United States Patent [191 [11] 3,989,800

Gansinger [451 Nov. 2, 1976

[54] ALKALI METAL GOLD CYANIDE METHOD Primary Examiner—-Earl C. Thomas

Attorney, Agent, or Firm—-Harry M. Weiss; Lowell E.
[75] Inventor: Grant N. Gansinger, Phoenix, Ariz. Clark
[73] Assignee: Motorola, Inc., Chicago, Ill.
[22] Filed: Feb. 18, 1975
[21] Appl. No.: 550,694 [57] ABSTRACT
Related US. Application Data This disclosure relates to a method for preparing alkali
[63] Continuation-impart of Ser. No. 427,747, Dec. 26, metal gold cyanide which has been found to be partic
1973, abandoned. ularly useful in gold electroplating operations in the
semiconductor industry in order to provide electrical
[52] US. Cl. ............................ .. 423/364; 204/43 G; contacts vto semiconductor devices. In the process,
204/46 G; 423/371 ?nely divided gold metal particles are reacted with hy
[51] Int. Cl.2 .......................................... .. C01C 3/11 drogen peroxide and alkali metal cyanide to produce
[58] Field of Search ........ .. 423/364, 371; 204/43 G, univalent alkali metal gold cyanide. The alkali metal
204/46 G gold cyanide is then acidi?ed with a mineral acid in
order to precipitate out gold cyanide. The gold cya
[56]‘ References Cited nide is subsequently removed by ?ltration, washed and
UNITED STATES PATENTS redissolved in a solution of alkali metal cyanide
thereby yielding the ?nal alkali metal gold cyanide
3,112,174 11/1963 Freedman..' ....................... .. 423/364
end product in its pure state.
OTHER PUBLICATIONS
Sneed et al., “Comprehensive Inorganic Chemistry”,
vol. 2, Copper, Silver & Gold, D. Van Nostrand Co., 5 Claims, No Drawings
Inc. New York, 1954, pp. 195-197, 230, 232.
 3,989,800
1
difficult to control on a small scale. Additionally, the
ALKALI METAL GOLD CYANIDE METHOD price or cost per ounce together with the pre-re?ning ,
This is a‘continuation-in-part of copending applica charges to‘ convert gold to potassium gold cyanide
tion Ser. No. 427,747 ?ledDec. 26, 1973 and now using the prior art techniques was extremely high.
abandoned. - ‘ ’ As a result, a need existed to ?nd a method for over
coming allof the above disadvantages associated with
BACKGROUND OF THE INVENTION . the prior art methods for producing potassium gold
1. Field of the Invention ' v cyanide. Additionally, the new method would have to
This invention relates generally to a method for pro produce potassium gold cyanide without the previous
ducing alkali metal gold cyanide and, more particu preprocessing step of producing the gold into a foil, but
larly, to a method for producingv alkali metal gold cya would utilize ?nely divided gold metal particles in the
nide starting from a mixture of ?nely divided’ gold form of gold sand‘which is the usual ?nal product of a
metal particles, hydrogen peroxide, and alkali metal gold reclaiming and re?ning process that exists in semi
cyanide. . conductor manufacturing gold salvage operations.
2. Background of the Prior Art 15
Potassium gold cyanide has become a very popular SUMMARY OF THE INVENTION
‘chemical compound in the semiconductor industry for It is an object of this invention to provide an im
use in electroplating gold to be used as contacts on proved method for producing alkali metal gold cya
semiconductor devices. As a result» of this great impor- ‘ nide.
tance of the potassium gold cyanide material,'it soon 20 It is another object of this invention to provide an
became very evident that improved processing tech improved method for producing alkali metal gold cya
niques were needed to handle the gold deposited mate nide by chemical means. ‘
rial that was not utilized in the fabrication of the gold Itis a still further object of this invention to produce
contacts for the semiconductor devices. In carrying out ‘pure alkali metal gold cyanide'starting with ?nely di
the electroplating process for depositing‘ gold onto the 25 vided gold metal particles. '
semiconductor devices, it often occurred that various Now it has been found-in accordance with this inven
other parts were coated with gold as it was dif?cult, if tion that pure alkali metal gold cyanide can be readily
not impossible, to selectively control the electroplating provided by a process which comprises reacting ?nely
process to only deposit gold onto the desired portions divided gold particles with hydrogenperoxide and al
of the semiconductor devices. The natural result of this kali metal cyanide to provide a reaction mixture con
additional or excess electroplating was that gold often taining alkali metal gold cyanide and soluble inorganic
was deposited onto objects such as holders for the by-products; acidifying the reaction mixture with a
semiconductor ~ products I or other; similar» objects that mineral acid to provide insoluble gold cyanide; remov
were an integral part of the electroplating ‘process. This ing said insoluble gold cyanide from the reaction mix
was recognized by the workers skilled- in the electro 35 ture; and reacting said insoluble gold cyanide with
plating arts and various techniques were tried to de alkali metal cyanide to produce alkali metal gold cya
velop methods for salvaging the gold deposited on un nide.
desired substrates. -
Many attempts at recycling the excess gold deposited DESCRIPTION OF THE INVENTION
onto undesired substrates utilized electrolysis which is More in detail, the process of this invention proceeds
an inherently slow process that moreover requires the in accordance with the following general equations
preprocessing of gold into anodes before being incor wherein M is an alkali metal, e.g., sodium, potassium,
porated into electrolytic potassium gold cyanide pro etc., HA is a mineral acid and A is the anion of a min
ducing cells. In order to obtain cyanide-free product, eral acid:
fractional crystallization was then employed as the 45
puri?cation process. Due to the physical properties of I
both cyanide and potassium gold chloride, fractional
crystallization is an inef?cient and therefor costly
method to separate the two substances. Although the
resultant ?nal product derived from the fractional crys 50 b. ",0, + MCN + ",0 -> Mr-rcon + NH;.
tallization process is substantially cyanide-free, its pu
rity, mainly with respect to silver contamination of the ll
starting material is relatively high and is not completely
removed by the fractional crystallization process. The
reason for this is that the potassium gold cyanide does 55
not undergo any puri?cation in the fractional crystalli II]
zation process and, thus, this prior art method was
generally found to be unsatisfactory for the more so AuCN + MCN -+ MlAu(CN):l.
phisticated semiconductor manufacturer’s use of high
purity potassium gold cyanide materials. I 60 The first step of the process comprises reacting ?nely
Variousattempts have been made to chemically pro divided gold particles with aqueous, hydrogen peroxide
duce potassium ‘gold cyanide; however, the people and alkali metal cyanide in a trimolecular reaction to
skilled in the art generally considered this approach to provide the corresponding alkali metal gold cyanide
be much more complex than the electrolysis method and alkali metal hydroxide. Generally 30% by weight
described above. For example, US. Pat. No. 3,1 12,174 65 aqueous hydrogen peroxide is employed, but the con
teaches that the preparation of this compound from centration is not critical. While the gold reacts with the
gold powder and potassium cyanide in the presence of hydrogen peroxide in accordance with equation] (a) to
an oxidizing agent such as air or a peroxide is slow and provide the alkali metal gold cyanide, a competing side
 3,989,800
3 . 4
reaction illustrated by equation I (b) also occurs. Ac- . EXAMPLE
cordingly, stoichiometric excesses of hydrogen perox
ide and alkali metal cyanide are generallypreferred in" ‘1.8’A suspension of 1 part gold particles in a solution of
parts ‘potassium cyanide and l2parts water was
order to compensate for' the loss of these reactants via 5 prepared. The suspension was heated to 58° — 61° C
the bimolecular reaction of hydrogen peroxide with and vigorously agitated, and 1.4 parts of 30% hydrogen
alkali metal cyanide. In order to control the reaction peroxide was addedv continuously over a 6 hour period
and optimize yields, the ?nely divided gold particles are while maintaining the temperature of the reaction mix
dissolved in alkali metal cyanide solution into which . ture within the above limits. After the particles of gold
hydrogen peroxide is added slowly andcontinuously. were dissolved in this solution, the pH was lowered to
While the reaction proceeds over a -wide temperature 0.5 with hydrochloric acid, thereby liberating prussic
acid'and a small amount of carbon dioxide and forming
range, temperatures from about 55° to about 65° C are insoluble yellow gold cyanide precipitate. When the
preferred. The products obtained in‘ this ?rst step are 7 liberation of prussic acid ceased, the precipitated gold
soluble in water, and thus further reaction is necessary cyanide was removed from the mixture by ?ltration and
in order to recover the desired alkali metal gold cyaé 15 washed free of chloride with 0.1% sulphuric acid. One
nide. part of the gold cyanide precipitate was then dissolved
ln the next step, the reaction solution is treated with at 85° C in an aqueous solution containing 0.3 parts of
_ an appropriate mineral acid to a pH of between about potassium cyanide forming potassium gold cyanide; the
potassium gold cyanide was then recovered by frac
0.5 to about 1.0 in order to provide insoluble gold tional crystallization.
cyanide in accordance withequation ll. Acids such as What is claimed is:
hydrochloric acid or sulfuric acid can be employed. l. A method for converting ?nely divided gold parti
The concentration of the acid is not critical since it is cles into an aqueous electroplating solution of pure
added until the desired pH is reached. The by-products alkali metal gold cyanide which comprises:v .
of this reaction are hydrogen cyanide, carbondioxide reacting said gold particles with hydrogenperoxide
and the alklai metal and ammonium salts‘ of the mineral and alkali metal cyanide to provide a reaction mix
acid, for example, potassium sulfate, potassium chlor ture comprising alkali metal gold cyanide and'solu
ble inorganic by-products;
ide, ammonium chloride, etc.“ - acidifying said reaction mixture with a mineral acid
The insoluble gold cyanide is then removed from the to provide insoluble gold cyanide;
reaction mixture by any suitable means such as ?ltra 3.0 removing said soluble gold cyanide from the reaction
tion, dissolved in aqueous alkali metal cyanide and "mixture; and;,
reacted therewith in accordance with equation III to reacting said insoluble gold cyanide with alkali metal
provide the desired alkali metal gold cyanide. The reac cyanideto produce alkali metal gold cyanide.
tion proceeds at room temperature, put preferably 2. The method of claim 1 wherein potassium gold
35 cyanide is provided by employing potassium cyanide as
elevated temperatures up to 100° C are employed. The the alkali metal cyanide. '
alkali metal gold cyanide can be used directly or sepa 3. The method of claim 2 wherein said reaction of
rated from the reaction mixture by conventional gold particles with hydrogen peroxide and alkali metal
means. Furthermore, it is obtained in high yields, that is cyanide is carried out at a temperature between about
95% or higher, and excellent purity. 40 55° and about 65° C. . r
While the reaction has been described with respect to 4. The method of claim 3 wherein sulfuric acid is
alkali metal gold cyanide, it is preferred to prepare employed as the mineral acid.
' 5. The method of claim 1 wherein said gold particles
potassium gold cyanide, which has particular/utility in are reacted with stoichiometric excesses of hydrogen
the semiconductor industry as previously discussed. 45 peroxide and alkali metal cyanide to provide the reac
The following example in which all parts are by . tion mixture comprising alkali metal gold cyanide and
weight will serve to illustrate the practice of this inven soluble inorganic by-products.
* * * =1: *
tion:

50

55..

65