CA1311713C - Baths of organic sulfonate solution for bismuth and bismuth alloy plating - Google Patents
Baths of organic sulfonate solution for bismuth and bismuth alloy platingInfo
- Publication number
- CA1311713C CA1311713C CA 519048 CA519048A CA1311713C CA 1311713 C CA1311713 C CA 1311713C CA 519048 CA519048 CA 519048 CA 519048 A CA519048 A CA 519048A CA 1311713 C CA1311713 C CA 1311713C
- Authority
- CA
- Canada
- Prior art keywords
- bismuth
- acid
- baths
- radical
- alloy plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 29
- 238000007747 plating Methods 0.000 title claims abstract description 17
- 229910001152 Bi alloy Inorganic materials 0.000 title claims abstract description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title description 2
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 8
- 150000001621 bismuth Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- -1 nitro, mercapto, sulfonyl Chemical group 0.000 claims abstract description 5
- 229910006069 SO3H Inorganic materials 0.000 claims abstract 2
- 239000004615 ingredient Substances 0.000 claims abstract 2
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 125000002877 alkyl aryl group Chemical group 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical group [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001624 naphthyl group Chemical group 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 239000002659 electrodeposit Substances 0.000 description 8
- 108010010803 Gelatin Proteins 0.000 description 4
- 239000001888 Peptone Substances 0.000 description 4
- 108010080698 Peptones Proteins 0.000 description 4
- 229940014259 gelatin Drugs 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 235000019319 peptone Nutrition 0.000 description 4
- OGNVQLDIPUXYDH-ZPKKHLQPSA-N (2R,3R,4S)-3-(2-methylpropanoylamino)-4-(4-phenyltriazol-1-yl)-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylic acid Chemical compound CC(C)C(=O)N[C@H]1[C@H]([C@H](O)[C@H](O)CO)OC(C(O)=O)=C[C@@H]1N1N=NC(C=2C=CC=CC=2)=C1 OGNVQLDIPUXYDH-ZPKKHLQPSA-N 0.000 description 3
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 2
- 229910016334 Bi—In Inorganic materials 0.000 description 2
- 229910016338 Bi—Sn Inorganic materials 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- JREOSEFCSTYCEW-UHFFFAOYSA-K OC(CS(=O)(=O)[O-])C.[Bi+3].OC(CS(=O)(=O)[O-])C.OC(CS(=O)(=O)[O-])C Chemical compound OC(CS(=O)(=O)[O-])C.[Bi+3].OC(CS(=O)(=O)[O-])C.OC(CS(=O)(=O)[O-])C JREOSEFCSTYCEW-UHFFFAOYSA-K 0.000 description 2
- 229910020816 Sn Pb Inorganic materials 0.000 description 2
- 229910020922 Sn-Pb Inorganic materials 0.000 description 2
- 229910008783 Sn—Pb Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- MNMKEULGSNUTIA-UHFFFAOYSA-K bismuth;methanesulfonate Chemical compound [Bi+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O MNMKEULGSNUTIA-UHFFFAOYSA-K 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical compound N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 description 1
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 1
- 229910002904 Bi-Co Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- CWCOBLKWMDSQME-UHFFFAOYSA-N C(C(O)C(O)C(=O)O)(=O)O.C(C(O)CO)(=O)O Chemical compound C(C(O)C(O)C(=O)O)(=O)O.C(C(O)CO)(=O)O CWCOBLKWMDSQME-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001024304 Mino Species 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- IUDUXJHMTJKWOO-UHFFFAOYSA-H [Bi+3].[Bi+3].OS(=O)(=O)C(CC([O-])=O)C([O-])=O.OS(=O)(=O)C(CC([O-])=O)C([O-])=O.OS(=O)(=O)C(CC([O-])=O)C([O-])=O Chemical compound [Bi+3].[Bi+3].OS(=O)(=O)C(CC([O-])=O)C([O-])=O.OS(=O)(=O)C(CC([O-])=O)C([O-])=O.OS(=O)(=O)C(CC([O-])=O)C([O-])=O IUDUXJHMTJKWOO-UHFFFAOYSA-H 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KIAYKYHZRPLPLD-UHFFFAOYSA-J benzenesulfonate tin(4+) Chemical compound [Sn+4].[O-]S(=O)(=O)c1ccccc1.[O-]S(=O)(=O)c1ccccc1.[O-]S(=O)(=O)c1ccccc1.[O-]S(=O)(=O)c1ccccc1 KIAYKYHZRPLPLD-UHFFFAOYSA-J 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- JALQQBGHJJURDQ-UHFFFAOYSA-L bis(methylsulfonyloxy)tin Chemical compound [Sn+2].CS([O-])(=O)=O.CS([O-])(=O)=O JALQQBGHJJURDQ-UHFFFAOYSA-L 0.000 description 1
- MKJZCTBDSBFQFT-UHFFFAOYSA-K bis-(4-methylphenyl)sulfonyloxybismuthanyl 4-methylbenzenesulfonate Chemical compound [Bi+3].Cc1ccc(cc1)S([O-])(=O)=O.Cc1ccc(cc1)S([O-])(=O)=O.Cc1ccc(cc1)S([O-])(=O)=O MKJZCTBDSBFQFT-UHFFFAOYSA-K 0.000 description 1
- YULRGTUQMXEFPH-UHFFFAOYSA-K bis[(2-sulfooxybenzoyl)oxy]bismuthanyl 2-sulfooxybenzoate Chemical compound [Bi+3].OS(=O)(=O)OC1=CC=CC=C1C([O-])=O.OS(=O)(=O)OC1=CC=CC=C1C([O-])=O.OS(=O)(=O)OC1=CC=CC=C1C([O-])=O YULRGTUQMXEFPH-UHFFFAOYSA-K 0.000 description 1
- FGOASOYWIIWNLA-UHFFFAOYSA-K bismuth benzenesulfonate Chemical compound C1(=CC=CC=C1)S(=O)(=O)[O-].[Bi+3].C1(=CC=CC=C1)S(=O)(=O)[O-].C1(=CC=CC=C1)S(=O)(=O)[O-] FGOASOYWIIWNLA-UHFFFAOYSA-K 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- 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
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
Landscapes
- 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)
Abstract
ABSTRACT OF THE DISCLOSURE
A bismuth or bismuth alloy plating bath comprises as essen-tial ingredients an organic sulfonic acid of the general formula (I) (X1)n-R-SO3H ------ (I) wherein R is a C1-5 alkyl radical, X1 is a halogen atom or hydroxyl, aryl, alkylaryl, carboxyl, or sulfonyl radical which may be in any optional position of the alkyl radical, and n is an integer of 0 to 3, or of the formula (II)
A bismuth or bismuth alloy plating bath comprises as essen-tial ingredients an organic sulfonic acid of the general formula (I) (X1)n-R-SO3H ------ (I) wherein R is a C1-5 alkyl radical, X1 is a halogen atom or hydroxyl, aryl, alkylaryl, carboxyl, or sulfonyl radical which may be in any optional position of the alkyl radical, and n is an integer of 0 to 3, or of the formula (II)
Description
c~ ~z~g ~,31~PI~'~
BATHS OF ORGANIC SULFONATE SOLUTION
FOR BISMUTH AND BISMUTH ALLOY PLATING
BACKGROUND OF T~, INVENTION
This invention relates to bismut;h and bismuth alloy plating baths. More particularly, it is concerned with bismuth and bismuth alloy electroplating baths which use an organic sulfonic acid as a co-soluble complex salt of` bismu~h and the ~etal other than bismuth and give smooth electroplated deposits without the emission of highly pollutlng matter.
Bismuth is extensively used as a lubricant in nuclear reactor construction as well as in such newly opened fields as the manu-facture of recti~ier and ohmic contacts. These applications require relatively thick plates, approximately from 30 to 100 ~m in thickness. With conventional complex salt baths such as *
perchlorate, glycerate-tartrate, and Trilon baths, however, the resulting deposits ~ree of trees dendrite are at best 10 ~m thick. Ordinary baths using no complex s~lt provide only coarse=
crystal films.
Fast progress of the electronic industry in recent years has created demands Lor various bismuth-base alloys of low-melting points. Increasing importance is being attached to these low=
melting solders because o~ the introduction o~ semiconductors with more and more dellcate thermal properties. Ordinary sol-ders, typi~ied by the Sn-Pb alloy, have the disadvanta~e of *Trademark v, ,., ,. , ; .~, 131~P3 so-called low-temperature brittleness. Component parts soldered with them become brittle when placed in environmcnts below ordi nary temperature, as are encountered by the soldered parts of devices and apparatus for use in superconductive and space development projects. For services in such severe environments, therefore, low-temperature resistant solders are desirable.
Examples are Bi-Sn, Bi-In, Bi-Pb, Bi-Co, Bi-Ni, Bi-Sb, Bi-In-Sn, and Bi-Sn-Pb alloys. Since the st;~ndard electrode potential of bismuth is far nobler than those of tin, indium, and lead, there occurs practically no codeposition of these alloying elements from their simple solution. To make their deposition potentials as close to one another as possible, a camplex salt bath must be used instead!
Varied 8i-Sn alloy plating baths, for example, in the ~orm of sulfate, chloride, perchlorate, boro~luoride, and alkali baths, have hitherto been reported. Nevertheless, because o~
the electric potential difference, it is dlfficult to codeposit a relatively large proportion of bismuth to tin, and an electro-deposit of the low-~elting alloy can hardl~ be obtained. As for the Bi-In alloy plating from a perchlorate bath, the limitation to the current density range over which the codeposit is formed makes it rarely possible to obtain thick, good alloy plates.
SU~ARY OF THE INVENTION
The present invention has resulted ~rom investigations made in view o~ the foregoine. It i9 ai~ed at providing a pl-tin~
" : :
`"': ' :
~:
~3:1~ 7~
bath which consists essentially of an organic sulfonic acid that seldom poses a pollution problem and salts of bismuth and a metal other than bismuth, and gives substantially better electrodepo-sits than those from conventional inorganic acid baths, and permits easy control of the bath in alloy plating, inasmuch as the electrodeposit composition is close to the metal proportion in the bath. Thus the investigations have led to the discovery of useful acids for the above purpose.
In the case of Bi-Sn alloy pl~ating, a major disadvantage is that, where the electric potential difference between tin and bismuth is too wide for the passage of current, bismuth can be lost by its contact deposition on the anode tin surface. It has now been found that the plating bath of the invention character-istically inhibits to a large measure the unwanted bismuth deposition on the anode tin surface.
DETAILED D~SCRIPTION OF THE INVENTION
The organic sulfon~c acids to be used in accordance with the invention are sulfonic acids as aliphatic or nonbenzene alicyclic compounds of the general formula ~I) (Xl) n ~ ~ -S Os~
wherein R is a Cl 5 alkyl radical, Xl is a halogen atom or hydroxyl 9 aryl, alkylaryl, carboxyl, or sulfonyl radical which may be in any optional position of the alkyl radical, and n is an integer of O to 3, and aromatic sulfonic acids having various substituen~s o~ The formula (I.) .' ' ~ .. ' ' ~ . .
.
~3~7 ~ 3 I~(X2)m ~
wherein X2 is a halogen atom or hydroxyl, alkyl, aryl, alkylaryl, aldehyde, carboxyl, nitro, mercapto, sulfonyl, or amino radical, or two Xz's which may combine with a benzene ring to form a naphthalene ring, and m is an lnteger of 0 to 3.
Examples of these organic sulfonic aclds are methanesulfonic, ethanesulfonic, propanesul~onic, 2-propanesulfonic, butanesulfon-ic, 2-butanesulfonic, pentanesulfonlc, chloropropanesulfonic, 2-hydroxyethane-l-sulfonic, 2-hydroxypropane-l-sulfonic, 2-hy-droxybutane-l-sul~onic, 2-hydroxypentanesulfonic, allylsulfonic, ~-sulfoacetic, 2- or 3-sulfopropionic, sul~osuccinic, sulfo-maleic, sulfofumaric, benzenesulfonic, toluenesulfonic~ xylene-sulfonic, nitrobenzenesulfonic, sulfobenzoic, sulfosalicylic, 2nd benzaldehydesuifonlc acids. These acids are used alone or as a mixture of two or more. Their bismuth salts and salts of metals other than bismuth are prepared in the usual manner.
A bismuth plating bath contains such an organic sul~onic acid and its bismuth salt. In the case o~ 2 bismuth alloy plating ~ath, such an organic sulfonic acid, its bismuth salt, and ano~her or two ar more metal salts are contained.
The total concentration of bi6muth and another metal salt of the organic sul~onic acid is, in terms of the metals, from 0.5 to 200 gJ~t preferably from lO to lO0 g/~. The concentration of the free organic .... :
-. .
. .
~ 3 ~
sulfonic acid to be pre~ent in the plating bath is stoichiometrically at least an equivalent to the concentration of the bismuth and other metal salts in the bath. Preferably, the concentration of the free organic sulfonic acid is 30-400 g/Q.
The plating bath of the invention may contain peptone, gela-tin, nonionic surfactant, or other additive effective in avoiding burnt deposits due to exeessive current lntensity and in inhibit-ing dendritic growth. The concentration of the additive usually ranges from 0.01 to 50 g~l, preferably from 0.05 to 20 g/l.
*
Among typical nonionic surfactants for this use are "Epon 740", "Liponox N-105", and "Neugen EN".
~ X A M P L E S
While the present invention is illustrated by the following several examples in which certain plating bath compositions and operating conditions are used, it should be noted that the inven~
tion is not limited thereto but may be ~ariously embodied with changes in the compositions and conditions to realize the objects of obtaining uniform, smooth plated deposits.
Throughout the examples, the outward appearance of the plate obtained was e~aluated by the Hull cell test.
Example 1 Bismuth (as bismuth methanesulfonate) 20 g/l Free methanesul~onic acid 150 "
Gelatin 5 "
Temperature 25C
Current density range 0.5-S A/dm *Trademark j!
. . .
' ' '. ', ' . ' ' ~3~7~3 Example 2 Bismuth tas bismuth 2-hydroxypropanesulfonate) 15 g/~
Free 2-hydroxypropanesulfonic acid 100 "
"Epon 740"
Temperature 30C
Current density range 0.2-3 A/dm2 Example 3 Bismuth (as bismuth sulfosuccinate) 30 g/2 Free sulfosuccinic acid . 200 Peptone 5 "
Temperature 20C
Current density range 1-6 A/dm2 Example 4 Bismuth (as bismuth p-phenolsulfonate) 25 g/~
Free p-phenolsulfonic acid 120 Peptone 2 Temperature 25C
Current density range 1-5 A/dm2 Example 5 Bismuth (as bismuth p-toluenesulfonate) 6 g/~
Free p-toluenesulfonic acid 150 Gelatin 3 "
Temperature 30C
Current density range 0.2-S A/dm2 , .
. ~ . ... .
13~7~3 Bismuth (as bismuth sulfosalicylate) 10 g/Q
Free sulfosalicylic acld 200 "
"Liponox N-105"
Temperature 30C
Current densit~ range 0.5-5 A/dm2 With the platin~ baths of Examples 1 to 6, Hull cell tests were conducted under the conditions of 1 A and 5 min. Each example gave a grayish white smooth electrodeposit.
Example 7 Bismuth ~as bismuth methanesulfonate) 2 g/Q
Divalent tin (as stannous methanesulfonate) 18 "
Free methanesulfonic acid 150 "
"Neugen EN" ` 5 "
Temperature 25C
Current density range 0.5-3 A/dm2 Example 8 Bismuth (as bismuth benzenesulfonate) 12 g/2 Divalent tin (as tin benzenesulfonate) 8 "
Free benzenesulfonic acid 120 "
Peptone 2 "
Temperature 30C
Current density range 0.2-5 A/dm2 Example 9 Bismuth (as bismuth 2-hydroxypropanesulfonate) 10 g/~
Divalent tin (as stannous 2-hydrox~propanesulfonate) : - 7 -.
''' ' , ' . . . ~
,. .
' ' : ' ' "
.
.
~' :. .
1 3 ~
5.6 "
Lead (as lead 2-hydroxypropanesulfonate) 4.4 "
Free 2-hydroxypropanesulfonic acid 180 "
Gelatin 7 "
Temperature 20C
Current density ran~e 0.1-3 A/dm2 The plating baths of Examples 7 to 9 were subjected to Hull cell tests under the conditions of 1 A and 5 minO All gave gray-ish white smooth electrodeposits.
In order to con~irm the composition of the electrodeposit formed by the bismuth alloy plating, plating was carried out by 600-coulomb constant current electrolysis, using a stainless steel plate (0,3 x 3 x 5 cm) as the cathode, with cathode rocking at a rate of 2 m/min, while ~arying the current density over a range of 0.5 - 3 A/dm2. After each run the electrodeposit formed was scraped off by a knife and dissolved in 6N-HN03 with the ~pplication of heat. Tin was separated and the bismuth in the solution was determined by the atomic absorption-spectroscopy, The results are given in Table 1.
T a b 1 e Dk (Ajdm2) 0.5 1.0 2.0 3.0 Bi in electrodeposit, % 26,0 20.4 13,8 15.3 Current efficiency, % 89.2gO.3 73.2 56.4 .
~ 8 ---
BATHS OF ORGANIC SULFONATE SOLUTION
FOR BISMUTH AND BISMUTH ALLOY PLATING
BACKGROUND OF T~, INVENTION
This invention relates to bismut;h and bismuth alloy plating baths. More particularly, it is concerned with bismuth and bismuth alloy electroplating baths which use an organic sulfonic acid as a co-soluble complex salt of` bismu~h and the ~etal other than bismuth and give smooth electroplated deposits without the emission of highly pollutlng matter.
Bismuth is extensively used as a lubricant in nuclear reactor construction as well as in such newly opened fields as the manu-facture of recti~ier and ohmic contacts. These applications require relatively thick plates, approximately from 30 to 100 ~m in thickness. With conventional complex salt baths such as *
perchlorate, glycerate-tartrate, and Trilon baths, however, the resulting deposits ~ree of trees dendrite are at best 10 ~m thick. Ordinary baths using no complex s~lt provide only coarse=
crystal films.
Fast progress of the electronic industry in recent years has created demands Lor various bismuth-base alloys of low-melting points. Increasing importance is being attached to these low=
melting solders because o~ the introduction o~ semiconductors with more and more dellcate thermal properties. Ordinary sol-ders, typi~ied by the Sn-Pb alloy, have the disadvanta~e of *Trademark v, ,., ,. , ; .~, 131~P3 so-called low-temperature brittleness. Component parts soldered with them become brittle when placed in environmcnts below ordi nary temperature, as are encountered by the soldered parts of devices and apparatus for use in superconductive and space development projects. For services in such severe environments, therefore, low-temperature resistant solders are desirable.
Examples are Bi-Sn, Bi-In, Bi-Pb, Bi-Co, Bi-Ni, Bi-Sb, Bi-In-Sn, and Bi-Sn-Pb alloys. Since the st;~ndard electrode potential of bismuth is far nobler than those of tin, indium, and lead, there occurs practically no codeposition of these alloying elements from their simple solution. To make their deposition potentials as close to one another as possible, a camplex salt bath must be used instead!
Varied 8i-Sn alloy plating baths, for example, in the ~orm of sulfate, chloride, perchlorate, boro~luoride, and alkali baths, have hitherto been reported. Nevertheless, because o~
the electric potential difference, it is dlfficult to codeposit a relatively large proportion of bismuth to tin, and an electro-deposit of the low-~elting alloy can hardl~ be obtained. As for the Bi-In alloy plating from a perchlorate bath, the limitation to the current density range over which the codeposit is formed makes it rarely possible to obtain thick, good alloy plates.
SU~ARY OF THE INVENTION
The present invention has resulted ~rom investigations made in view o~ the foregoine. It i9 ai~ed at providing a pl-tin~
" : :
`"': ' :
~:
~3:1~ 7~
bath which consists essentially of an organic sulfonic acid that seldom poses a pollution problem and salts of bismuth and a metal other than bismuth, and gives substantially better electrodepo-sits than those from conventional inorganic acid baths, and permits easy control of the bath in alloy plating, inasmuch as the electrodeposit composition is close to the metal proportion in the bath. Thus the investigations have led to the discovery of useful acids for the above purpose.
In the case of Bi-Sn alloy pl~ating, a major disadvantage is that, where the electric potential difference between tin and bismuth is too wide for the passage of current, bismuth can be lost by its contact deposition on the anode tin surface. It has now been found that the plating bath of the invention character-istically inhibits to a large measure the unwanted bismuth deposition on the anode tin surface.
DETAILED D~SCRIPTION OF THE INVENTION
The organic sulfon~c acids to be used in accordance with the invention are sulfonic acids as aliphatic or nonbenzene alicyclic compounds of the general formula ~I) (Xl) n ~ ~ -S Os~
wherein R is a Cl 5 alkyl radical, Xl is a halogen atom or hydroxyl 9 aryl, alkylaryl, carboxyl, or sulfonyl radical which may be in any optional position of the alkyl radical, and n is an integer of O to 3, and aromatic sulfonic acids having various substituen~s o~ The formula (I.) .' ' ~ .. ' ' ~ . .
.
~3~7 ~ 3 I~(X2)m ~
wherein X2 is a halogen atom or hydroxyl, alkyl, aryl, alkylaryl, aldehyde, carboxyl, nitro, mercapto, sulfonyl, or amino radical, or two Xz's which may combine with a benzene ring to form a naphthalene ring, and m is an lnteger of 0 to 3.
Examples of these organic sulfonic aclds are methanesulfonic, ethanesulfonic, propanesul~onic, 2-propanesulfonic, butanesulfon-ic, 2-butanesulfonic, pentanesulfonlc, chloropropanesulfonic, 2-hydroxyethane-l-sulfonic, 2-hydroxypropane-l-sulfonic, 2-hy-droxybutane-l-sul~onic, 2-hydroxypentanesulfonic, allylsulfonic, ~-sulfoacetic, 2- or 3-sulfopropionic, sul~osuccinic, sulfo-maleic, sulfofumaric, benzenesulfonic, toluenesulfonic~ xylene-sulfonic, nitrobenzenesulfonic, sulfobenzoic, sulfosalicylic, 2nd benzaldehydesuifonlc acids. These acids are used alone or as a mixture of two or more. Their bismuth salts and salts of metals other than bismuth are prepared in the usual manner.
A bismuth plating bath contains such an organic sul~onic acid and its bismuth salt. In the case o~ 2 bismuth alloy plating ~ath, such an organic sulfonic acid, its bismuth salt, and ano~her or two ar more metal salts are contained.
The total concentration of bi6muth and another metal salt of the organic sul~onic acid is, in terms of the metals, from 0.5 to 200 gJ~t preferably from lO to lO0 g/~. The concentration of the free organic .... :
-. .
. .
~ 3 ~
sulfonic acid to be pre~ent in the plating bath is stoichiometrically at least an equivalent to the concentration of the bismuth and other metal salts in the bath. Preferably, the concentration of the free organic sulfonic acid is 30-400 g/Q.
The plating bath of the invention may contain peptone, gela-tin, nonionic surfactant, or other additive effective in avoiding burnt deposits due to exeessive current lntensity and in inhibit-ing dendritic growth. The concentration of the additive usually ranges from 0.01 to 50 g~l, preferably from 0.05 to 20 g/l.
*
Among typical nonionic surfactants for this use are "Epon 740", "Liponox N-105", and "Neugen EN".
~ X A M P L E S
While the present invention is illustrated by the following several examples in which certain plating bath compositions and operating conditions are used, it should be noted that the inven~
tion is not limited thereto but may be ~ariously embodied with changes in the compositions and conditions to realize the objects of obtaining uniform, smooth plated deposits.
Throughout the examples, the outward appearance of the plate obtained was e~aluated by the Hull cell test.
Example 1 Bismuth (as bismuth methanesulfonate) 20 g/l Free methanesul~onic acid 150 "
Gelatin 5 "
Temperature 25C
Current density range 0.5-S A/dm *Trademark j!
. . .
' ' '. ', ' . ' ' ~3~7~3 Example 2 Bismuth tas bismuth 2-hydroxypropanesulfonate) 15 g/~
Free 2-hydroxypropanesulfonic acid 100 "
"Epon 740"
Temperature 30C
Current density range 0.2-3 A/dm2 Example 3 Bismuth (as bismuth sulfosuccinate) 30 g/2 Free sulfosuccinic acid . 200 Peptone 5 "
Temperature 20C
Current density range 1-6 A/dm2 Example 4 Bismuth (as bismuth p-phenolsulfonate) 25 g/~
Free p-phenolsulfonic acid 120 Peptone 2 Temperature 25C
Current density range 1-5 A/dm2 Example 5 Bismuth (as bismuth p-toluenesulfonate) 6 g/~
Free p-toluenesulfonic acid 150 Gelatin 3 "
Temperature 30C
Current density range 0.2-S A/dm2 , .
. ~ . ... .
13~7~3 Bismuth (as bismuth sulfosalicylate) 10 g/Q
Free sulfosalicylic acld 200 "
"Liponox N-105"
Temperature 30C
Current densit~ range 0.5-5 A/dm2 With the platin~ baths of Examples 1 to 6, Hull cell tests were conducted under the conditions of 1 A and 5 min. Each example gave a grayish white smooth electrodeposit.
Example 7 Bismuth ~as bismuth methanesulfonate) 2 g/Q
Divalent tin (as stannous methanesulfonate) 18 "
Free methanesulfonic acid 150 "
"Neugen EN" ` 5 "
Temperature 25C
Current density range 0.5-3 A/dm2 Example 8 Bismuth (as bismuth benzenesulfonate) 12 g/2 Divalent tin (as tin benzenesulfonate) 8 "
Free benzenesulfonic acid 120 "
Peptone 2 "
Temperature 30C
Current density range 0.2-5 A/dm2 Example 9 Bismuth (as bismuth 2-hydroxypropanesulfonate) 10 g/~
Divalent tin (as stannous 2-hydrox~propanesulfonate) : - 7 -.
''' ' , ' . . . ~
,. .
' ' : ' ' "
.
.
~' :. .
1 3 ~
5.6 "
Lead (as lead 2-hydroxypropanesulfonate) 4.4 "
Free 2-hydroxypropanesulfonic acid 180 "
Gelatin 7 "
Temperature 20C
Current density ran~e 0.1-3 A/dm2 The plating baths of Examples 7 to 9 were subjected to Hull cell tests under the conditions of 1 A and 5 minO All gave gray-ish white smooth electrodeposits.
In order to con~irm the composition of the electrodeposit formed by the bismuth alloy plating, plating was carried out by 600-coulomb constant current electrolysis, using a stainless steel plate (0,3 x 3 x 5 cm) as the cathode, with cathode rocking at a rate of 2 m/min, while ~arying the current density over a range of 0.5 - 3 A/dm2. After each run the electrodeposit formed was scraped off by a knife and dissolved in 6N-HN03 with the ~pplication of heat. Tin was separated and the bismuth in the solution was determined by the atomic absorption-spectroscopy, The results are given in Table 1.
T a b 1 e Dk (Ajdm2) 0.5 1.0 2.0 3.0 Bi in electrodeposit, % 26,0 20.4 13,8 15.3 Current efficiency, % 89.2gO.3 73.2 56.4 .
~ 8 ---
Claims
1. A bismuth or bismuth alloy plating bath comprising as essential ingredients an or-ganic sulfonic acid of the general formula (X1)n - R - SO3H
wherein R is a C1-5 allyl radical, X1 is a halogen atom or hydroxyl, carboxyl, or sulfonyl radical which may be in any optional position of the alkyl radical, and n is an integer of 0 to 3, and a bismuth salt of the acid or a mixture of the bismuth salt of the acid and one or more other metal salts of the acid, said bismuth or bismuth alloy salts of the organic acid being used at a concentration, in terms of the respective metallic elements, of 0.5 to 200 g per liter of the bath, and the concen-tration of free organic sulfonic acid being 30 to 400 g per liter of the bath.
wherein R is a C1-5 allyl radical, X1 is a halogen atom or hydroxyl, carboxyl, or sulfonyl radical which may be in any optional position of the alkyl radical, and n is an integer of 0 to 3, and a bismuth salt of the acid or a mixture of the bismuth salt of the acid and one or more other metal salts of the acid, said bismuth or bismuth alloy salts of the organic acid being used at a concentration, in terms of the respective metallic elements, of 0.5 to 200 g per liter of the bath, and the concen-tration of free organic sulfonic acid being 30 to 400 g per liter of the bath.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP156361/1986 | 1986-07-04 | ||
| JP61156361A JPH0781196B2 (en) | 1986-07-04 | 1986-07-04 | Bismuth and bismuth alloy plating baths from organic sulfonates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1311713C true CA1311713C (en) | 1992-12-22 |
Family
ID=15626076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 519048 Expired - Lifetime CA1311713C (en) | 1986-07-04 | 1986-09-25 | Baths of organic sulfonate solution for bismuth and bismuth alloy plating |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0255558B1 (en) |
| JP (1) | JPH0781196B2 (en) |
| CA (1) | CA1311713C (en) |
| DE (1) | DE3682679D1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0765206B2 (en) * | 1988-09-22 | 1995-07-12 | 上村工業株式会社 | Bismuth-tin alloy electroplating method |
| JPH0765207B2 (en) * | 1988-09-22 | 1995-07-12 | 上村工業株式会社 | Bismuth-tin alloy electroplating method |
| AU632464B2 (en) * | 1988-10-14 | 1993-01-07 | Atochem North America, Inc. | A method, bath and cell for the electrodeposition of tin-bismuth alloys |
| JP2983548B2 (en) * | 1988-10-14 | 1999-11-29 | アトケム ノース アメリカ，インコーポレイティド | Electroplating of tin-bismuth alloy |
| JP2819180B2 (en) * | 1990-02-22 | 1998-10-30 | 信康 土肥 | Tin-lead-bismuth alloy plating bath |
| US5227046A (en) * | 1991-10-07 | 1993-07-13 | Unisys Corporation | Low temperature tin-bismuth electroplating system |
| JP3274232B2 (en) * | 1993-06-01 | 2002-04-15 | ディップソール株式会社 | Tin-bismuth alloy plating bath and plating method using the same |
| JP4728462B2 (en) * | 2000-02-29 | 2011-07-20 | 日本リーロナール有限会社 | Tin electroplating solution and plating method |
| US6736954B2 (en) * | 2001-10-02 | 2004-05-18 | Shipley Company, L.L.C. | Plating bath and method for depositing a metal layer on a substrate |
| DE102005016819B4 (en) * | 2005-04-12 | 2009-10-01 | Dr.-Ing. Max Schlötter GmbH & Co KG | Electrolyte, process for the deposition of tin-bismuth alloy layers and use of the electrolyte |
| JP7508077B2 (en) * | 2019-04-03 | 2024-07-01 | 奥野製薬工業株式会社 | Bi-Sb alloy plating solution for electroplating |
| CN113293409B (en) * | 2021-05-28 | 2022-06-24 | 中南大学 | A kind of method for electrolytic preparation of dense and flat bismuth metal |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5967387A (en) * | 1982-10-08 | 1984-04-17 | Hiyougoken | Tin, lead and tin-lead alloy plating baths |
| US4565610A (en) | 1983-12-22 | 1986-01-21 | Learonal, Inc. | Bath and process for plating lead and lead/tin alloys |
| US4565609A (en) | 1983-12-22 | 1986-01-21 | Learonal, Inc. | Bath and process for plating tin, lead and tin-lead alloys |
-
1986
- 1986-07-04 JP JP61156361A patent/JPH0781196B2/en not_active Expired - Lifetime
- 1986-09-22 DE DE8686113044T patent/DE3682679D1/en not_active Expired - Lifetime
- 1986-09-22 EP EP19860113044 patent/EP0255558B1/en not_active Expired
- 1986-09-25 CA CA 519048 patent/CA1311713C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3682679D1 (en) | 1992-01-09 |
| EP0255558B1 (en) | 1991-11-27 |
| JPS6314887A (en) | 1988-01-22 |
| EP0255558A1 (en) | 1988-02-10 |
| JPH0781196B2 (en) | 1995-08-30 |
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