(19)

&
(11) EP 1 695 938 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C01G 3/10 (2006.01)
11.11.2009 Bulletin 2009/46
(86) International application number:
(21) Application number: 04770977.9 PCT/JP2004/010714

(22) Date of filing: 28.07.2004 (87) International publication number:

WO 2005/023715 (17.03.2005 Gazette 2005/11)

(54) HIGH PURITY COPPER SULFATE AND METHOD FOR PRODUCTION THEREOF
HOCHREINES KUPFERSULFAT UND HERSTELLUNGSVERFAHREN DAFR
SULFATE DE CUIVRE A PURETE ELEVEE ET PROCEDE DE FABRICATION ASSOCIE

(84) Designated Contracting States: (74) Representative: Hoarton, Lloyd Douglas Charles
DE Forrester & Boehmert
Pettenkoferstrasse 20-22
(30) Priority: 04.09.2003 JP 2003312118 80336 Munich (DE)

(43) Date of publication of application: (56) References cited:

30.08.2006 Bulletin 2006/35 WO-A-2004/022486 JP-A- 9 202 619
JP-A- 57 155 399 JP-A- 61 083 625
(73) Proprietor: Nippon Mining & Metals Co., Ltd. US-A- 4 362 607
Minato-ku
Tokyo (JP) DATABASE WPI Week 199517 Derwent
Publications Ltd., London, GB; AN 1995-128113
(72) Inventors: XP002430495 & JP 07 053213 A (SUMITOMO
SHINDO, Yuichiro, METAL MINING CO) 28 February 1995
187-4, Usuba, Hanakawa-cho (1995-02-28)
Kitaibaraki-shi, Ibaraki 319-1535 (JP)
TAKEMOTO, Kouichi,
187-4, Usuba, Hanakawa-cho
Kitaibaraki-shi, Ibaraki 319-1535 (JP)
EP 1 695 938 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 1 695 938 B1

Description

TECHNICAL FIELD

5 [0001] The present invention relates to a manufacturing method of high purity copper sulfate including the steps of
dissolving commercially available copper sulfate crystals (purity, for instance, is 95 to 99.9wt%) in purified water or acid,
and thereafter removing impurities, and to the high purity copper sulfate obtained thereby. The starting raw material
does not have to be copper sulfate crystals, and may be a resultant solution of dissolving copper in acid containing
sulfuric acid, or copper sulfate crystals manufactured therefrom.
10
BACKGROUND ART

[0002] Copper sulfate (Cu2SO4) is a white-colored powder, but this generally refers to as a pentahydrate (CuSO4-
5H2O), and is an azurite blue crystal.
15 [0003] Copper sulfate is being used as an electrolytic solution, pigment, insecticide, antiseptic, mordant, battery ma-
terial, medicine and so on. In particular, when copper sulfate is to be used as the electroplating solution for electronic
components such as a semiconductor device, high purity copper sulfate is sought after. Commercially available copper
sulfate has a purity level of 95 to 99.9wt%, and it is necessary to purify this further in order to realize a purity level of 4N
to 5N or higher.
20 [0004] As conventional technology, disclosed is a method of obtaining copper sulfate with low Ni content by using
electrolytic copper powder, which was electrodeposited and collected from an electrolytic solution, as the raw material,
dipping this in acid to selectively dissolve and remove Ni, filtering the resultant solution and thereafter dissolving the
copper powder in sulfuric acid to realize crystallization (e.g., refer to Japanese Patent Laid-Open Publication No.
2001-10817).
25 [0005] Further, also disclosed is technology for obtaining copper sulfate with a low nickel content by making copper
sulfate containing nickel into an aqueous solution, heating this to 80C or higher, and collecting the copper sulfate crystals
that are separated and settled as a result of the heating in order to realize concentrated recrystallization (e.g., refer to
Japanese Patent Laid-Open Publication No. 2001-31419).

30 DISCLOSURE OF THE INVENTION

[0006] An object of the present invention is to provide a manufacturing method of high purity copper sulfate capable
of efficiently removing impurities at a low cost by dissolving commercially available copper sulfate crystals in purified
water or acid and thereafter subjecting this to the refining process, and high purity copper sulfate obtained thereby.
35 [0007] The present invention provides:

The present invention provides a high purity copper sulfate wherein the content of Ag impurities is less than 0.01
wtppm, metalloid element impurities of As, Sb and Bi are respectively less than 0.1 wtppm, radioactive elements of
U and Th are respectively less than 0.001 wtppm, heavy metal elements of Fe, Cr and Ni are respectively less than
40 0.1 wtppm, and having a purity of 99.99wt% or higher.

[0008] In one embodiment, undissolved residue of 1Pm or greater in water exists in an amount of 100 residues/L or
less, and having a purity of 99.99wt% or higher.
[0009] In another embodiment, the high purity copper sulfate has a purity of 99.999wt% or higher.
45 [0010] Another embodiment of the present invention provides a manufacturing method of the above high purity copper
sulfate including the steps of dissolving copper sulfate having a purity of 95 to 99.9wt% in purified water or acid and
subjecting this to active carbon treatment and solvent extraction in order to realize recrystallization.

Effect of the Invention

50
[0011] The present invention yields a superior effect in that it is capable of efficiently removing impurities by dissolving
commercially available copper sulfate having a purity level of 95 to 99.9wt% in purified water or acid and thereafter
subjecting this to solvent extraction and active carbon treatment, and thereby manufacturing high purity copper sulfate
at a low cost.
55
BRIEF DESCRIPTION OF THE DRAWINGS

[0012]

2
 EP 1 695 938 B1

FIG. 1 is a diagram showing the flow of the manufacturing method of high purity copper sulfate.

BEST MODE FOR CARRYING OUT THE INVENTION

5 [0013] Examples of analytical values of commercially available copper sulfate are shown in Table 1. As shown in
Table 1, copper sulfate contains transition metals such as iron, nickel and cobalt, and impurities such as Ca, Cr, Al and
Si in amounts of roughly 0.5 to 100wtppm, respectively. Further, roughly several ppm of Ag, As, Sb and Bi are also
contained therein.
[0014] In addition to the above, foreign matters such as impurities or oxides; for instance, several to several ten wtppm
10 of alkali elements such as Na and K; and several ten wtppb of radio active elements such as U and Th are also contained
therein.
[0015] Although it is also possible to dissolve commercially available copper metal or copper scrap in sulfuric acid
and to use this as copper sulfate, in such a case, the foregoing impurities will still be contained therein.
[0016] As described above, particularly when using copper sulfate as the electroplating solution for electronic com-
15 ponents such as a semiconductor device, it is necessary to use copper sulfate having a high purity of 99.99wt% or
higher. In particular, since Ag will become electrodeposited on the plating film and cause problems such as contamination,
it must be reduced.
[0017] Ag is very similar to Cu, and is an element that is difficult to remove. Further, since it does not have any adverse
effect on the electrical conduction property, conventionally, this was never intentionally removed. Nevertheless, a defect
20 has been discovered in that the slight content of Ag in the electroplated film would cause the plated film to become hard
and brittle.
[0018] With the plating wiring having this kind of defect, problems would arise in that such wiring would break or
disconnect under stress. Therefore, in order to avoid this kind of defect, it is necessary to reduce Ag as much as possible;
that is, to reduce Ag to 1wtppm or less.
25 [0019] Further, metalloid element impurities of As, Sb and Bi are easily engulfed in the plated film, and must be reduced
since they similarly cause the contamination of the plated film.
[0020] When As, Sb and Bi are engulfed in the thin film wiring, there is a problem in that the electrical conduction
property will become inferior, and the resistivity will become high. Therefore, it is desirable to make these impurities to
be within the foregoing scope.
30 [0021] In addition to the above, impurities such as organic matter and foreign matter are also contained, and these
will become undissolved residue in water, and similarly cause the contamination of the plated film. Thus, these impurities
must be reduced to 100 residues/L or less. Specifically, this undissolved residue caused problems the thinner the wiring
width of the semiconductor became. This was overlooked in the past.
[0022] In particular, upon embedding in a trench, there was a problem in that the embedding could not be conducted
35 or would be insufficient as a result of being obstructed by foreign matter. In order to reduce the generation of defective
goods, the existence of undissolved residue is a problem that can no longer be overlooked, and it is therefore desirable
to make such undissolved residue to be within the foregoing scope.
[0023] Generally speaking, it is desirable that the conditions for reducing Ag, reducing As, Sb, Bi and undissolved
residue are all fulfilled, but there are cases that the conditions would not cause a particular problem depending on the
40 purpose or characteristic of the wiring. In other words, such conditions may be suitably selected depending on which
characteristic is important. Therefore, the conditions may be adjusted independently. The present invention covers all
such cases.
[0024] The foregoing copper sulfate is dissolved in purified water or acid such as diluted sulfuric acid at room temper-
ature, and this is thereafter subject to solvent extraction. Further, active carbon treatment is performed to remove
45 impurities such as organic matter and foreign matter as well as noble metals such as Ag. The removal of impurities such
as organic matter and foreign matter and oil films, and the removal of noble metals such as Ag via active carbon treatment
do not exist in conventional technology, and such removal process is a new discovery and method provided by the
present invention.
[0025] Thereafter, impurities such as organic matter and foreign matter are filtered and removed. When there is
50 undissolved foreign matter and the like, these are also filtered and removed.
[0026] Next, the solution or filtrate that dissolved copper sulfate is heated to a temperature of roughly 50 to 100C,
and subject to evaporative concentration. After performing evaporative concentration, this is cooled to room temperature,
and crystals are deposited thereby.

55

3
 EP 1 695 938 B1

[Table 1]
Impurity Element Raw Material Example 1 Example 2* Example 3 Comparative Example 1
B 1 <0.01 <0.01 <0.01 0.7
5
Na 13 <0.1 0.7 <0.1 7
Mg 0.8 <0.01 <0.01 <0.01 0.5
Al 3.2 <0.1 <0.1 <0.1 1.6

10 Si 17 0.5 0.7 0.2 8

P 2.3 0.3 <0.1 0.1 1.1
CI 8.5 0.5 0.7 <0.1 3.5
K 3.1 <0.1 0.3 <0.1 1.2
15
Ca 3.5 <0.1 0.8 <0.1 1.0
Ti 0.4 <0.01 <0.01 <0.01 0.3
Cr 18.1 <0.1 0.9 <0.1 9.5
20 Mn 0.2 <0.1 <0.1 <0.1 0.1
Fe 81 <0.1 7.6 <0.1 8.5
Co 3.5 <0.1 0.35 <0.1 1.5
Ni 4.3 <0.1 0.43 <0.1 1.2
25
Ag 2.5 <0.01 0.1 <0.01 1.5
As 4.8 <0.1 0.32 <0.1 3.2
Sb 2.4 <0.1 0.15 <0.1 1.3
30 Bi 2.1 <0.1 0.18 <0.1 1.8
Th 0.02 <0.001 0.001 <0.001 0.01
U 0.01 <0.001 0.001 <0.001 0.007
Undissolved Residue in 150 None None None 110
35
Water (Residue /L)
* Example 2 does not form part of the present invention.

[0027] Thereafter, this is cooled to room temperature, crystals of copper sulfate are deposited, and these are filtered
40 to obtain blue-colored high purity copper sulfate. The initial crystals may be removed as necessary.
[0028] It is desirable that the filtrate after the ultimate filtration is 2 to 40wt% of the original fluid volume. This is in order
to prevent impurities such as Na and K from getting mixed into the crystals by remaining non-crystallized copper sulfate
in a residual liquid.
[0029] The drying temperature is preferably 40 to 100C. If the temperature is less than 40C, too much time will be
45 required for removing the adsorption moisture, and if the temperature exceeds 100C, this is not preferable since the
adhesive moisture of pentahydrates will be removed and the form of copper sulfate will change. The impurities after the
foregoing refining process are similarly shown in Table 1.
[0030] The various impurities shown in Table 1 are reduced respectively to 1ppm or 0.1 ppm or less, and high purity
copper sulfate having a purity level of 4N to 5N is obtained. Incidentally, among the elements shown in Table 1, although
50 there are certain elements (for instance Na, Si, Cl, Ca, Cr, Fe, Co and Ni) that are contained in amounts slightly more
than Ag or As, Sb and Bi, these impurities will remain in the bath as ions when using these impurities as a copper sulfate
solution, and it is unlikely that these will enter the film wiring. Thus, no problems will arise with the level of these impurities
shown in Table 1. The flow of the manufacturing method of high purity copper sulfate according to the present invention
is shown in FIG. 1.
55
Examples

[0031] The Examples are now explained. Incidentally, these Examples are merely illustrative, and the present invention

4
 EP 1 695 938 B1

shall in no way be limited thereby. In other words, the present invention shall only be limited by the scope of claim for a
patent, and shall include the various modifications other than the Examples of this invention.

(Example 1)
5
[0032] 250g of commercially available copper sulfate crystals (Cu2SO4-5H2O) having a purity level of 99.9wt% and
containing the impurities shown in Table 1 were dissolved in 1000ml of diluted sulfuric acid at room temperature.
[0033] Next, this was subject to solvent extraction with D2EHPA. This was further subject to active carbon treatment
in order to remove impurities such as organic matter and Ag as well as foreign matter. This was thereafter heated to
10 900C or higher, and water was evaporated in a prescribed amount. Crystals started to appear from around 700ml, and
ended at 200ml.
[0034] Next, this was cooled to room temperature in order to deposit refined copper sulfate crystals, and the crystals
were filtered. Since there is a risk that impurities such as Na and K could get mixed into the refined copper sulfate when
evaporation is increased extremely, evaporation was stopped midway in order to obtain a residual liquid.
15 [0035] When this high purity copper sulfate was redissolved and was filtered, there was no undissolved residue of
1Pm or greater in water. The results are shown in Table 1.
[0036] As shown in Table 1, the various impurities listed in Table 1 have been reduced respectively to 1wtppm or
0.1wtppm or less, and high purity copper sulfate having a purity level of 4N to 5N or higher was obtained. With the
processes shown in Example 1 of the present invention, a significant improvement in purity has been confirmed.
20 [0037] These impurities are particularly disfavored in the copper plating to circuits or wirings upon manufacturing a
semiconductor device or the like, and the reduction of such impurities is extremely effective.

(Example 2)

25 [0038] Example 2 does not form part of the claimed invention.

[0039] The same raw material as with Example 1 was used, and, without subjecting this to solvent extraction, only
the active carbon treatment and the subsequent processes of Example 1 were performed. The results are shown in
Table 1.
[0040] As shown in Table 1, although slightly inferior to Example 1, only Fe was 7.6wtppm, and the other impurities
30 have been reduced to 1wtppm or 0.1wtppm or less, and high purity copper sulfate having a purity level of 4N to 5N or
higher was obtained. Further, when this high purity copper sulfate was redissolved and was filtered, there was no
undissolved residue of 1Pm or greater in water.
[0041] With the processes shown in Example 2, a significant improvement in purity has been confirmed. These im-
purities are particularly disfavored in the copper plating to circuits or wirings upon manufacturing a semiconductor device
35 or the like, and the reduction of such impurities is extremely effective.

(Example 3)

[0042] Copper scrap raw material having the same purity level as with Example 1 was used, and the same processes
40 as with Example 1 were performed. The results are shown in Table 1.
[0043] As shown in Table 1, impurities have been reduced to 1 wtppm or 0.1wtppm or less, and high purity copper
sulfate having a purity level of 4N to 5N or higher was obtained. Further, when this high purity copper sulfate was
redissolved and was filtered, there was no undissolved residue of 1Pm or greater in water when.
[0044] With the processes shown in Example 3 of the present invention, a significant improvement in purity has been
45 confirmed. These impurities are particularly disfavored in the copper plating to circuits or wirings upon manufacturing a
semiconductor device or the like, and the reduction of such impurities is extremely effective.

(Comparative Example 1)

50 [0045] The same raw material as with Example 1 was used, and, without subjecting this to solvent extraction and
active carbon treatment, the same processes as with Example 1 were performed for recrystallization. The results are
shown in Table 1.
[0046] As shown in Table 1, reduction of impurities was hardly achieved. Further, when this high purity copper sulfate
was redissolved and was filtered, undissolved residue of 1Pm or greater in water existed in an amount of 110 residues/L.
55 [0047] The improvement in purity could not be achieved with the Comparative Example, and these impurities caused
problems in that impurities which are particularly disfavored in the copper plating to circuits or wirings upon manufacturing
a semiconductor device or the like remained in large quantities.

5
 EP 1 695 938 B1

Industrial Applicability

[0048] The present invention yields a superior effect in that it is capable of efficiently removing impurities by dissolving
commercially available copper sulfate having a purity level 95 to 99.9wt% in purified water or acid and thereafter subjecting
5 this to solvent extraction or active carbon treatment, and thereby manufacturing high purity copper sulfate at a low cost,
and is extremely useful as an electrolytic solution, pigment, insecticide, antiseptic, mordant, battery material, medicine
and so on, as well as the electroplating solution for electronic components such as a semiconductor device.

10 Claims

1. High purity copper sulfate wherein the content of Ag impurities is less than 0.01 wtppm, metalloid element impurities
of As, Sb and Bi are respectively less than 0.1 wtppm, radioactive elements of U and Th are respectively less than
0.001 wtppm, heavy metal elements of Fe, Cr and Ni are respectively less than 0.1 wtppm, and having a purity of
15 99.99wt% or higher.

2. High purity copper sulfate according to claim 1, wherein undissolved residue of 1 Pm or greater in water exists in
an amount of 100 residues/L or less, and having a purity of 99.99wt% or higher.

20 3. High purity copper sulfate according to claim 1 or claim 2, having a purity of 99.999wt% or higher.

4. A manufacturing method of high purity copper sulfate according to any one of claims 1 to 3, including the steps of
dissolving copper sulfate having a purity of 95 to 99.9wt% in purified water or acid and subjecting this to active
carbon treatment and solvent extraction in order to realize recrystallization.
25

Patentansprche

1. Hochreines Kupfersulfat, wobei der Gehalt von Ag-Verunreinigungen unter 0,01 Gew.-ppm liegt, die Verunreinigun-
30 gen der Halbmetallelemente As, Sb und Bi jeweils unter 0,1 Gew.-ppm liegen, die radioaktiven Elemente U und Th
jeweils unter 0,001 Gew.-ppm liegen, die Schwermetallelemente Fe, Cr und Ni jeweils unter 0,1 Gew.-ppm liegen,
und mit einer Reinheit von mindestens 99,99 Gew.-%.

2. Hochreines Kupfersulfat gem Anspruch 1, wobei ein unaufgelster Rest von mindestens 1Pm in Wasser in einer
35 Menge von hchstens 100 Resten/L vorhanden ist, und mit einer Reinheit von mindestens 99,99 Gew.-%.

3. Hochreines Kupfersulfat gem Anspruch 1 oder Anspruch 2 mit einer Reinheit von mindestens 99,999 Gew.-%.

4. Verfahren zur Herstellung von hochreinem Kupfersulfat gem einem der Ansprche 1 bis 3, das die Schritte zur
40 Auflsung von Kupfersulfat mit einer Reinheit von 95 bis 99,9 Gew.-% in gereinigtem Wasser oder Sure und zu
dessen Unterziehung unter eine Aktivkohlebehandlung und Solventextraktion zur Durchfhrung einer Rekristallisa-
tion enthlt.

45 Revendications

1. Du sulfate de cuivre de haute puret o le contenu dimpurets Ag est infrieur 0,01 ppm poids, les impurets
dlments mtallodes As, Sb et Bi sont respectivement infrieures 0,1 ppm poids, les lments radioactifs U et
Th sont respectivement infrieurs 0,001 ppm poids, les lments de mtaux lourds Fe, Cr et Ni sont respectivement
50 infrieurs 0,1 ppm poids, et ayant une puret de 99,99 % poids ou plus.

2. Du sulfate de cuivre de haute puret selon la revendication 1, o un rsidu non dissous de 1 Pm ou plus dans leau
existe dans une quantit de 100 rsidus/l ou moins, et ayant une puret de 99,99 % poids ou plus.

55 3. Du sulfate de cuivre de haute puret selon la revendication 1 ou la revendication 2, ayant une puret de 99,999 %
poids ou plus.

4. Un procd de fabrication dun sulfate de cuivre de haute puret selon nimporte laquelle des revendications 1 3,

6
 EP 1 695 938 B1

comprenant les tapes consistant dissoudre du sulfate de cuivre ayant une puret de 95 99,9 % poids dans de
leau purifie ou de lacide et soumettre cela un traitement par charbon actif et une extraction par solvant afin
de raliser une recristallisation.

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EP 1 695 938 B1

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 EP 1 695 938 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the readers convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

JP 2001010817 A [0004] JP 2001031419 A [0005]