WO1992002663A1 - Stabiles, stromloses, wässriges, saures goldbad zur abscheidung von gold und dessen verwendung - Google Patents
Stabiles, stromloses, wässriges, saures goldbad zur abscheidung von gold und dessen verwendung Download PDFInfo
- Publication number
- WO1992002663A1 WO1992002663A1 PCT/DE1991/000624 DE9100624W WO9202663A1 WO 1992002663 A1 WO1992002663 A1 WO 1992002663A1 DE 9100624 W DE9100624 W DE 9100624W WO 9202663 A1 WO9202663 A1 WO 9202663A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gold
- stable
- acid
- deposition
- bath
- Prior art date
Links
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000010931 gold Substances 0.000 title claims abstract description 34
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 34
- 230000008021 deposition Effects 0.000 title claims abstract description 13
- 239000011260 aqueous acid Substances 0.000 title abstract 2
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 239000008139 complexing agent Substances 0.000 claims description 17
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- -1 carboxymethylene Chemical group 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- KSXHZOTTWSNEHY-UHFFFAOYSA-N 3-[3-(2-cyanoethoxy)-2,2-bis(2-cyanoethoxymethyl)propoxy]propanenitrile Chemical group N#CCCOCC(COCCC#N)(COCCC#N)COCCC#N KSXHZOTTWSNEHY-UHFFFAOYSA-N 0.000 description 1
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- DLEPCXYNAPUMDZ-UHFFFAOYSA-N butan-2-ylphosphonic acid Chemical compound CCC(C)P(O)(O)=O DLEPCXYNAPUMDZ-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 1
- CBMIPXHVOVTTTL-UHFFFAOYSA-N gold(3+) Chemical compound [Au+3] CBMIPXHVOVTTTL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
Definitions
- the invention relates to a stable, currentless, aqueous, acidic gold bath for the deposition of gold and its use.
- the bath according to the invention containing the anion tetracyano gold (III), a complexing agent or a mixture of several complexing agents, an acid or an acid mixture, is suitable for electroless deposition of gold on metals that are less noble than gold, as well as on alloys thereof Metals.
- Gold baths for the electroless deposition of gold are already known, for example from the documents DE-PS 3640028, US Pat. No. 4,830,668 and GB-PS 20 99 460. These are gold baths which predominantly contain an alkali metal dicyanoaurate - (I) or Contain Alkalitetracyanoaurat- (III), a complexing agent and a reducing agent. All these baths generally have an unsatisfactory stability and decompose with the deposition of metallic gold or gold (I) cyanide.
- the object of the present invention is to deposit in the acidic range from the tetracyano gold (III) gold onto metals or their alloys and at the same time to provide a more stable gold bath.
- REPLACEMENT LEAF N-bis (carboxymethylene) -1-aminoethane-l, 1-diphosphonic acid and 2-phosphonobutane-l, 2,4-tricartvonic acid have proven particularly useful as complexing agents in the baths according to the invention.
- a particular advantage of the bath according to the invention is that layers up to 0.5 ⁇ m are already obtained with gold contents in the bath of 1.0 g / 1 gold.
- the bath thus enables the gold-plating of alloys that are common in the semiconductor industry, for example iron-nickel-cobalt alloys and chemically reductively deposited nickel alloys such as nickel-phosphorus, nickel-boron and pure nickel.
- carboxymethylene-amino-alkyl-phosphenoic acids and / or phosphonalkyl carboxylic acids are used as complexing agents, which allow a substantial increase in the deposition rate and higher layer thicknesses, which was not foreseeable.
- the acids used are, for example, sulfuric acid or phosphoric acid or mixtures thereof.
- the basic composition of the bath according to the invention is, for example, as follows:
- the working temperature of the bath is usually between 70 and 90 ° C. It was found that there is no decomposition of the bath even at higher temperatures, e.g. for the precipitation of elemental gold. Another advantage of the bath is that it can be used repeatedly and that the gold salt can be replenished as required.
- the bath according to the invention has a constant deposition rate up to layer thicknesses of 0.5 ⁇ m, which is dependent on the gold content and the temperature.
- the bath according to the invention can be used for gold layers of soldered connections which result from crystal or wire bonding, which is of particular technical value.
- the high deposition speed also enables use in decorative gilding. A uniform yellow layer can be observed after seconds.
- the stable bath compositions listed below can be used to deposit very uniform and ductile coatings under the working conditions listed.
- the invention also relates to the use of the gold baths according to the invention for the deposition of gold on metals which are less noble than gold or on alloys of these metals.
- Potassium tetracyanoaurate-III 6.0 g / i complex 2-phosphonobutane-1,2,4-tricarboxylic acid 40.0 ml / 1 sulfuric acid / phosphoric acid 1 50.0 ml / 1 pH value less than 1 temperature 60 ° C
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Manufacture And Refinement Of Metals (AREA)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE59104436T DE59104436D1 (de) | 1990-08-02 | 1991-08-01 | Stabiles, stromloses, wässriges, saures goldbad zur abscheidung von gold und dessen verwendung. |
| US07/978,690 US5322552A (en) | 1990-08-02 | 1991-08-01 | Stable, electroless, aqueous, acidic gold bath for depositing gold and the use thereof |
| EP91913280A EP0542771B1 (de) | 1990-08-02 | 1991-08-01 | Stabiles, stromloses, wässriges, saures goldbad zur abscheidung von gold und dessen verwendung |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4024764.3 | 1990-08-02 | ||
| DE4024764A DE4024764C1 (en, 2012) | 1990-08-02 | 1990-08-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992002663A1 true WO1992002663A1 (de) | 1992-02-20 |
Family
ID=6411638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/DE1991/000624 WO1992002663A1 (de) | 1990-08-02 | 1991-08-01 | Stabiles, stromloses, wässriges, saures goldbad zur abscheidung von gold und dessen verwendung |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5322552A (en, 2012) |
| EP (1) | EP0542771B1 (en, 2012) |
| JP (1) | JPH05509360A (en, 2012) |
| AT (1) | ATE117740T1 (en, 2012) |
| DE (2) | DE4024764C1 (en, 2012) |
| TW (1) | TW241312B (en, 2012) |
| WO (1) | WO1992002663A1 (en, 2012) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19745601A1 (de) * | 1997-10-08 | 1999-04-15 | Fraunhofer Ges Forschung | Lösung und Verfahren zum stromlosen Abscheiden von Goldschichten |
| DE19745602C1 (de) * | 1997-10-08 | 1999-07-15 | Atotech Deutschland Gmbh | Verfahren und Lösung zur Herstellung von Goldschichten |
| DE102009041264A1 (de) | 2009-09-11 | 2011-03-24 | IPHT Jena Institut für Photonische Technologien e.V. | Verfahren zur Herstellung von optisch aktiven Nanostrukturen |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5935306A (en) * | 1998-02-10 | 1999-08-10 | Technic Inc. | Electroless gold plating bath |
| JP4116718B2 (ja) * | 1998-11-05 | 2008-07-09 | 日本リーロナール有限会社 | 無電解金めっき方法及びそれに使用する無電解金めっき液 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3614090C1 (en) * | 1986-04-25 | 1987-04-30 | Heraeus Gmbh W C | Bath for the currentless deposition of gold layers |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4374876A (en) * | 1981-06-02 | 1983-02-22 | Occidental Chemical Corporation | Process for the immersion deposition of gold |
| US4474838A (en) * | 1982-12-01 | 1984-10-02 | Omi International Corporation | Electroless direct deposition of gold on metallized ceramics |
| DE3640028C1 (de) * | 1986-11-24 | 1987-10-01 | Heraeus Gmbh W C | Saures Bad fuer das stromlose Abscheiden von Goldschichten |
| DE3707817A1 (de) * | 1987-03-09 | 1988-09-22 | Schering Ag | Stabilisiertes alkalisches goldbad zur stromlosen abscheidung von gold |
| US4919720A (en) * | 1988-06-30 | 1990-04-24 | Learonal, Inc. | Electroless gold plating solutions |
-
1990
- 1990-08-02 DE DE4024764A patent/DE4024764C1/de not_active Expired - Lifetime
-
1991
- 1991-08-01 AT AT91913280T patent/ATE117740T1/de not_active IP Right Cessation
- 1991-08-01 WO PCT/DE1991/000624 patent/WO1992002663A1/de active IP Right Grant
- 1991-08-01 EP EP91913280A patent/EP0542771B1/de not_active Expired - Lifetime
- 1991-08-01 US US07/978,690 patent/US5322552A/en not_active Expired - Fee Related
- 1991-08-01 JP JP3512501A patent/JPH05509360A/ja active Pending
- 1991-08-01 DE DE59104436T patent/DE59104436D1/de not_active Expired - Fee Related
-
1992
- 1992-09-04 TW TW081107004A patent/TW241312B/zh active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3614090C1 (en) * | 1986-04-25 | 1987-04-30 | Heraeus Gmbh W C | Bath for the currentless deposition of gold layers |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19745601A1 (de) * | 1997-10-08 | 1999-04-15 | Fraunhofer Ges Forschung | Lösung und Verfahren zum stromlosen Abscheiden von Goldschichten |
| DE19745602C1 (de) * | 1997-10-08 | 1999-07-15 | Atotech Deutschland Gmbh | Verfahren und Lösung zur Herstellung von Goldschichten |
| DE19745601C2 (de) * | 1997-10-08 | 2001-07-12 | Fraunhofer Ges Forschung | Lösung und Verfahren zum stromlosen Abscheiden von Goldschichten sowie Verwendung der Lösung |
| US6336962B1 (en) | 1997-10-08 | 2002-01-08 | Atotech Deutschland Gmbh | Method and solution for producing gold coating |
| DE102009041264A1 (de) | 2009-09-11 | 2011-03-24 | IPHT Jena Institut für Photonische Technologien e.V. | Verfahren zur Herstellung von optisch aktiven Nanostrukturen |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE117740T1 (de) | 1995-02-15 |
| US5322552A (en) | 1994-06-21 |
| EP0542771A1 (de) | 1993-05-26 |
| TW241312B (en, 2012) | 1995-02-21 |
| DE4024764C1 (en, 2012) | 1991-10-10 |
| JPH05509360A (ja) | 1993-12-22 |
| DE59104436D1 (de) | 1995-03-09 |
| EP0542771B1 (de) | 1995-01-25 |
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