EP0853139A1 - Electrolyte for electroless gold plating - Google Patents
Electrolyte for electroless gold plating Download PDFInfo
- Publication number
- EP0853139A1 EP0853139A1 EP97121804A EP97121804A EP0853139A1 EP 0853139 A1 EP0853139 A1 EP 0853139A1 EP 97121804 A EP97121804 A EP 97121804A EP 97121804 A EP97121804 A EP 97121804A EP 0853139 A1 EP0853139 A1 EP 0853139A1
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- European Patent Office
- Prior art keywords
- electrolyte
- order
- gold
- potassium
- sodium
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- 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.)
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- 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
Definitions
- the invention relates to an electrolyte for reductive gold deposition and a process for reductive gold deposition.
- the reductive and therefore electroless gold plating is gaining more and more of importance, especially in applications where very small structures, that have no electrical connection should be gold-plated.
- the so far known Electrolytes for reductive gold deposition have the serious one Disadvantage that they are not sufficiently stable, as it is in the known Electrolytes very spontaneously decompose. Because of that resulting lack of bath stability is therefore the use of the known Electrolytes for reductive gold deposition on a technical scale only very much difficult possible. It is therefore an object of the invention to provide an electrolyte for reductive gold
- the measures according to the invention are advantageous created an electrolyte in which a spontaneous reduction and thus its Destruction is largely suppressed. This results in high bath stability, so that the electrolyte according to the invention on a technical scale for reductive Gold plating can be used.
- Another advantageous development of the invention provides that as a reaction accelerator Thallium I ions the electrolyte according to the invention as a reaction accelerator are clogged.
- the electrolyte according to the invention has potassium, sodium or Ammonium gold I cyanide or the corresponding gold III cyanide compounds on the order of 0.1 g / l to about 20 g / l gold, with preference is that the gold content of the aforementioned compounds in the range of about 0.5 g / l to about 5 g / l.
- a second component of the electrolyte described is free potassium, sodium or Ammonium cyanide in the order of about 0.1 g / l to 25 g / l, it being preferred that the proportion of the aforementioned free cyanides in the range from about 3 g / l to 6 g / l.
- the electrolyte has potassium, sodium or ammonium sulfite in one Of the order of about 0.1 g / l to 50 g / l, with it being preferred that the The content of the aforementioned sulfite is in the range of approximately 5 g / l to 15 g / l.
- the electrolyte has an aromatic (mono-, di- or tri-) nitro compound, e.g. 3,5-dinitrobenzoic acid, on the order of approximately 0.01 g / l to about 10 g / l, again it being preferred that the concentration the aforementioned acid is in the range of about 0.05 to 1.0 g / l.
- aromatic (mono-, di- or tri-) nitro compound e.g. 3,5-dinitrobenzoic acid
- Another component of the electrolyte described is free alkali, the is preferably present as potassium or sodium hydroxide.
- concentration of the free alkali is of the order of about 1 g / l to 100 g / l, the Range of about 10 g / l to 25 g / l is preferred.
- Another component of the electrolyte are one or more complexing agents from the group of hydroxycarboxylic acids, phosphonic acids, nitriloacetic acids or ethylenediamine acetic acids on the order of about 1 g / L to 50 g / l with an optimum of 10 g / l to 30 g / l.
- the electrolyte described has one or more reducing agents from the group of boranes or boranates, the proportion of these reducing agents on the order of about 0.1 g / l to 50 g / l with a Optimal from approx. 1 g / l to 10 g / l.
- an optional reaction accelerator preferably a water soluble thallium I compound be provided in the order of 0.1 mg / l to about 100 mg / l is added to the electrolyte, the preferred range of the aforementioned Compound ranges from about 1 mg / l to 20 mg / l.
- a temperature of approximately is used to carry out the reductive gold deposition 60 ° to 95 ° of the electrolyte and in particular the range from 75 ° to 85 ° C preferred.
- the electrolyte described above was used at a bath temperature at 80 ° C a circuit board coated with chemical nickel and 0.1 ⁇ exchange gold in 20 min. reinforced to an approx. 0.4 ⁇ gold layer, whereby the reductive Gold plating produced gold layer has a purity of 99.9%.
- the layer produced from the electrolyte described is suitable therefore to a particularly high degree for gold wire bonding.
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- 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)
- Electroplating And Plating Baths Therefor (AREA)
- Chemically Coating (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
Die Erfindung betrifft einen Elektrolyten für eine reduktive Goldabscheidung sowie ein Verfahren zur reduktiven Goldabscheidung.The invention relates to an electrolyte for reductive gold deposition and a process for reductive gold deposition.
Die reduktive und daher außenstromlose Goldabscheidung gewinnt immer mehr an Bedeutung, insbesondere in Anwendungen, bei denen sehr kleine Strukturen, die keine elektrische Anbindung haben, vergoldet werden sollen. Die bis jetzt bekannten Elektrolyte zur reduktiven Goldabscheidung besitzen aber den gravierenden Nachteil, daß sie nicht hinreichend stabil sind, da es bei den bekannten Elektrolyten sehr häufig zu einer Spontanzersetzung kommt. Aufgrund der daraus resultierenden mangelnden Badstabilität ist daher der Einsatz der bekannten Elektrolyte zur reduktiven Goldabscheidung im technischen Maßstab nur sehr schwierig möglich. Es ist daher Aufgabe der Erfindung, einen Elektrolyten zur reduktiven GoldabThe reductive and therefore electroless gold plating is gaining more and more of importance, especially in applications where very small structures, that have no electrical connection should be gold-plated. The so far known Electrolytes for reductive gold deposition have the serious one Disadvantage that they are not sufficiently stable, as it is in the known Electrolytes very spontaneously decompose. Because of that resulting lack of bath stability is therefore the use of the known Electrolytes for reductive gold deposition on a technical scale only very much difficult possible. It is therefore an object of the invention to provide an electrolyte for reductive gold
scheidung sowie ein diesen Elektrolyten nutzendes Verfahren zu schaffen, bei dem eine hinreichend große Badstabilität gegeben ist, um einen Einsatz im technischen Maßstab zu ermöglichen.separation and to create a process using these electrolytes which has a sufficiently large bath stability to be used in technical To enable scale.
Diese Aufgabe ist erfindungsgemäß dadurch gelöst, daß der Elektrolyt für ein reduktives Goldbad
- Kalium-, Natrium- oder Ammoniumgold-I-cyanid oder Gold-III-cyanidverbindungen in einer Größenordnung von ungefähr 0,1 g/l bis ungefähr 20 g/l,
- freies Kalium-, Natrium- oder Ammoniumcyanid in einer Größenordnung von ungefähr 0,1 g/l bis 25 g/l,
- Kalium-, Natrium- oder Ammoniumsulfit in einer Größenordnung von ungefähr 0,1 g/l bis ungefähr 50 g/l,
- eine aromatische Nitroverbindung in einer Größenordnung von ungefähr 0,01 g/l bis ungefähr 10 g/l,
- freies Alkali in einer Größenordnung von ungefähr 1 g/l bis ungefähr 100 g/l,
- einen oder mehrere Komplexbildner aus der Gruppe der Hydroxycarbonsäuren. Phosphonsäuren, Nitriloessigsäuren oder Aethylendiaminessigsäuren in einer Größenordnung von ungefähr 1 g/l bis ungefähr 50 g/l,
- ein oder mehrere Reduktionsmittel aus der Gruppe der Borane oder Boranate in einer Größenordnung von 0,1 g/l bis 50 g/l
- Potassium, sodium or ammonium gold-I-cyanide or gold-III-cyanide compounds in the order of about 0.1 g / l to about 20 g / l,
- free potassium, sodium or ammonium cyanide in the order of about 0.1 g / l to 25 g / l,
- Potassium, sodium or ammonium sulfite in the order of about 0.1 g / l to about 50 g / l,
- an aromatic nitro compound on the order of about 0.01 g / l to about 10 g / l,
- free alkali in the order of about 1 g / l to about 100 g / l,
- one or more complexing agents from the group of hydroxycarboxylic acids. Phosphonic acids, nitriloacetic acids or ethylenediamine acetic acids in a range from approximately 1 g / l to approximately 50 g / l,
- one or more reducing agents from the group of the boranes or boranates in the order of 0.1 g / l to 50 g / l
Durch die erfindungsgemäßen Maßnahmen wird in vorteilhafter Art und Weise ein Elektrolyt geschaffen, bei dem eine spontane Ausreduktion und damit dessen Zerstörung weitgehend unterdrückt ist. Hierdurch resultiert eine hohe Badstabilität, so daß der erfindungsgemäße Elektrolyt im technischen Maßstab zur reduktiven Goldabscheidung einsetzbar ist.The measures according to the invention are advantageous created an electrolyte in which a spontaneous reduction and thus its Destruction is largely suppressed. This results in high bath stability, so that the electrolyte according to the invention on a technical scale for reductive Gold plating can be used.
Eine weitere vorteilhafte Weiterbildung der Erfindung sieht vor, daß als Reaktionsbeschleuniger Thallium-I-Ionen dem erfindungsgemäßen Elektrolyten als Reaktionsbeschleuniger zugesetzt sind.Another advantageous development of the invention provides that as a reaction accelerator Thallium I ions the electrolyte according to the invention as a reaction accelerator are clogged.
Weitere Einzelheiten und Vorteile der Erfindung sind dem Ausführungsbeispiel zu entnehmen, das im folgenden beschrieben wird:Further details and advantages of the invention are the embodiment refer to the following:
Der erfindungsgemäße Elektrolyt weist als ersten Bestandteil Kalium-, Natrium- oder Ammoniumgold-I-cyanid bzw. die entsprechenden Gold-III-cyanidverbindungen in einer Größenordnung von 0,1 g/l bis ungefähr 20 g/l Gold auf, wobei bevorzugt wird, daß der Goldgehalt der vorgenannten Verbindungen im Bereich von ungefähr 0,5 g/l bis ungefähr 5 g/l liegt.The electrolyte according to the invention has potassium, sodium or Ammonium gold I cyanide or the corresponding gold III cyanide compounds on the order of 0.1 g / l to about 20 g / l gold, with preference is that the gold content of the aforementioned compounds in the range of about 0.5 g / l to about 5 g / l.
Eine zweite Komponente des beschriebenen Elektrolyten ist freies Kalium-, Natrium- oder Ammoniumcyanid in einer Größenordnung von ungefähr 0,1 g/l bis 25 g/l, wobei bevorzugt wird, daß der Anteil der vorgenannten freien Cyanide im Bereich von ungefähr 3 g/l bis 6 g/l liegt.A second component of the electrolyte described is free potassium, sodium or Ammonium cyanide in the order of about 0.1 g / l to 25 g / l, it being preferred that the proportion of the aforementioned free cyanides in the range from about 3 g / l to 6 g / l.
Desweiteren weist der Elektrolyt Kalium-, Natrium- oder Ammoniumsulfit in einer Größenordnung von ungefähr 0,1 g/l bis 50 g/l auf, wobei bevorzugt wird, daß der Gehalt des vorgenannten Sulfits im Bereich von ungefähr 5 g/l bis 15 g/l liegt.Furthermore, the electrolyte has potassium, sodium or ammonium sulfite in one Of the order of about 0.1 g / l to 50 g / l, with it being preferred that the The content of the aforementioned sulfite is in the range of approximately 5 g / l to 15 g / l.
Desweiteren weist der Elektrolyt eine aromatische (mono-, di- oder tri-) Nitroverbindung, z.B. 3,5-Dinitrobenzoesäure, in der Größenordnung von ungefähr 0,01 g/l bis ungefähr 10 g/l auf, wobei wiederum bevorzugt wird, daß die Konzentration der vorgenannten Säure in den Bereich von ungefähr 0,05 bis 1,0 g/l liegt.Furthermore, the electrolyte has an aromatic (mono-, di- or tri-) nitro compound, e.g. 3,5-dinitrobenzoic acid, on the order of approximately 0.01 g / l to about 10 g / l, again it being preferred that the concentration the aforementioned acid is in the range of about 0.05 to 1.0 g / l.
Ein weiterer Bestandteil des beschriebenen Elektrolyten ist freies Alkali, das vorzugsweise als Kalium- oder Natriumhydroxid vorliegt. Die Konzentration des freien Alkalis liegt in der Größenordnung von ungefähr 1 g/l bis 100 g/l, wobei der Bereich von ungefähr 10 g/l bis 25 g/l bevorzugt wird.Another component of the electrolyte described is free alkali, the is preferably present as potassium or sodium hydroxide. The concentration of the free alkali is of the order of about 1 g / l to 100 g / l, the Range of about 10 g / l to 25 g / l is preferred.
Ein weiterer Bestandteil des Elektrolyten sind ein oder mehrere Komplexbildner aus der Gruppe der Hydroxycarbonsäuren, Phosphonsäuren, Nitriloessigsäuren oder Aethylendiaminessigsäuren in einer Größenordnung von ungefähr 1 g/l bis 50 g/l mit einem Optimum von 10 g/l bis 30 g/l.Another component of the electrolyte are one or more complexing agents from the group of hydroxycarboxylic acids, phosphonic acids, nitriloacetic acids or ethylenediamine acetic acids on the order of about 1 g / L to 50 g / l with an optimum of 10 g / l to 30 g / l.
Desweiteren weist der beschriebene Elektrolyt einen oder mehrere Reduktionsmittel aus der Gruppe der Borane oder Boranate auf, wobei der Anteil dieser Reduktionsmittel in der Größenordnung von ungefähr 0,1 g/l bis 50 g/l mit einem Optimum von ca. 1 g/l bis 10 g/l liegt.Furthermore, the electrolyte described has one or more reducing agents from the group of boranes or boranates, the proportion of these reducing agents on the order of about 0.1 g / l to 50 g / l with a Optimal from approx. 1 g / l to 10 g / l.
Um die Reaktion des Elektrolyten zu beschleunigen, kann optional noch ein Reaktionsbeschleuniger, vorzugsweise eine wasserlösliche Thallium-I-Verbindung vorgesehen sein, die in einer Größenordnung von 0,1 mg/l bis ungefähr 100 mg/l dem Elektrolyten zugesetzt wird, wobei der bevorzugte Bereich der vorgenannten Verbindung im Bereich von ungefähr 1 mg/l bis 20 mg/l liegt. To accelerate the reaction of the electrolyte, an optional reaction accelerator, preferably a water soluble thallium I compound be provided in the order of 0.1 mg / l to about 100 mg / l is added to the electrolyte, the preferred range of the aforementioned Compound ranges from about 1 mg / l to 20 mg / l.
Versuche haben ergeben, daß eine bevorzugte Zusammensetzung des Elektrolyten im wesentlichen wie folgt lautet:
- 1,0 g/l Gold als freies Kaliumgold-I-cyanid,
- 5,0 g/l freies Kaliumcyanid,
- 50 g/l 1-Hydroxid-ethan-1.1-diphosphonsäure,
- 10 g/l Kaliumsulfit
- 0,2 g/l 3,5-Dinitrobenzoesäure,
- 22 g/l freies Kaliumhydroxid
- 5,0 g/l Dimethylaminboran,
- 1.0 g / l gold as free potassium gold i-cyanide,
- 5.0 g / l free potassium cyanide,
- 50 g / l 1-hydroxide-ethane-1,1-diphosphonic acid,
- 10 g / l potassium sulfite
- 0.2 g / l 3,5-dinitrobenzoic acid,
- 22 g / l free potassium hydroxide
- 5.0 g / l dimethylamine borane,
Zur Durchführung der reduktiven Goldabscheidung wird eine Temperatur von ungefähr 60° bis 95° des Elektrolyten und insbesondere der Bereich von 75° bis 85°C bevorzugt.A temperature of approximately is used to carry out the reductive gold deposition 60 ° to 95 ° of the electrolyte and in particular the range from 75 ° to 85 ° C preferred.
Mit dem vorstehend beschriebenen Elektrolyten wurde bei einer Badtemperatur von 80°C eine mit Chemisch-Nickel und 0,1 µ Austauschgold beschichtete Leiterplatte in 20 min. auf eine ca. 0,4 µ Goldschicht verstärkt, wobei die durch die reduktive Goldabscheidung erzeugte Goldschicht eine Reinheit von 99,9 % aufweist. Die aus dem beschriebenen Elektrolyten hergestellte Schicht eignet sich daher in besonders hohem Maße für eine Golddraht-Bondung.The electrolyte described above was used at a bath temperature at 80 ° C a circuit board coated with chemical nickel and 0.1 µ exchange gold in 20 min. reinforced to an approx. 0.4 µ gold layer, whereby the reductive Gold plating produced gold layer has a purity of 99.9%. The layer produced from the electrolyte described is suitable therefore to a particularly high degree for gold wire bonding.
Zusammenfassend ist festzustellen, daß durch die beschriebenen Maßnahmen, die im wesentlichen aus einer Kombination von Gold mit Sulfit, welches die erwünschte Badstabilität bewirkt, mit einer aromatischen (mono-, di- oder tri-) Nitroverbindung, z.B. 3,5-Dinitrobenzoesäure, und mit freiem Cyanid bestehen, eine hohe Badstabilität eines reduktiven Goldbades erzielt wird, die es nun erlaubt, eine reduktive Goldabscheidung im technischen Maßstab durchzuführen.In summary, it can be stated that the measures described which is essentially a combination of gold with sulfite, which is the desired one Bath stability, with an aromatic (mono-, di- or tri-) nitro compound, e.g. 3,5-dinitrobenzoic acid, and insist with free cyanide, one high bath stability of a reductive gold bath is achieved, which now allows one perform reductive gold plating on an industrial scale.
Claims (15)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19651900A DE19651900A1 (en) | 1996-12-13 | 1996-12-13 | Electrolyte for reductive gold deposition |
DE19651900 | 1996-12-13 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0853139A1 true EP0853139A1 (en) | 1998-07-15 |
EP0853139B1 EP0853139B1 (en) | 2001-10-10 |
Family
ID=7814613
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97121804A Expired - Lifetime EP0853139B1 (en) | 1996-12-13 | 1997-12-11 | Electrolyte for electroless gold plating |
Country Status (2)
Country | Link |
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EP (1) | EP0853139B1 (en) |
DE (2) | DE19651900A1 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02133594A (en) * | 1988-11-14 | 1990-05-22 | Shinko Electric Ind Co Ltd | Gold plating solution |
US5232492A (en) * | 1992-01-23 | 1993-08-03 | Applied Electroless Concepts Inc. | Electroless gold plating composition |
EP0702099A1 (en) * | 1994-08-19 | 1996-03-20 | Electroplating Engineers of Japan Limited | Electroless gold plating solution |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2225026A (en) * | 1988-11-22 | 1990-05-23 | American Chem & Refining Co | Electroless gold plating composition |
JP2927142B2 (en) * | 1993-03-26 | 1999-07-28 | 上村工業株式会社 | Electroless gold plating bath and electroless gold plating method |
US5338343A (en) * | 1993-07-23 | 1994-08-16 | Technic Incorporated | Catalytic electroless gold plating baths |
EP0697470A1 (en) * | 1994-08-19 | 1996-02-21 | Electroplating Engineers of Japan Limited | Electroless gold plating solution |
-
1996
- 1996-12-13 DE DE19651900A patent/DE19651900A1/en not_active Withdrawn
-
1997
- 1997-12-11 DE DE59704863T patent/DE59704863D1/en not_active Expired - Fee Related
- 1997-12-11 EP EP97121804A patent/EP0853139B1/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02133594A (en) * | 1988-11-14 | 1990-05-22 | Shinko Electric Ind Co Ltd | Gold plating solution |
US5232492A (en) * | 1992-01-23 | 1993-08-03 | Applied Electroless Concepts Inc. | Electroless gold plating composition |
EP0702099A1 (en) * | 1994-08-19 | 1996-03-20 | Electroplating Engineers of Japan Limited | Electroless gold plating solution |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 9026, Derwent World Patents Index; Class M11, AN 90-198989, XP002062526 * |
Also Published As
Publication number | Publication date |
---|---|
DE59704863D1 (en) | 2001-11-15 |
DE19651900A1 (en) | 1998-06-18 |
EP0853139B1 (en) | 2001-10-10 |
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