischen Abscheiden eines Kupferniederschlages mit einem das Gemisch enthaltenden Bad |
| US20060183328A1 (en) * | 1999-05-17 | 2006-08-17 | Barstad Leon R | Electrolytic copper plating solutions |
| US20110198227A1 (en) * | 2003-05-12 | 2011-08-18 | Arkema Inc. | High purity electrolytic sulfonic acid solutions |
| WO2013176796A1 (en) | 2012-05-25 | 2013-11-28 | Macdermid Acumen,Inc. | Additives for producing copper electrodeposits having low oxygen content |
| EP2963158A1 (en) | 2014-06-30 | 2016-01-06 | Rohm and Haas Electronic Materials LLC | Plating method |
| EP3162921A1 (en) | 2015-10-27 | 2017-05-03 | Rohm and Haas Electronic Materials LLC | Method of electroplating copper into a via on a substrate from an acid copper electroplating bath |
| CN107429415A (zh) * | 2015-03-26 | 2017-12-01 | 三菱综合材料株式会社 | 使用了磷盐的电镀液 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4076600A (en) * | 1976-12-20 | 1978-02-28 | R. O. Hull & Company, Inc. | Leveling agent for acid zinc electroplating baths and method |
| JPH0762021B2 (ja) * | 1986-11-05 | 1995-07-05 | 第一工業製薬株式会社 | 第４ホスホニウム化合物の製造方法 |
| JPH0720978B2 (ja) * | 1987-06-24 | 1995-03-08 | 株式会社クラレ | ホスホニウム塩ならびにその製造方法 |
| DE4211140A1 (de) * | 1992-04-03 | 1993-10-07 | Basf Ag | Phosphoniumsalze und ihre Verwendung als Glanzmittel für wäßrig-saure galvanische Nickelbäder |
| WO2016152983A1 (ja) * | 2015-03-26 | 2016-09-29 | 三菱マテリアル株式会社 | ホスホニウム塩を用いためっき液 |
| US12394841B2 (en) | 2019-01-24 | 2025-08-19 | Octet Scientific, Inc. | Zinc battery elecrtolyte additive |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1163114B (de) * | 1962-02-13 | 1964-02-13 | Dehydag Gmbh | Galvanische Metallbaeder |
-
1972
- 1972-01-26 DE DE2204326A patent/DE2204326C3/de not_active Expired
- 1972-12-22 US US00317720A patent/US3778357A/en not_active Expired - Lifetime
- 1972-12-29 IT IT33935/72A patent/IT973212B/it active
-
1973
- 1973-01-22 GB GB319473A patent/GB1423530A/en not_active Expired
- 1973-01-23 IE IE109/73A patent/IE37141B1/xx unknown
- 1973-01-24 JP JP1020773A patent/JPS5625517B2/ja not_active Expired
- 1973-01-25 FR FR7302563A patent/FR2169222B1/fr not_active Expired
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5849171A (en) * | 1990-10-13 | 1998-12-15 | Atotech Deutschland Gmbh | Acid bath for copper plating and process with the use of this combination |
| US20030010646A1 (en) * | 1999-05-17 | 2003-01-16 | Barstad Leon R. | Electrolytic copper plating solutions |
| US20060183328A1 (en) * | 1999-05-17 | 2006-08-17 | Barstad Leon R | Electrolytic copper plating solutions |
| US20040045832A1 (en) * | 1999-10-14 | 2004-03-11 | Nicholas Martyak | Electrolytic copper plating solutions |
| DE10261852B3 (de) * | 2002-12-20 | 2004-06-03 | Atotech Deutschland Gmbh | Gemisch oligomerer Phenaziniumverbindungen und dessen Herstellungsverfahren, saures Bad zur elektrolytischen Abscheidung eines Kupferniederschlages, enthaltend die oligomeren Phenaziniumverbindungen, sowie Verfahren zum elektrolytischen Abscheiden eines Kupferniederschlages mit einem das Gemisch enthaltenden Bad |
| US7872130B2 (en) | 2002-12-20 | 2011-01-18 | Atotech Deutschland Gmbh | Mixture of oligomeric phenazinium compounds and acid bath for electrolytically depositing a copper deposit |
| US9399618B2 (en) | 2003-05-12 | 2016-07-26 | Arkema Inc. | High purity electrolytic sulfonic acid solutions |
| US20110198227A1 (en) * | 2003-05-12 | 2011-08-18 | Arkema Inc. | High purity electrolytic sulfonic acid solutions |
| WO2013176796A1 (en) | 2012-05-25 | 2013-11-28 | Macdermid Acumen,Inc. | Additives for producing copper electrodeposits having low oxygen content |
| US9243339B2 (en) | 2012-05-25 | 2016-01-26 | Trevor Pearson | Additives for producing copper electrodeposits having low oxygen content |
| EP2963158A1 (en) | 2014-06-30 | 2016-01-06 | Rohm and Haas Electronic Materials LLC | Plating method |
| CN107429415A (zh) * | 2015-03-26 | 2017-12-01 | 三菱综合材料株式会社 | 使用了磷盐的电镀液 |
| US10174434B2 (en) | 2015-03-26 | 2019-01-08 | Mitsubishi Materials Corporation | Plating solution using phosphonium salt |
| CN107429415B (zh) * | 2015-03-26 | 2019-08-23 | 三菱综合材料株式会社 | 使用了磷盐的电镀液 |
| EP3162921A1 (en) | 2015-10-27 | 2017-05-03 | Rohm and Haas Electronic Materials LLC | Method of electroplating copper into a via on a substrate from an acid copper electroplating bath |
| US10988852B2 (en) | 2015-10-27 | 2021-04-27 | Rohm And Haas Electronic Materials Llc | Method of electroplating copper into a via on a substrate from an acid copper electroplating bath |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1423530A (en) | 1976-02-04 |
| FR2169222A1 (enrdf_load_stackoverflow) | 1973-09-07 |
| DE2204326A1 (de) | 1973-08-02 |
| DE2204326B2 (de) | 1980-08-21 |
| IT973212B (it) | 1974-06-10 |
| DE2204326C3 (de) | 1981-07-09 |
| IE37141L (en) | 1973-07-26 |
| IE37141B1 (en) | 1977-05-11 |
| JPS5625517B2 (enrdf_load_stackoverflow) | 1981-06-12 |
| FR2169222B1 (enrdf_load_stackoverflow) | 1976-05-14 |
| JPS4886741A (enrdf_load_stackoverflow) | 1973-11-15 |
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