US006086779A

United States Patent (19) 11 Patent Number: 6,086,779

Bishop et al. (45) Date of Patent: Jul. 11, 2000
54 COPPER ETCHING COMPOSITIONS AND 5,358,602 10/1994 Sutcliffe et al. ........................ 156/656
METHOD FOR ETCHING COPPER 5,554.211 9/1996 Bokisa et al. ....... ... 106/1.22
5,620,612 4/1997 Kukanskis et al. . ... 216/18
75 Inventors: Craig V. Bishop, Lakewood; John R. 5,747,098 5/1998 Larson ...................................... 427/58
Kochilla, Cleveland; Robert J.
Durante, Parma Hts.; George S. Primary Examiner William Powell
Bokisa, North Olmstead, all of Ohio Attorney, Agent, or Firm-Renner, Otto, Boiselle & Sklar
73) Assignee: McGean-Rohco, Inc., Cleveland, Ohio ABSTRACT
This
IS iinvention relates
1 hi composition
to an aqueous etching ition ffor
21 Appl. No.: 09/260,169 etching metallic copper comprising
22 Filed: Mar. 1, 1999 (a) an acid,
7 (b) a copper complexing agent,
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -2 1693.216 it to c) a metal1 capable
capable OT having a multiplicitv
of having ltiplicity Of
of OXClation
oxidati
52) * - rigging 5 / r 5 /20; States which is present in one of its higher positive
58) Field
e
of
O
S eaCl 1634; 216/105; 2 2....,2.
.... . . . . ......... . . . . .......... . . . • as .4,
Oxidation States and which metal forms a composition
Soluble Salt, and
216/13, 20, 34, 93, 105; 438/754 d oxygen wherein
h h concentration off the
the the high
higher posi
56) References Cited tVe OXClation
idati State metal in the
1 in th COmpOSIt On isS greater
position g
than about 4 grams/liter of composition.
U.S. PATENT DOCUMENTS The invention also relates to a proceSS for etching metallic
3,650,957 3/1972 Shipley et al...................... 252/79.4 X copper comprising contacting the Surface of a copper Sub
4,280.887 7/1981 Konstantouros . ... 204/150 Strate with the aqueous etching compositions of the inven
4,395,302 7/1983 Courduvelis ..... ... 156/642 tion. A method of regenerating a spent aqueous etching
4,466,859 8/1984 Nelson ......... ... 156/646 composition of the invention which has been used for
4,525.240 6/1985 Elias et al. 252/79.2 X etching metallic copper also is described.
4,545,877 10/1985 Hillis ....................................... 204/130
4,636,282 1/1987 Wong ............... 156/659.1
5,279,641 1/1994 Narisawa et al. ......................... 75/353 31 Claims, No Drawings
 6,086,779
1 2
COPPER ETCHING COMPOSITIONS AND (c) a metal capable of having a multiplicity of oxidation
METHOD FOR ETCHING COPPER States which is present in one of its higher positive
Oxidation States and which metal forms a composition
FIELD OF THE INVENTION Soluble Salt, and
This invention relates to aqueous etching compositions 5 (d) oxygen wherein the concentration of the higher posi
for etching metallic copper, to methods for etching metallic tive oxidation State metal in the composition is greater
copper, metallic copper which has been etched by contact than about 4 grams/liter of composition.
with the aqueous etching compositions of the invention, and The invention also relates to a proceSS for etching metallic
to a method of regenerating the spent aqueous copper copper comprising contacting the Surface of a copper Sub
etching compositions of the present invention. Strate with the aqueous etching compositions of the inven
tion. A method of regenerating a spent aqueous etching
BACKGROUND OF THE INVENTION composition of the invention which has been used for
etching metallic copper also is described.
Etching of metals, and particularly of copper, is carried
out in a large number of industrial processes, both for the 15 DESCRIPTION OF THE PREFERRED
cleaning of copper Surfaces, and in order to provide a desired EMBODIMENTS
pattern on the copper Surface. An example of the application Aqueous etching compositions of the present invention
of the later technique is in the production of “printed which are useful for etching metallic copper comprise
circuits' in which a layer of copper on an insulated Substrate
is etched away in predetermined areas to provide a desired (a) an acid,
pattern of conducting copper on the Surface of the insulating (b) a copper complexing agent,
Substrate. (c) a metal capable of having a multiplicity of oxidation
Copper which is used in printed wiring board (PWB) or States which is present in one of its higher positive
printed circuit board (PCB) fabrication often is etched prior Oxidation States and which metal forms a composition
to processes Such as the application of resists or the appli 25 Soluble Salt, and
cation of bonding agents Such as oxides, immersion tin, or (d) oxygen,
coupling agents Such as Silane. The etching results in a wherein the concentration of the higher positive oxidation
physical roughening of the copper Surface which provides State metal in the composition is greater than about 4 grams
increased Surface areas for bonding. per liter of composition.
A variety of etching compositions have been Suggested in The acid which is included in the aqueous etching com
the prior art for the production of printed circuit boards, and positions may be any acid or mixture of acids which is
these etching compositions include ferric chloride, cupric Strong enough to etch the copper or copper alloy in the
chloride, various ammoniacal etchants, etc. More recently, presence of the other ingredients in the etching composition.
etching compositions which comprise mixtures of an acid The etching compositions generally will contain from about
Such as Sulfuric acid and oxidizing agentS Such as hydrogen 35 20 to about 400 grams of acid, preferably from about 50 to
peroxide have been developed and utilized. The advantages about 150 grams of acid per liter of composition. Sufficient
of the peroxide Sulfuric acid System include competitively acid should be present in the etching composition to provide
low cost and in Situ recovery of copper from the used etching a pH of from 0 to about 6, or more often, from about 0 to
composition in the form of copper Sulfate or copper metal. about 3.
The composition from which the copper has been recovered 40 The acid utilized in the etching compositions of the
can be regenerated by replenishment of the hydrogen per present invention may be mineral acids, organic acids or
oxide. Such etching compositions provide for the recovery mixtures thereof. Examples of mineral acids include Sulfuric
of valuable copper and minimize the environmental burden acid, perchloric acid, hydrochloric acid, fluoroboric acid,
otherwise arising from the disposition of used etching com phosphoric acid, etc. Sulfuric acid is a particularly preferred
positions. Various Sulfuric acid/hydrogen peroxide etching 45 mineral acid. Examples of organic acids Which may be
compositions are described in, for example, U.S. Pat. Nos. utilized include carboxylic acids Such as acetic acid, alkane
3,801,512, 4,130,454, 3,668,131 and 3,463,733. Sulfonic acids, alkanol Sulfonic acids, or mixtures thereof.
It is an ongoing problem to bond organic materials to The alkane Sulfonic acids may be represented by the
metal Surfaces such as copper. When the bond between the following formula, R-SOH, wherein R is an alkyl group
metal Surface and an organic material is exposed to heat, 50 containing from about 1 to about 18, or from about 1 to
delamination may occur. Multilayer printed circuit boards about 12 carbon atoms. Examples of alkane Sulfonic acids
(PCBs) are typically constructed by interleaving imaged include methane Sulfonic acid, ethane Sulfonic acid, propane
conductive layers, Such as one containing copper with Sulfonic acid, butane Sulfonic acid, pentane Sulfonic acid,
non-conductive layerS Such as a partially cured B-stage resin hexane Sulfonic acid, decane Sulfonic acid and dodecane
55 Sulfonic acid.
(i.e., a prepreg) into a multilayer Sandwich which is then The alkanol Sulfonic acids may be represented by the
bonded together by applying heat and pressure. The con
ductive layer, i.e., the copper circuitry, does not bond well to following formula: (CH)-CH(OH)-(CH), SOH
the non-conducted B-stage resin prepreg. Often, intermedi wherein n is from 0 to about 10, m is from 1 to about 11 and
ate layers are used to bond the B-stage prepreg to the copper the Sum of m+n is from 1 up to about 12. The hydroxy group
circuitry. 60 of the alkanol Sulfonic acids may be a terminal or internal
hydroxy group. Examples of useful alkanol Sulfonic acids
SUMMARY OF THE INVENTION include hydroxyethyl Sulfonic acid, hydroxypropyl Sulfonic
acid, hydroxybutyl Sulfonic acid, hydroxypentyl Sulfonic
This invention relates to an aqueous etching composition acid, hydroxyhexyl Sulfonic acid, and hydroxydodecyl Sul
for etching metallic copper comprising 65 fonic acid.
(a) an acid, The alkane Sulfonic acids and alkanol Sulfonic acids are
(b) a copper complexing agent, available commercially and can also be prepared by a
 6,086,779
3 4
variety of methods known in the art. One method comprises cyclic organic acid having up to about 12 carbon atoms and
the catalytic Oxidation of mercaptains or aliphatic Sulfides especially the lower aliphatic monocarboxylic acid reaction
having the formula RSR wherein R or R2 are alkyl products with thiourea e.g., acylthioureas, and the mineral
groups having from 1 to about 18 carbon atoms and n is a acid Salts of thiourea e.g., thiourea mono- or di-Sulfate.
positive integer between 1 and 6. The metal Salts of Such The imidazole-thiones useful in the baths of the invention
acids are prepared, for example, by dissolving a metal oxide include imidazole-2-thiones which are represented by the
in a hot concentrated acqueous composition of an alkane or Formula II:
alkanol Sulfonic acid.
A Second essential component of the compositions of the S
present invention is at least one complexing agent Selected
from the group consisting of urea and thiourea compounds, A-N1 n N-B
amidines, and imidazole thiones. Specific examples of urea
compounds include urea, urea nitrate, urea oxalate, CH-CH
1-acetylurea, 1-benzylurea, 1-butylurea, 1,1-diethylurea,
1,1-diphenylurea, 1-hydroxyurea, etc. Examples of useful 15
urea compounds are found in Holtzman et al., U.S. Pat. No. wherein A and B are the same or different -RY groups
4,657,632, which is incorporated herein by reference. wherein R is a linear, branched or cyclic hydrocarbylene
The thiourea compounds may be represented by the group containing up to 12 carbon atoms, and Y is a
Formula I: hydrogen, halogen, cyano, Vinyl, phenyl, or ether moiety.
In one embodiment, the complexing agent is a 1,3-
dialkylimidazole-2-thione compound (where A and B are
each individually alkyl or cycloalkyl groups), and the thione
where compound may be unsymmetrical (A and B are different) or
R", R, R and R' are each independently symmetrical (A and B are the same). Preferably, the com
(1) H; 25 plexing agents are unsymmetrical Such as (where A is
(2) alkyl or alkenyl groups having up to about 6 carbon methyl or ethyl and B is an alkyl or cycloalkyl group
atoms, containing from 3 to 6 carbon atoms). Preferably, when A is
(3) aryl, aralkyl, or alkaryl groups having up to about 12 methyl, B is a C-C alkyl or cycloalkyl group, and when A
carbon atoms,
is ethyl, B is a C-C alkyl or cycloalkyl group. An example
of an unsymmetrical compound is 1-methyl-3-
(4) cycloalkyl, cycloalkylalkyl, or alkylcycloalkyl groups propylimidazole-2-thione.
having up to about 12 carbon atoms, Alternatively, Symmetrical 1,3-dialkylimidazole-2-thione
(5) R' C(X) where R may be the same as groups (2) compounds may be used and the dialkyl groups are the same
through (4) as defined above, and X is O or S; and alkyl or cycloalkyl groups containing from 1 to 6 carbon
(6) CHOH. 35 atoms. An example of this class of complexing agents is
Mineral acid Salts of the thiourea compounds may also be 1,3-dimethylimidazole-2-thione.
used. The imidiazole-2-thione complexing agents are described
The thiourea compound used in the present invention in U.S. Pat. No. 5,554,211, issued to Bokisa et al. This patent
comprises either thiourea or the various art known is incorporated herein by reference for its disclosure of the
derivatives, homologs, or analogs thereof. Compounds that 40 thiones.
may be employed in this respect comprise 2,4-dithiobiuret, Another useful copper complexing agent is at least one
2,4,6-trithiotriuret, alkoxy ethers of isothiourea; thiocyanu amidine compound. The amidine compounds may Le char
ric acid (trimer of thiourea); monalkyl or dialkyl thiourea, acterized by the Formula III:
where the alkyl group comprises a lower alkyl group, having
up to about four carbon atoms Such as diethyl thiourea or 45 RC(=NH)NH, (III)
monoethyl thiourea; Saturated or unsaturated cyclic hydro
carbons mono- or disubstituted thioureas Such as naphthyl and the acid Salts thereof wherein R is hydrogen, a hydroxyl
thiourea, diphenyl thiourea, cyclohexyl thiourea and the group, an aliphatic, alicyclic, aromatic or heterocyclic
like, where the cyclic hydrocarbons have up to about ten group, an amino group, an amidino group, and amidinoaryl
carbon atoms; the disulfide of thiourea; thio-imidol (the 50 group, a carboxyalkyl group, or an -NHR' group wherein
reaction product of thiourea and Sodium hydroxide); thio R" is an aliphatic, alicyclic, aminoalkyl, amidoalkyl or
carbamic acid esters (the reaction products of thiourea and carboxyalkyl group.
an alcohol comprising ROH where R is a saturated or The acid Salts include Salts. Such as the formates, acetates,
unsaturated aliphatic or cyclic group having up to about ten hydrochlorides, carbonates, etc. of Such amidines. The ali
carbon atoms) the oligomers of thiourea and formaldehyde, 55 phatic and alkyl groups contain from one to about 10 or
e.g., monomethylol, dimethylol, and trimethylol thioureas, more carbon atoms, whereas the alicyclic and aromatic (or
S-alkyl pseudo thioureas (manufactured by the reaction of aryl) groups contain from about 6 to about 20 or more
thiourea with an iodo lower alkane Such as iodo methane carbon atoms, and the heterocyclic groups contain from
where the lower alkyl group contains up to about five carbon about 4 to about 20 carbon atoms.
atoms); thiocarbonic acid esters of thiourea and ROH, (R 60 Examples of Such amidines are as follows. The list is
as defined above) especially where R is lower alkyl; the exemplary only and is not to be considered as a limitation on
reaction product of a Saturated or unsaturated aliphatic or the above formula.
 6,086,779

Formula Name

R
Hydrogen H-C(=NH)NH, formamidine
Hydroxyl HO-C(=NH)NH, isourea
Aliphatic CHC(=NH)NH, ethanamidine
CHCH 4-ethylhexanamidine
CHCHCH-CHCHC(=NH)NH,
Alicyclic CH-C(=NH)NH Cyclohexanecarboximidine
Pyrrole-2-carboxamidine
|
N

C(FNH)NH2

Heterocyclic HN(HN=)C
2
2.6-diazonaphthalene-3,7-
21 NN Dicarboxamide

N 21
N C(FNH)NH2.
Aromatic 2-naphthamidine
C(=NH)NH2

CHs-C(=NH)NH, Benzamidine
Amino HN-C(-NH)NH, guanidine
Aminoalkyl HNCHCHC(=NH)NH, 1-aminopropanamidine
Amidinoalkyl HNCHN=)C(CH),C(=NH)NH, pentanediamidine
Amidino HN(NH=)C-C(=NH)NH, ethanediamidine
Amidinoaryl HN(HN=)C-CH-C(=NH)NH, 1,4-benzenedicarboxamidine
Carboxyalkyl HNCHN=)C(CH2)COOH 4-carbaminidoylbutanoic acid
R" =

Aliphatic CHNHC(=NH)NH, methyl guanidine

Alicyclic Cyclohexyl guanidine
NHC(=NHONH2

Amidino HN(HN=)C-NH-C(=NH)NH, biguanide

Aminoalkyl HN(CH.)NH-C(=NH)NH, aminobutylguanidine
Carboxylalkyl HNCHN=)C-NH-CHCOOH 3-guanidinoacetic acid
HN(HN=)C-NH-(CH2)COOH 3-guanidinobutanoic acid
amidoalkyl HN(HN=)C-NH-CHCHCONH, 3-guanidino propionamide
Heterocyclic 2-guanidinobenzimidazole

The amount of the complexing agent included in the 55 (e.g., 2-ethoxy ethanol), ketones (e.g., acetone), aprotic
etching compositions may be varied over a wide range Such Solvents (e.g., dimethyl formamide, dimethyl Sulfoxide,
as from about 5 g to about 200 grams per liter of compo acetonitrile, etc.), etc.
sition. More often the baths will contain from about 5 to 120 Another essential component of the etching compositions
grams/liter and preferably from about 15 to about 75 grams of the present invention is one or more metals capable of
of the complexing agent per liter of composition. Preferably having a multiplicity of oxidation States, which metal is
the complexing agent is thiourea or 1-methyl-3-propyl 60 present in one of its higher positive oxidation States, and
imidazole-2-thione (PTI). which metal forms a composition Soluble Salt. Examples of
When the solubility of the complexing agent in the Such metals include tin, lead, platinum, and palladium which
etching composition is low, a coSolvent may be added to have positive oxidation States of +2 and +4, bismuth and
Solubilize the complexing agent and thereby enhance its antimony which have positive oxidation States of +3 and +5;
activity in the etching composition. Suitable coSolvents 65 and cerium and titanium which have positive oxidation
include water-miscible Solvents Such as alcohols, (e.g., states of +3 and +4. Particularly preferred examples of
ethanol), glycols (e.g., ethylene glycol), alkoxy alkanols higher oxidation State metals useful in the present invention
 6,086,779
7 8
include tin (+4), bismuth (+5), lead (+4) and cerium (+4). compounds containing a hydroxy, mercapto or amino group.
Tin present in a composition as Stannic ion is most preferred. Examples of materials containing hydroxyl groups include
The aqueous compositions of the present invention con alkyl phenols, Styrenated phenols, fatty alcohols, fatty acids,
taining one or more of the above described metals in the polyalkylene glycols, etc. Examples of materials containing
higher positive oxidation State can be prepared, for example, amino groups include alkylamines and polyamines, fatty
by dissolving a metal oxide or Sulfate wherein the metal in acid amides, etc.
the metal oxide or Sulfate is in its higher positive oxidation Examples of nonionic Surfactants include ether containing
State in the aqueous acid composition. For example, an Surfactants which may be produced by treating fatty alcohols
aqueous etching composition containing Stannic ions can be or alkyl or alkoxy substituted phenols or naphthols with
produced by dissolving a colloidal dispersion of tin (IV) exceSS ethylene oxide or propylene oxide. The alkyl group
oxide in sulfuric acid and water. Alternatively, tin (IV) may contain from about 14 to about 24 carbon atoms and
Sulfate can be dissolved in the aqueous acid composition. may be derived from a long chain fatty alcohol, Such as oleyl
The etching compositions of the present invention contain alcohol or Stearyl alcohol. Nonionic polyoxyethylene com
more than 4 grams per liter of the metal in the higher pounds are described in U.S. Pat. No. 3,855,085, which is
oxidation State. AS the etching process proceeds, Stannic ion 15 incorporated by reference. Polyoxyethylene compounds are
is reduced to Stannous ion, and the copper is removed from available commercially under the general trade designations
the copper Substrate is incorporated into the etching com “Surfynol” by Air Products and Chemicals, Inc. of Wayne,
position as a copper complex formed by reaction of the Pa., under the designation “Pluronic' or “Tetronic' by
dissolved cupric ions and the copper complexing agent BASF Wyandotte Corp. of Wyandotte, Mich., and under the
present in the composition. The Stannous ion is reconverted designation “Surfonic' by Huntsmern Corporation of
to Stannic ion by oxidation with air. Houston, TeX.
Another essential component of the etching compositions Alkoxylated amine, long chain fatty amine, long chain
of the present invention is dissolved oxygen or air. Typically, fatty acid, alkanol amines, diamines, amides, alkanol amides
the amount of oxygen present in a composition will range and polyglycol type Surfactants known in the art are also
from about 1 to about 15 mgs per liter of composition, more 25 useful. One type of amine useful Surfactant is the group of
often, from about 5 to about 9 mgs per liter of composition. Surfactants obtained by the addition of a mixture of propy
The amount of dissolved oxygen in the composition should lene oxide and ethylene oxide to diamines. More
be an amount Sufficient to oxidize at least part of the metal Specifically, compounds formed by the addition of propylene
present in the composition in its lower oxidation State to a oxide to ethylene diamine followed by the addition of
higher oxidation State; for example, to oxidize Stannous ion ethylene oxide are useful and are available commercially
to Stannic ion. from BASF Wyandotte, Ind. Chemical Group under the
In one preferred embodiment of the present invention, general trade designation "Tetronic'.
OXygen or air is used as the eXclusive oxidizing agent, and Carbowax-type Surfactants, which are polyethylene gly
the etching composition is free of other typical oxidizing cols having different molecular weights, also are useful.
agents Such as peroxides, perSulfates, peroxySulfates, 35 Other known nonionic glycol derivatives, Such as polyalky
permanganates, chromic acid, and metals other than those lene glycol ethers and methoxy polyethylene glycols, are
specifically identified above. available commercially and may be utilized as Surfactants.
In one embodiment, the amount of oxygen present in the Ethylene oxide condensation products with fatty acids
aqueous etching compositions is Sufficient to maintain the also are useful nonionic Surfactants. Many of these are
concentration of Stannous ions in the compositions to leSS 40 available commercially under the general tradename “Etho
than about 2 grams per liter of composition by oxidation of fat’ from Armak Ind. Examples of these surfactants include
the Stannous ion to Stannic ion. In another embodiment, the condensates of coco acids, oleic acid, etc. Ethylene oxide
concentration of dissolved copper in the etching composi condensates of fatty acid amides, e.g., oleamide, also are
tions should be maintained below about 2.5 grams of copper available from Armak Ind.
per liter of composition. As will be described more fully 45 Polyoxyalkylated glycols, phenols and/or naphthols may
below, the copper concentration can be reduced by precipi also be included. Many of these condensates are available
tating the copper complex from the used (spent) etching commercially under such trade names as “Tween” from ICI
composition. America, “Triton” from Rohm & Haas Co., “Tergitol' from
The etching compositions of the present invention may be Union Carbide, and “Igepal’ from General Aniline and Film
prepared by dissolving the above-described components in 50 Corp.
water in any order. Generally, the components will dissolve The Surfactants utilized in the atching compositions also
in water at ambient temperatures, but it may be helpful in may be amphoteric Surfactants. The preferred amphoteric
Some instances if the mixture is prepared at slightly higher Surfactants include betaines and Sulfobetaines, and Sulfated
temperatures. or Sulfonated adducts of the condensation products of eth
The etching composition also may include one or more 55 ylene oxide and/or propylene oxide with an alkyl amine or
Surfactants compatible with each of the metal Salts, the acids diamine. Examples of these Surfactants include lauryldim
and the complexing agent. The etching composition may ethylammonium betaine, Stearyl dimethylammonium
optionally contain at least one Surfactant in a concentration betaine, a Sulfated adduct of an ethoxylated alkylamine,
from about 0.01 to about 100 grams per liter of bath and Triton QS-15 (Rohm & Haas Co.), a sodium salt of a
more preferably from about 0.05 to about 20 grams per liter 60 Sulfonated lauric derivative, Miranol HS, and a sodium salt
of bath. The Surfactant may be at least one Surfactant of a Sulfonated oleic acid, Miranol OS.
including amphoteric, nonionic, cationic, or anionic Surfac Cationic Surfactants also are useful in the etching com
tants, or mixtures thereof. More often, the Surfactant is at positions and may be Selected from higher alkyl amine Salts,
least one cationic or anionic Surfactant; or mixtures thereof. quaternary ammonium Salts, alkylpyridinium Salts and alkyl
The nonionic Surfactants are preferred. 65 imidazolium Salts. Examples of the above described cationic
A variety of nonionic Surfactants include the condensation Surfactants, in the form of Salts, are lauryltrimethylammo
products of ethylene oxide and/or propylene oxide with nium Salt, Stearyltrimethylammonium Salt, octadecyldimeth
 6,086,779
9 10
ylethylammonium Salt, dimethylbenzyllaurylammonium EXAMPLE 2
Salt, octadecyldimethylbenzylammonium Salt, triethylben
Zylammonium Salt, laurylpyridinium Salt, dodecylpi The procedure of Example 1 is repeated except that an
colinium Salt, 1-hydroxyethyl-1-ben Zyl-2- equivalent amount of 1-methyl-3-propyl-imidazole-2-thione
laury limidazolinium Salt, 1-hydroxyethyl-1-benzyl-2- (PTI) is substituted for the thiourea.
oleylimidazolinium Salt, Stearylamine acetate, laurylamine EXAMPLE 3
acetate, and octadecylamine acetate.
Cationic Surfactants obtained by condensation of various The procedure of Example 1 is repeated except that the
amounts of ethylene oxide or propylene oxide with primary Sulfuric acid is replaced by an equivalent amount of methane
fatty amines are useful and are prepared by condensing Sulfonic acid.
various amounts of ethylene oxide with primary fatty amines
which may be a single amine or a mixture of amines Such as EXAMPLE 4
are obtained by the hydrolysis of tallow oils, sperm oils, The procedure of Example 1 is repeated except that the
coconut oils, etc. Specific examples of fatty acid amines Sulfuric acid is replaced by an equivalent amount of acetic
containing from 8 to 30 carbon atoms include Saturated, as 15
acid.
well as unsaturated, aliphatic amines Such as octyl amine,
decyl amine, lauryl amine, Stearyl amine, oleyl amine, EXAMPLE 5
myristyl amine, palmityl amine, dodecyl amine, and octa
decyl amine. Alkoxylated amines, e.g., coconut fatty amine, The procedure of Example 1 is repeated except that the
Stearyl amine, and tallow amine, are available from the Sulfuric acid is replaced by an equivalent amount of hydro
Armak Chemical Division of Akzona, Inc., Chicago, Ill., chloric acid.
under the general trade designation "Ethomeen”. Specific
examples of such products include “Ethomeen C/15” “Eth EXAMPLE 6
omeen C/20”, “C/25”, “Ethomeen S/15” and “S/20” and The procedure of Example 1 is repeated except that the tin
“Ethomeen T/15” and “T/25”. Commercially available 25
(IV) is replaced by an equivalent amount of bismuth (V).
examples of the alkoxylated diamines include
“Ethoduomeen T/13" and “T/20” which are ethylene oxide The etching compositions of the present invention are
condensation products of N-tallow trimethylene diamine useful for etching and removing copper from metallic cop
containing about 3 and 10 moles of ethylene oxide per mole per Surfaces, and the used or spent copper etching compo
of diamine respectively. Sition can be renewed inexpensively and with relative ease.
The amine ethoxylate Surfactants exhibit the characteris No new species are generated during the etching process
tics of both cationic and nonionic Surfactants with the except for water and the copper complex. In one
nonionic properties increasing at the higher levels of ethoxy embodiment, the composition is continuously renewed by
lation. That is, as the level of ethoxylation increases, the the presence of the oxygen which oxidizes any metal present
ethoxylated amine behaves more like a nonionic Surfactant. 35 in a lower oxidation State which is generated during the
Useful Surfactants are available commercially Such as from etching process to the metal in a higher oxidation State. AS
Texaco Chemical Company under the trade designation noted earlier, the metal in the higher oxidation State is a
“M-300 Series”, such as M-302, M-305, M-310, M-315 and critical component of the present invention. For example,
M-320 which contain a total to 2, 5, 10, 15 and 20 moles of when the metal in the etching composition is tin, the etching
ethylene oxide respectively. 40 composition originally contains Stannic ion formed by the
The Surfactants also may be anionic Surfactants. dissolution of Stannic compound Such as Stannic oxide or
Examples of useful anionic Surfactants include Sulfated alkyl Stannic Sulfate. AS the etching proceSS proceeds, Stannic ion
alcohols, Sulfated lower ethoxylated alkyl alcohols, and their is reduced to Stannous ion and copper metal is oxidized to
Salts. Such as alkali metal Salts. Examples of Such Surfactants cupric ions according to the following equation
include sodium lauryl sulfate (Duponol C or QC from 45
DuPont), Sodium mixed long chain alcohol Sulfates avail
able from DuPont under the designation Duponol WN, The cupric ions are dissolved in the etching composition and
Sodium octyl sulfate available from Alcolac, Ltd. under the form a Soluble complex with the complexing agent. Oxygen
designation Sipex OLS, Sodium tridecyl ether sulfate (Sipex present in the etching composition then oxidizes the Stan
EST), sodium lauryl ether sulfate (Sipon ES), magnesium 50 nous ion to Stannic ion as follows.
lauryl Sulfate (Sipon LM), the ammonium salt of lauryl
sulfate (Sipon L-22), diethanolamino lauryl Sulfate (Sipon Sn'+O(g)->Sn+’OH
LD), sodium dodecylbenzene sulfonate (Siponate DS), etc. The hydroxyl ions react with the sulfuric acid as follows.
The following examples illustrate the preparation of the
etching compositions of the present invention. Unless oth 55
HSO+2OH->HO+SO?
erwise indicated in the following examples and elsewhere in
the written description and claims, all parts and percentages AS copper ion begins to build up in the working etching
are by weight, and temperatures are in degrees centigrade. composition, the copper can be removed by precipitating the
EXAMPLE 1.
copper complex Such as by, for example, lowering the
60 temperature of the used etching composition. Copper com
A composition containing 10 grams of Stannic ion per liter plexing agent can be easily added to the working etching
of composition is produced by dissolving 83 grams per liter composition to restore the concentration of the copper
of a 15% tin(IV) oxide colloidal dispersion (purchased from complexing agent to the desired level.
Alfa Aesar, product code 40026), 60 grams of thiourea per Copper can be recovered from the copper complex which
liter of composition, 100 grams of Sulfuric acid per liter of 65 is precipitated as a crystalline Salt (e.g., copper thiourea
composition, and water. Oxygen is dissolved in the compo Sulfate) by electrowinning as described in more detail in
Sition by bubbling oxygen through the mixture. U.S. Pat. No. 5,211,831 (Vitale etal), which patent is hereby
 6,086,779
11 12
incorporated by reference. The complexing agent (e.g., the copper concentration is about 2 grams per liter of
thiourea) also can be recovered and reused in the etching composition. The resulting composition is chilled, and cop
composition. per complex is precipitated. Thiourea is added back to the
Another procedure for removing dissolved copper from etching composition to restore the original chemistry.
the working etching composition is to Subject the Spent
etching composition to filtration using, for example, a 0.1 EXAMPLE I
micron filter to remove any colloidal Stannic oxide, and the The procedure of Example A is repeated except that the
filtrate is then passed through a column containing a chelat temperature of the etching composition is maintained at
ing resin (e.g., a bis-picolylamine) to remove copper. The about 110 F. In this Example, similar results are obtained in
resulting filtrate is essentially free of copper but retains the 20 seconds.
original thiourea and Sulfuric acid. The filtered colloidal While the invention has been explained in relation to its
Stannic oxide can then be recombined with the composition, preferred embodiments, it is to be understood that various
and when air is bubbled through this resulting composition,
the original Starting chemistry has been restored. Only modifications thereof will become apparent to those skilled
atmospheric oxygen and a Small amount of acid has been 15 in the art upon reading the Specification. Therefore, it is to
consumed. be understood that the invention disclosed herein is intended
The utility of the copper etching compositions of the to cover Such modifications as fall within the Scope of the
present invention is illustrated by the following examples. appended claims.
What is claimed is:
EXAMPLEA 1. An aqueous etching composition for etching metallic
A3 inch by 3 inch, 1 ounce High Temperature Elongation copper comprising:
(HTE) copper laminate is cleaned in an alkaline cleaner, (a) an acid,
rinsed with water, and exposed to a spray of the etching (b) a copper complexing agent,
composition of Example 1 for 45 Seconds at ambient tem (c) a metal capable of having a multiplicity of oxidation
perature. The copper laminate is then rinsed using water, 25 States which is present in one of its higher positive
dried and examined using a Scanning electron microscope Oxidation States and which metal forms a composition
(SEM) with an attached Energy Dispersive X-ray Spectrom Soluble Salt, and
eter. The resulting Surface is found to have a morphology (d) oxygen,
which is etched, and the Surface does not appear to contain wherein the concentration of the higher positive oxidation
an immersion tin coating. State metal in the composition is greater than about 4 grams
EXAMPLEB per liter of composition.
The procedure of Example A is repeated wherein the 2. The composition of claim 1 wherein the metal (c) also
copper laminate is weighed before and after treatment. The is present in a lower positive oxidation State, and the
concentration of this lower oxidation State metal is less than
amount of copper removed from the Side exposed to the 35
about 2 grams per liter of composition.
Spray is about 82 mg. This corresponds to an average 80tt 3. The composition of claim 1 also containing copper, and
inch copper removal which is similar to the average copper the concentration of copper is less than about 2.5 grams per
removed by a Sulfuric acid/peroxide or Sodium perSulfate liter of composition.
copper etch. 4. The composition of claim 1 wherein the acid is a
40
EXAMPLE C mineral acid.
The procedure of Example A is repeated, and the Sprayed 5. The composition of claim 1 wherein the acid is an
organic acid.
composition is captured in a separate container. Examination 6. The composition of claim 1 wherein the acid is Sulfuric
of the captured composition demonstrates that copper is acid.
dissolved, and that Stannous ion has formed. Bubbling air 45
7. The composition of claim 1 wherein the metal is
through the captured composition quickly converts the Stan Selected from the group consisting of tin, bismuth, lead, and
nous ion back to the Stannic oxidation State. cerium.
EXAMPLED 8. The composition of claim 1 wherein the acid is Sulfuric
acid and the metal is tin.
The procedure of Example A is repeated except that the 50
9. The composition of claim 1 wherein the copper com
etching composition of Example 2 is utilized. plexing agent is a thiourea or an imidazole-thione.
EXAMPLEE 10. The composition of claim 1 containing greater than
The procedure of Example A is repeated except that the about 4 grams per liter of Stannic ion.
etching composition of Example 3 is utilized. 55
11. The composition of claim 10 containing less than
about 2 grams per liter of Stannous ion.
EXAMPLE F 12. An aqueous acid etching composition for etching
The procedure of Example A is repeated except that the metallic copper comprising:
etching composition of Example 4 is utilized. (a) Sulfuric acid,
60 (b) a copper complexing agent which is a urea, a thiourea,
EXAMPLE G an amidine or an imidazole-thione,
The procedure of Example A is repeated except that the (c) a metal Selected from tin, bismuth, or cerium present
etching composition of Example 5 is utilized. in its higher positive oxidation State, and
EXAMPLE H
(d) oxygen,
65 wherein the concentration of the higher positive oxidation
The procedure of Example A is repeated utilizing the State metal is greater than about 4 grams per liter of
Same etching composition on Several copper laminates until composition.
 6,086,779
13 14
13. The composition of claim 12 containing from about 50 27. The process of claim 26 wherein the composition also
to about 150 grams of Sulfuric acid per liter of composition. contains less than about 2 grams per liter of Stannous ion.
14. The composition of claim 12 wherein the metal is tin. 28. The process of claim 19 wherein the composition
15. The composition of claim 12 containing from about 10 contains from about 50 to about 150 grams per liter of
to about 120 grams of the copper complexing agent per liter Sulfuric acid.
of composition. 29. A proceSS for preparing an aqueous acid etching
16. An aqueous etching composition for etching metallic composition for etching metallic copper which comprises
copper comprising: mixing
(a) an acid, 1O (a) an acid,
(b) a copper complexing agent which is a urea, a thiourea, (b) a copper complexing agent,
an amidine, or an imidazole-thione,
(c) greater than about 4 grams of Stannic ions per liter of (c) a metal capable of having a multiplicity of oxidation
composition, States and which is present in the mixture in one of its
higher positive oxidation States, which metal forms a
(d) less than about 2 grams of Stannous ions per liter of 15 composition Soluble Salt,
composition, and
(e) oxygen. (d) oxygen, and
17. The composition of claim 16 also containing less than (e) water, wherein the concentration of the higher positive
about 2.5 grams of copper per liter of composition. Oxidation State metal in the composition is greater than
18. The composition of claim 16 containing from about 50 about 4 grams per liter of composition.
to about 150 grams of Sulfuric acid per liter of composition. 30. A method of regenerating a spent aqueous etching
19. A process for etching copper comprising contacting composition used for etching metallic copper comprising:
the Surface of a copper Substrate with the aqueous etching (a) an acid,
composition of claim 1. (b) a copper complex,
20. The process of claim 19 wherein the acid in the 25 (c) a metal capable of having a multiplicity of oxidation
composition is a mineral acid. States and which is present in the composition in one of
21. The process of claim 19 wherein the acid in the its higher positive oxidation States, and
composition is an organic acid. (d) dissolved oxygen,
22. The process of claim 19 wherein the acid in the Said proceSS comprising removing the copper complex
composition is Sulfuric acid. formed during the etching process by crystallization or by
23. The process of claim 19 wherein the metal is selected resin exchange.
from the group consisting of tin, bismuth, lead, and cerium.
24. The process of claim 19 wherein the metal is tin. 31. Metallic copper, the surface of which has been etched
25. The process of claim 19 wherein the a copper com by contact with the aqueous acid etching composition of
plexing agent is a thiourea or an imidazole-thione. 35 claim 1.
26. The process of claim 24 wherein the composition
contains more than about 4 grams per liter of Stannic ion.