CN108689426A - The manufacturing method of copper sulphate, its manufacturing method and its solution, plating solution, the manufacturing method of semiconductor circuit base plate and e-machine - Google Patents
The manufacturing method of copper sulphate, its manufacturing method and its solution, plating solution, the manufacturing method of semiconductor circuit base plate and e-machine Download PDFInfo
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- CN108689426A CN108689426A CN201810269118.2A CN201810269118A CN108689426A CN 108689426 A CN108689426 A CN 108689426A CN 201810269118 A CN201810269118 A CN 201810269118A CN 108689426 A CN108689426 A CN 108689426A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses copper sulphate, the manufacturing methods of its manufacturing method and its solution, plating solution, the manufacturing method of semiconductor circuit base plate and e-machine.Specifically, the present invention provides the manufacturing method of a kind of copper sulphate reducing concentration of iron, copper-bath, plating solution, the manufacturing method of copper sulphate, the manufacturing method of semiconductor circuit base plate and e-machine.The present invention is a kind of copper sulphate, a concentration of 0.08 mass ppm or less of Fe.
Description
Technical field
The present invention relates to a kind of copper sulphate, copper-bath, plating solution, the manufacturing method of copper sulphate, semi-conductor electricity roadbeds
The manufacturing method of plate and the manufacturing method of e-machine.
Background technology
Copper sulphate be widely used in electrolyte, pigment, insecticide, preservative, mordant, battery material, medicine,
The raw material etc. of the electroplate liquid of the electronic components such as semiconductor device.
Such as it is used as and can be used in electrolyte, pigment, insecticide, preservative, mordant, battery material, medicine, partly leads
The copper sulphate of the raw material of the electroplate liquid of the electronic components such as body device etc., in No. 3987069 bulletins (patent document 1) of Japanese Patent No.
In recorded the transition metal such as purity 99.99wt% or more and Fe, Cr, Ni be 3wtppm high purity copper sulfates below.In addition,
The high-purity sulphur for the purity for having purity 99.999wt% or more is recorded in Japanese Patent No. 3943583 (patent document 2)
Sour copper.
[Xian Youjishuwenxian ]
[Zhuan Liwenxian ]
[Patent document 1]No. 3987069 bulletins of Japanese Patent No.
[Patent document 2]No. 3943583 bulletins of Japanese Patent No..
Invention content
[Invent the Ke Ti ] to be solved;
However, according to various requirement in recent years, for than the high-purity sulphur recorded in patent document 1 and patent document 2
The demand that sour copper further reduced the copper sulphate of impurity improves.
Such as in the case where using raw material of the copper sulphate as electroless copper bath, there are the following problems:It is fine along with wiring
Change and contain iron in the copper sulphate as the raw material of electroless copper bath, thus reduces the electric conductivity of copper sheet film.
In view of the project, the present invention provides a kind of copper sulphate reducing concentration of iron, copper-bath, plating solution, sulphur
The manufacturing method of the manufacturing method of sour copper, the manufacturing method of semiconductor circuit base plate and e-machine.
[Solve the Ji Shushouduan ] of project;
The copper sulphate of embodiments of the present invention in one form, a concentration of 0.08 mass ppm or less of Fe.
The copper-bath of embodiments of the present invention is carried out obtained by liquidization using the copper sulphate in one form
Copper-bath.
The copper-bath of embodiments of the present invention in one form, a concentration of 0.019 mass ppm or less of Fe.
The copper-bath of embodiments of the present invention is in another form, a concentration of 0.016 mass ppm or less of Fe.
The copper-bath of embodiments of the present invention is in another form, a concentration of 0.012 mass ppm or less of Fe.
The manufacturing method of copper sulphate of the present invention includes in one form:Copper raw material will be made to be dissolved in obtained in the concentrated sulfuric acid
Copper sulphate material solution carry out heating concentration, will heating concentration after copper sulphate material solution with 15 DEG C/hr of cooling velocity with
Under cooled down, by the rate of recovery for the precipitate being precipitated by the cooling become 3~50% in a manner of recycle precipitate.
The plating solution of embodiments of the present invention in one form, a concentration of 0.018 mass ppm or less of Fe.
The plating solution of embodiments of the present invention is in another form, a concentration of 0.012 mass ppm or less of Fe.
The manufacturing method of the semiconductor circuit base plate of embodiments of the present invention includes in one form:Use the plating
Liquid carries out copper facing.
The manufacturing method of the e-machine of embodiments of the present invention is to use to utilize the semi-conductor electricity in one form
Semiconductor circuit base plate manufactured by the manufacturing method of base board and manufacture e-machine.
[Fa Mingxiaoguo ]
According to the present invention it is possible to provide a kind of copper sulphate reducing concentration of iron, copper-bath, plating solution, copper sulphate
Manufacturing method, the manufacturing method of the manufacturing method of semiconductor circuit base plate and e-machine.
Specific implementation mode
Hereinafter, the copper sulphate to embodiments of the present invention is described in detail.The sulfuric acid of embodiments of the present invention
Copper is a concentration of 0.05 mass ppm copper sulphate below of a concentration of 0.08 mass ppm or less, preferably Fe of Fe.By by copper sulphate
In Fe concentration be set as 0.08 mass ppm hereinafter, raw material for example in the copper sulphate of application present embodiment as copper plating bath
In the case of, the Fe in copper sheet film can be inhibited to be precipitated or form copper crystal defect because Fe is precipitated.As a result, shape can be made
At semiconductor wafer, printed base plate, semiconductor integrated circuit substrates or the integrated electricity of these semiconductor of use for having the copper sheet film
The electrical characteristics of road or e-machine etc. improve.In addition it is also possible to which the copper sulphate of present embodiment is applied to electrolyte, face
Material, insecticide, preservative, mordant, battery material, and be possible to be also applied to medicine etc..
The copper sulphate of embodiments of the present invention is in turn following copper sulphate, is met in (3-1) below~(3-5)
Any one, two, three, four or five:
A concentration of 1.0 mass ppm or less of (3-1) In,
A concentration of 0.05 mass ppm or less of (3-2) Tl,
A concentration of 1.0 mass ppm or less of (3-3) Sn,
A concentration of 1.0 mass ppm or less of (3-4) Ag,
A concentration of 0.2 mass ppm or less of (3-5) Al.
The copper sulphate of embodiments of the present invention is in turn following copper sulphate, is met in (4-1) below~(4-5)
Either one or two of, two, three, four or five:
A concentration of 0.5 mass ppm or less of (4-1) In,
A concentration of 0.05 mass ppm or less of (4-2) Tl,
A concentration of 0.5 mass ppm or less of (4-3) Sn,
A concentration of 0.8 mass ppm or less of (4-4) Ag,
A concentration of 0.15 mass ppm or less of (4-5) Al.
The copper sulphate of embodiments of the present invention is in turn following copper sulphate, is met in (5-1) below~(5-5)
Either one or two of, two, three, four or five:
A concentration of 0.2 mass ppm or less of (5-1) In,
A concentration of 0.05 mass ppm or less of (5-2) Tl,
A concentration of 0.2 mass ppm or less of (5-3) Sn,
A concentration of 0.3 mass ppm or less of (5-4) Ag,
A concentration of 0.1 mass ppm or less of (5-5) Al.
The copper sulphate of embodiments of the present invention is in turn following copper sulphate, is met in (6-1) below~(6-5)
Either one or two of, two, three, four or five:
A concentration of 0.2 mass ppm or less of (6-1) In,
A concentration of 0.05 mass ppm or less of (6-2) Tl,
A concentration of 0.2 mass ppm or less of (6-3) Sn,
A concentration of 0.05 mass ppm or less of (6-4) Ag,
A concentration of 0.09 mass ppm or less of (6-5) Al.
The copper sulphate of embodiments of the present invention is in turn following copper sulphate, is met in (7-1) below~(7-5)
Either one or two of, two, three, four or five:
A concentration of 0.2 mass ppm or less of (7-1) In,
A concentration of 0.05 mass ppm or less of (7-2) Tl,
A concentration of 0.2 mass ppm or less of (7-3) Sn,
A concentration of 0.045 mass ppm or less of (7-4) Ag,
A concentration of 0.05 mass ppm or less of (7-5) Al.
The each element concentration of the copper sulphate of embodiments of the present invention is according to measured by the following method.
(concentration analysis of Al, Na, K, Co, Cr, Ni, Zn, Ca, Mg, Cd, Mn, Pb)
The concentration analysis of Al, Na, K, Co, Cr, Ni, Zn, Ca, Mg, Cd, Mn, Pb in copper sulphate are to pass through electrolysis
After removing copper removal, measured by atom light absorption method.Measuring device manufactures (Agilent using Varian (Varian) company
(Agilent) company manufacture) without NITRATE BY FLAME ATOMIC light absorbing device AA280Z/GTA120 (Zeeman atomic extinction spectrophotometer).
The sample 1g of copper sulphate and ultra-pure water are added in the volumetric flask of 10mL in advance, sample is made to be dissolved in ultra-pure water
In.Then, using ultra-pure water to the volumetric flask carry out constant volume (into volumetric flask be added ultra-pure water until volumetric flask graticule with
The operation of the bottom alignment of the meniscus of liquid in volumetric flask), and make the copper sulfate solution of 10mL.Then, in anode
And cathode (Double-electrode type) uses Pt electrodes (a concentration of 99.95 mass % or more of Pt), to the copper sulfate solution that is obtained into
4 hours constant potential polarizations of row remove copper from the copper sulfate solution.Then, it is filled using the no NITRATE BY FLAME ATOMIC extinction
It sets and each concentration of Al, Na, K, Co, Cr, Ni, Zn, Ca, Mg, Cd, Mn, Pb is measured.Herein, the ultra-pure water is set as leading
Electric rate is the water of 0.05882 μ S/cm or less (resistivity (specific resistance) is 17.0M Ω cm or more).The quality of sulfuric acid copper sample
The balance of 4 digits after precision balance use used in measuring can be measured to decimal point.Measured value is used to the 4th digit.This
Outside, the concentration of the titer without NITRATE BY FLAME ATOMIC light absorbing device of each element is set as 1 mass ppb.In addition, 4 hours constant potentials
Polarization is that electric current is set as 0.15A and is carried out 60 minutes, then, electric current is set after electric current is set as 0.1A progress 30 minutes
It is set to 0.25A to carry out 150 minutes.
Each element concentration is calculated using calculating formula below.
Element-specific concentration (quality ppb) × dissolving in concentration (quality ppm)=copper sulfate solution of element-specific
Quality (g) × 10 of the sulfuric acid copper sample for the quality (g) of the aqueous solution of the sulfuric acid copper sample taken/taken-3(quality ppm/ matter
Measure ppb) concentration of element (quality ppb) × 10 (g)/1 (g) × 10 in=copper sulfate solution-3(quality ppm/ mass ppb)
In addition, the sample quality of the copper sulphate of the calculating formula, which uses, utilizes the value measured by precision balance.Dissolving
The quality of the aqueous solution of the sulfuric acid copper sample taken is set as 10g.
(concentration analysis of Sn and As)
The concentration analysis of Sn and As in copper sulphate are after being detached Sn and As with copper by coprecipitation below, to pass through
Atom light absorption method measures.Measuring device manufactures (Agilent (Agilent) corporation using Varian (Varian) company
Make) without NITRATE BY FLAME ATOMIC light absorbing device AA280Z/GTA120 (Zeeman atomic extinction spectrophotometer).
In advance by the lanthanum nitrate hexahydrate (La (NO of the sample 2g of copper sulphate, ultra-pure water and 5 mass %3)3·6H2O)
Aqueous solution 1mL is mixed, and is made sulfuric acid copper dissolution and is made copper sulfate solution.Then, ammonia is added in copper sulfate solution
Water and the pH value of the copper sulfate solution is set as 10~11.By excessively adding ammonium hydroxide, and make because produced by addition ammonium hydroxide
Copper hydroxide by the form of the misfit object of copper and ammonium ion dissolve.By adding the ammonium hydroxide, lanthanum becomes hydroxide,
And with Sn and As coprecipitations.Then, using filter paper, generated sediment is isolated from liquid.To the precipitation obtained
Object adds aqueous solution of nitric acid (the concentrated nitric acid volume of 50vol%:Ultrapure water volume=1:1,50~80 DEG C of temperature), keep sediment molten
Xie Hou is dried.Then, dilute hydrochloric acid (the concentrated hydrochloric acid volume made by ultra-pure water and hydrochloric acid is utilized:Ultrapure water volume=1:9)
Make the solid obtained after drying dissolving, the solution obtained is added in the volumetric flask of 20mL.In addition, using hydrogen cloride concentration
For 36 mass % concentrated hydrochloric acid as the concentrated hydrochloric acid.Then, constant volume is carried out to the volumetric flask (to add into volumetric flask ultrapure
Water is until the operation that the graticule of volumetric flask is aligned with the bottom of the meniscus of the liquid in volumetric flask), and make the measurement of 20mL
Use solution.Then, obtained measurement solution is used, and uses the no NITRATE BY FLAME ATOMIC light absorbing device, to each of Sn and As
Concentration measures.Herein, it is that (resistivity (specific resistance) is 0.05882 μ S/cm or less that the ultra-pure water, which is set as conductivity,
17.0M Ω cm or more) water.Precision balance use used in the mass measurement of copper sulphate can measure to decimal point after 4
The balance of digit.Measured value is used to the 4th digit.The concentration of the titer without NITRATE BY FLAME ATOMIC light absorbing device of each element is set as 50
Quality ppb.
Each element concentration is calculated using calculating formula below.
The concentration (quality ppb) of element-specific in the concentration (quality ppm) of element-specific=measurement solution × measurement
With sample quality (g) × 10 of quality (g)/copper sulphate of solution-3It is specific in (quality ppm/ mass ppb)=measurement solution
The concentration (quality ppb) of element × 20 (g)/2 (g) × 10-3(quality ppm/ mass ppb)
In addition, the sample quality of the copper sulphate of the calculating formula, which uses, utilizes the value measured by precision balance.It measures
It is set as 20g with the quality of solution.
(concentration analysis of Fe, In, Tl, Ag, Ti)
The concentration analysis of Fe, In, Tl, Ag, Ti in copper sulphate can be carried out by ICP-MS methods.Specifically, sharp
The ICP mass spectrometers manufactured with 500 times of ultra-pure water dilute sulphuric acid copper samples and utilization SII nanosecond science and technology company
(SPW9700) it measures, shows measured result.
Concentration analysis using Fe, In, Tl, Ag, Ti in the copper sulphate of the ICP-MS methods can pass through side below
Method carries out.
(1) sample 1 (g) of copper sulphate is taken.In addition, precision balance use used in the mass measurement of copper sulphate can survey
It measures to the balance of 4 digits after decimal point.Measured value is used to the 4th digit.
(2) sample of the copper sulphate of (1) by described in is added to ultra-pure water in the volumetric flask of 500mL, and then, utilization is ultrapure
Water (containing dust technology as needed) carries out constant volume until alignment weighs line and makes copper sulfate solution.Herein, described ultrapure
Water is set as the water that conductivity is 0.05882 μ S/cm or less (resistivity (specific resistance) is 17.0M Ω cm or more).In addition, described
The conductivity of water can be measured based on JIS K0552 (1994).In addition, the ultra-pure water can for example use ADVANTEC
The commercially available Ultrapure Water Purifiers such as the Ultrapure Water Purifiers RFU400 series of TOYO limited liability companies manufacture are manufactured.
(3) the ICP mass spectral analyses such as the ICP mass spectrometers (SPW9700) of SII nanosecond science and technology company manufacture is utilized to fill
It sets, the concentration of Fe, In, Tl, Ag, Ti in copper sulfate solution made in (2) is measured.The sulfuric acid that will be obtained
The concentration of Fe, In, Tl, Ag, Ti in copper liquor are set to CFe (quality ppb), CIn (quality ppb), CTl (quality
Ppb), CAg (quality ppb), CTi (quality ppb).
The concentration of Fe, In, Tl, Ag, Ti in copper sulphate are calculated by following formula.
Fe concentration (quality ppm)=the Fe concentration (quality ppb) in the aqueous solution of the sulfuric acid copper sample taken × is taken
Quality (g) × 10 of the sulfuric acid copper sample for the quality (g) of the aqueous solution of sulfuric acid copper sample/taken-3(quality ppm/ mass ppb)=
CFe (quality ppb) × (500 (g)) × 10-3(quality ppm/ mass ppb)/1 (g)=0.500 × CFe (quality ppm)
In concentration (quality ppm)=the In concentration (quality ppb) in the aqueous solution of the sulfuric acid copper sample taken × is taken
Quality (g) × 10 of the sulfuric acid copper sample for the quality (g) of the aqueous solution of sulfuric acid copper sample/taken-3(quality ppm/ mass ppb)=
CIn (quality ppb) × (500 (g)) × 10-3(quality ppm/ mass ppb)/1 (g)=0.500 × CIn (quality ppm)
Tl concentration (quality ppm)=the Tl concentration (quality ppb) in the aqueous solution of the sulfuric acid copper sample taken × is taken
Quality (g) × 10 of the sulfuric acid copper sample for the quality (g) of the aqueous solution of sulfuric acid copper sample/taken-3(quality ppm/ mass ppb)=
CTl (quality ppb) × (500 (g)) × 10-3(quality ppm/ mass ppb)/1 (g)=0.500 × CTl (quality ppm)
Ag concentration (quality ppm)=the Ag concentration (quality ppb) in the aqueous solution of the sulfuric acid copper sample taken × is taken
Quality (g) × 10 of the sulfuric acid copper sample for the quality (g) of the aqueous solution of sulfuric acid copper sample/taken-3(quality ppm/ mass ppb)=
CAg (quality ppb) × (500 (g)) × 10-3(quality ppm/ mass ppb)/1 (g)=0.500 × CAg (quality ppm)
Ti concentration (quality ppm)=the Ti concentration (quality ppb) in the aqueous solution of the sulfuric acid copper sample taken × is taken
Quality (g) × 10 of the sulfuric acid copper sample for the quality (g) of the aqueous solution of sulfuric acid copper sample/taken-3(quality ppm/ mass ppb)=
CTi (quality ppb) × (500 (g)) × 10-3(quality ppm/ mass ppb)/1 (g)=0.500 × CTi (quality ppm)
In addition, the sample quality of the copper sulphate of the calculating formula, which uses, utilizes the value measured by precision balance.It measures
It is set as 500g with the quality of solution.
(concentration analysis of Cl)
Cl concentration (chloride ion concentration) is measured using the chromatography of ions.Specifically, using peace (Dionex) is worn
The ion chromatograph (ICS-1500 types) of company's manufacture measures.
It can be carried out by the following method using the analysis of the Cl concentration in the copper sulphate of the chromatography of ions.
(1) sample 1 (g) of copper sulphate is taken.In addition, precision balance use used in the mass measurement of copper sulphate can survey
It measures to the balance of 4 digits after decimal point.Measured value is used to the 4th digit.
(2) sample of the copper sulphate of (1) by described in is added to ultra-pure water in the volumetric flask of 100mL, is then utilized ultrapure
Water carries out constant volume until alignment weighs line and makes copper sulfate solution.Herein, it is 0.05882 that the ultra-pure water, which is set as conductivity,
The water of μ S/cm or less (resistivity (specific resistance) is 17.0M Ω cm or more).In addition, the conductivity of the water can be based on JIS
K0552 (1994) is measured.In addition, the ultra-pure water can for example use ADVANTEC TOYO limited liability companies to manufacture
The commercially available Ultrapure Water Purifiers such as Ultrapure Water Purifiers RFU400 series manufactured.
(3) use the ion chromatograph (ICS-1500 types) for wearing the manufacture of peace (Dionex) company to sulphur made in (2)
Cl concentration in sour copper liquor measures.Cl concentration in the copper sulfate solution obtained is set as CCl (quality
ppb)。
The concentration of the Cl in copper sulphate is calculated by formula below.
Cl concentration (quality ppm)=the Cl concentration (quality ppb) in the aqueous solution of the sulfuric acid copper sample taken × is taken
Quality (g) × 10 of the sulfuric acid copper sample for the quality (g) of the aqueous solution of sulfuric acid copper sample/taken-3(quality ppm/ mass ppb)=
CCl (quality ppb) × (100 (g)) × 10-3(quality ppm/ mass ppb)/1 (g)=0.100 × CCl (quality ppm)
In addition, the sample quality of the copper sulphate of the calculating formula, which uses, utilizes the value measured by precision balance.It measures
It is set as 100g with the quality of solution.
About the copper sulphate of present embodiment, total a concentration of 30 mass ppm of the metal impurities other than Cu is hereinafter, one
Implement to add up to 25 mass ppm hereinafter, adding up to 20 mass ppm hereinafter, in another implementation in another implementation pattern in pattern
15 mass ppm or less are added up in pattern.
In the present embodiment, " total concentration of the metal impurities other than Cu " be by Na, K, Co, Cr, Ni, Zn, Al,
Ca, Mg, Cd, Mn, Pb, Sn, As, Cl, Fe, Ag, Tl, Ti, In are analyzed as analysis object, by each element obtained
Total concentration is set as total concentration of the metal impurities other than Cu.
Fe, In, Tl, Ag, Sn concentration (quality ppm) in copper sulphate is by being measured with the identical method.
In addition, the other elements also by with it is described it is identical in a manner of measure.
Total organic carbon (TOC) concentration preferably 10 mass ppm in copper sulphate are hereinafter, it is preferred that 5 mass ppm are hereinafter, it is preferred that 1 matter
Ppm is measured hereinafter, preferably 0.1 mass ppm or less in turn.TOC concentration in copper sulphate is that always had using what Shimadzu Seisakusho Ltd. manufactured
Machine carbon meter (TOC-V) and measure.In addition, the measurement of total organic carbon be use with the copper concentration in copper sulfate solution become 25~
The mode of 50g/L makes sulfuric acid copper sample be dissolved in institute in the ultra-pure water water of 17.0M Ω cm or more (resistivity (specific resistance) for)
The copper sulfate solution of acquisition and carry out.In addition, total organic carbon (TOC) concentration in copper sulphate is calculated using formula below
Go out.
Organic carbon concentration (quality in the aqueous solution of the sulfuric acid copper sample for organic carbon concentration (quality ppm)=taken
Ppb) × quality (g) of the aqueous solution of the sulfuric acid copper sample taken/quality (g) × 10 of the sulfuric acid copper sample taken-3(quality
Ppm/ mass ppb)
The copper sulphate of embodiments of the present invention can the anhydride containing copper sulphate and/or copper sulphate hydrate.Make
For the hydrate of copper sulphate, can enumerate:Copper sulphate monohydrate, copper sulphate trihydrate, copper sulfate pentahydrate etc..In addition,
The copper sulphate of embodiments of the present invention can also contain the hydrate of well known copper sulphate.In addition, in this case specification, application
In the case of using the vocabulary for having " copper sulphate " in the scope of the claims, abstract, should " copper sulphate " be set as include copper sulphate anhydride
And/or the concept including the hydrate of copper sulphate.
In addition, the concentration of its copper sulphate of the copper sulphate of present embodiment is (assuming that copper sulphate is all as the feelings of pentahydrate
The concentration of the copper sulfate pentahydrate of condition) it is 99.9 mass % or more and 99.999 mass % hereinafter, being in an implementation pattern
99.9 mass % or more and 99.995 mass % are hereinafter, be 99.9 mass % or more and 99.992 matter in another implementation pattern
% is measured hereinafter, being 99.9 mass % or more and 99.99 mass % in another implementations pattern hereinafter, being in another implementation pattern
99.9 mass % are less than 99.99 mass %.
About the concentration of copper sulphate, display by following formula evaluated obtained by result.
The measurement of copper concentration in sulfuric acid copper sample is measured by sodium thiosulfate titration.
The measurement method (sodium thiosulfate titration) of copper concentration is as described below.
The sulfuric acid copper sample for taking specific quantity, is allowed to be dissolved in ultra-pure water, and make a concentration of 255g/L of copper sulphate
Copper sulfate solution.4 digits after precision balance use used in the mass measurement of sulfuric acid copper sample can be measured to decimal point
Balance.Herein, it is that (resistivity (specific resistance) is 17.0M Ω to 0.05882 μ S/cm or less that the ultra-pure water, which is set as conductivity,
Cm or more) water.Measured value is used to the 4th digit.Then, the operation of (1) below (2) is carried out.
(1) the copper sulfate solution 2mL, the potassium iodide of excessive addition are taken.
Potassium iodide is added into copper sulfate solution, thus carries out reaction below.
2Cu2++4KI→2CuI+I2+4K+
(2) by using sodium thiosulfate to the I that is generated in the reaction of (1)2Amount is titrated and is measured.Specifically,
Until the purple for being titrated to iodine disappears and becomes gonorrhoea liquid.Then, the amount of substance for calculating sodium thiosulfate used in titration (is rubbed
You).
I2+2Na2S2O3→Na2S4O6+2NaI
It will be set as copper contained in sulfuric acid copper sample with the same amount of amount of substance (mole) of sodium thiosulfate being added dropwise
Amount of substance.
Copper concentration is measured according to following formula.
Amount of substance (mol) × copper of copper contained in the quality (g) of copper contained in sulfuric acid copper sample=sulfuric acid copper sample
Atomic weight (g/mol)=iodine (I2) titration needed for sodium thiosulfate amount of substance (mol) × copper atomic weight (g/mol)
The quality of copper contained in the quality (g) of copper sulfate pentahydrate contained in sulfuric acid copper sample=sulfuric acid copper sample
(g)×3.9292009
(assuming that copper sulphate is all as copper sulfate pentahydrate).
Quality (g)/sulfuric acid of copper sulfate pentahydrate contained in the concentration (quality %) of copper sulphate=sulfuric acid copper sample
The matter of the sulfuric acid copper sample of the quality (g) of copper in quality (g) × 100 (%)=sulfuric acid copper sample of copper sample × 3.9292009/
It measures (g) × 100 (%)
The manufacturing method of the copper sulphate of embodiments of the present invention is illustrated.
First, it is heated while being stirred the raw material containing copper in reactive tank with concentrated sulfuric acid aqueous solution,
Thus the dissolution of raw material containing copper is made to obtain copper sulphate material solution in concentrated sulfuric acid aqueous solution.Stirring means have no special limit
System, such as air can be blown into and be stirred.
As the raw material containing copper, commercially available cupric sulphate crystal (95~99.9 mass % of concentration) can be used.The sulfuric acid
Contain the impurity such as Na, Mg, Al, Ca, In, Sn, Ag, Fe in copper crystallization.Alternatively, can use is had by the aqueous dissolution of the concentrated sulfuric acid
Solution obtained by the cathode copper of 99.99% or more purity is as the raw material containing copper.As the concentrated sulfuric acid, can use commercially available dense
Sulfuric acid (95~99.9 mass % of sulfuric acid concentration).The preferred ultra-pure water of water used in the aqueous solution of the concentrated sulfuric acid.The ultra-pure water
The preferred 15M Ω cm or more of resistivity.Its reason is:It is the ultra-pure water of 15M Ω cm or more by using resistivity, and has
The case where impurity such as described Na, Mg, Al, Ca, In, Sn, Ag, Fe in the aqueous solution of the concentrated sulfuric acid can be reduced, and have further
The case where reducing the concentration of elements such as the Fe in obtained copper sulphate.The more preferable 15.5M Ω of resistivity of the ultra-pure water
Cm or more, more preferable 16.0M Ω cm or more, more preferable 16.5M Ω cm or more, more preferable 17.0M Ω cm or more.
Then, copper sulphate material solution is heated to such as 40~100 DEG C, preferably from about 100 DEG C on one side, makes copper sulphate on one side
Moisture evaporation in material solution carries out concentration until the copper concentration of copper sulphate material solution becomes such as 100~250g/L.It is logical
The copper sulphate material solution that will be concentrated is crossed to cool down at leisure in reactive tank, can make copper sulphate (such as copper sulphate five be hydrated
Object) crystallization be precipitated.
In cooling step, it is important that the temperature of the copper sulphate material solution after concentrating heating becomes cooling and terminates temperature
Cooling velocity control before degree is speed appropriate.That is, showing following tendency:Cooling velocity is slower, more becomes close to flat
The condition of weighing apparatus becomes difficult to containing impurity in the copper sulphate of precipitation, and impurity can remain in copper sulphate material solution.Therefore,
So that cooling velocity is become slower, can more reduce aluminium in the copper sulphate of precipitation etc. constitute copper sulfate pentahydrate element (Cu, S,
O, H) other than element concentration.
Specifically, the temperature (such as 100 DEG C) when the temperature of copper sulphate material solution is concentrated from heating becomes cooling
The cooling velocity (speed that the temperature of copper sulphate material solution reduces) of copper sulphate material solution before end temp is set as 15
DEG C/hr hereinafter, more preferably be set as 10 DEG C/hr hereinafter, be preferably set to 7 DEG C/hr in turn hereinafter, be more preferably set as in turn 5 DEG C/hr with
Under.Cooling means is not particularly limited, such as can apply water cooling, slow cooling, air cooling, use the cooling sides such as the cooling of heat exchanger
Method.
By cooling step, the precipitate of copper sulphate is obtained from copper sulphate material solution.The copper sulphate obtained is susceptible greatly
Principal component is copper sulfate pentahydrate under condition.After the precipitate of the copper sulphate obtained is separated by solid-liquid separation and is dried, carry out
Air-flow is transported and is individually packed, thus to obtain the copper sulphate (crystalline articles) of present embodiment.
In cooling step, the recycling condition of the precipitate of copper sulphate is preferably adjusted.That is, by selectively recycling by institute
The precipitate for stating cooling step and initial stage precipitation, can recycle the precipitate of the less copper sulphate of impurity.Specifically, more satisfactory
To become 3~50%, more preferable 5~35% and then preferably 5~25% with the rate of recovery by the cooling precipitate being precipitated
Mode recycles the precipitate of copper sulphate.The rate of recovery is evaluated by following formula.
The rate of recovery (%)=(sulphur when copper concentration (g/L)-copper sulphate in the copper sulfate solution of stoste stops being precipitated
Copper concentration (g/L) in sour copper liquor)/stoste copper sulfate solution in copper concentration (g/L × 100)
As to make the rate of recovery of the precipitate of copper sulphate be in the method in the range of 3~50%, for more satisfactory
Such as the temperature (cooling end temp) of the copper sulfate solution when recycling copper sulphate as 50~90 DEG C, preferably 50~80 DEG C
In the case of, terminate the recycling of copper sulphate precipitate.
Ultra-pure water equal solvent is added in the copper sulphate (crystalline articles) of present embodiment, so that the copper sulphate is dissolved in molten
In agent, thus to obtain the copper-bath of present embodiment.As to dissolve the solvent of copper sulphate, can enumerate:Water, one kind
Or a variety of organic solvents, one or more inorganic solvents or comprising select Free water, one or more organic solvents and one kind or
The solvent of one or more of the group that a variety of inorganic solvents are formed.As organic solvent, alcohol, aromatic hydrocarbon, fat can be used
Fat acid, chain type hydrocarbon, ring type hydrocarbon, organic acid.In addition, as inorganic solvent, the nothings such as sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid can be used
Machine acid etc..In addition, in the case where using water as solvent, copper sulfate solution can be obtained.
The preferred 15.0M Ω cm or more of the resistivity of used ultra-pure water, more excellent when using the copper sulfate solution
Select 15.5M Ω cm or more, more preferable 16.0M Ω cm or more, more preferable 16.5M Ω cm or more, and then more preferable 17.0M
Ω cm or more.Its reason is:By using the ultra-pure water that resistivity is 15M Ω cm or more, and sulfuric acid can be reduced by having
The case where concentration of the impurity such as Na, Mg, Al, Ca, In, Sn, Ag, Fe in copper liquor.
The copper concentration of the copper-bath is 50~100g/L or so.In addition, the Fe concentration in the copper-bath
It is preferred that 0.019 mass ppm hereinafter, more preferable 0.016 mass ppm hereinafter, more preferable 0.012 mass ppm or less in turn.In addition,
TOC concentration preferably 1.20 mass ppm or less in the copper-bath.TOC concentration in the copper-bath is excellent in turn
1.10 mass ppm are selected hereinafter, more preferable 1.0 mass ppm is hereinafter, more preferable 0.9 mass ppm or less in turn in turn.
Plating solution can be made using the copper sulphate or copper-bath.The Fe concentration of the plating solution of present embodiment
For 0.018 mass ppm hereinafter, it is preferred that 0.012 mass ppm or less.
The plating solution of present embodiment so meet any of (8-1) below~(8-5), two, three, four
Or five:
A concentration of 0.2 mass ppm or less of (8-1) In,
A concentration of 0.01 mass ppm or less of (8-2) Tl,
A concentration of 0.3 mass ppm or less of (8-3) Sn,
A concentration of 0.4 mass ppm or less of (8-4) Ag,
A concentration of 0.04 mass ppm or less of (8-5) Al.
The plating solution of present embodiment so meet any of (9-1) below~(9-5), two, three, four
Or five:
A concentration of 0.13 mass ppm or less of (9-1) In,
A concentration of 0.01 mass ppm or less of (9-2) Tl,
A concentration of 0.2 mass ppm or less of (9-3) Sn,
A concentration of 0.3 mass ppm or less of (9-4) Ag,
A concentration of 0.020 mass ppm or less of (9-5) Al.
The plating solution of present embodiment so meet any of (10-1) below~(10-5), two, three, four
It is a or five:
A concentration of 0.08 mass ppm or less of (10-1) In,
A concentration of 0.01 mass ppm or less of (10-2) Tl,
A concentration of 0.1 mass ppm or less of (10-3) Sn,
A concentration of 0.2 mass ppm or less of (10-4) Ag,
A concentration of 0.013 mass ppm or less of (10-5) Al.
In addition, the preferred copper concentration of the plating solution of present embodiment is 50~100g/L.And then preferably copper concentration be 50~
90g/L。
It is 99.9 mass % or more and 99.999 mass % or less that the plating solution of present embodiment, which can use the purity,
Copper sulphate and prepare, can by using the plating solution carry out copper facing.In the one of the present invention implements pattern, it can use
Semiconductor circuit base plate obtained by copper facing is carried out using the plating solution, manufactures e-machine.
[Shi Shili ]
Hereinafter, the embodiment of the present invention is indicated together with comparative example, these embodiments are to be more fully understood by this
Invention and its advantage and provide, but be not intended to limit invention.
By the commercially available copper sulphate (Cu as copper raw material:99% or more, Na:10ppm,Mg:1.5ppm,Al:4.5ppm,
Ca:3.9ppm,In:5.6ppm,Sn:10ppm,Ag:3.5ppm,Fe:It is 8.5ppm) the super of 15M Ω cm or more with resistivity
Pure water is mixed, and is carried out heating stirring at 100 DEG C and is made copper sulphate material solution.Then, the sulfuric acid copper raw material is molten
Liquid moves in thickener, is kept for 2~10 hours for 100 DEG C in temperature, thus makes the moisture evaporation in copper sulphate material solution, carry out
Concentration is until copper concentration becomes 150~250g/L.Copper sulphate material solution after heating is concentrated moves in crystallization slot, in crystallization
In slot, temperature shown in table 1 is cooled to cooling velocity shown in table 1.By processed material after cooling carry out pumping filtering with into
Row is separated by solid-liquid separation, and the precipitate of copper sulphate (copper sulfate pentahydrate) thereby is achieved.By making the precipitate of copper sulphate dry,
And obtain the crystalline articles of the copper sulphate of Examples 1 to 6 and comparative example 1~3.
For the copper sulphate of Examples 1 to 6 and comparative example 1~3, by the measurement method, in copper sulphate Na, K,
The concentration of Co, Cr, Ni, Zn, Al, Ca, Mg, Cd, Mn, Pb, Sn, As, Cl, Fe, Ag, Tl, Ti and In and the concentration of copper sulphate into
Row measures.By the impurity element in copper sulphate be set as Na, K, Co, Cr, Ni, Zn, Al, Ca, Mg, Cd, Mn, Pb, Sn, As, Cl,
Fe, Ag, Tl, Ti and In, by total concentration of total impurity being set as other than Cu of the analysis result of these concentration.By embodiment
1~6 and comparative example 1~3 copper sulphate in the concentration of Fe, Al, In, Tl, Sn, Ag, total concentration of impurity, total organic carbon
(TOC) measurement result of concentration is shown in table 1.
Copper sulfate solution is made using the copper sulphate of Examples 1 to 6 and comparative example 1~3, it is special shown in addition is following
Determine additive and makes electroplate liquid.Using chemical vapor deposition (CVD) method, make SiO2Membrane stack accumulates on silicon.By sputter, at this
SiO2The surface of film is provided as the Ta layers of barrier layer.Then, by sputter, and then the Cu for forming on Ta layers thickness 80nm is brilliant
Kind layer, then forms the copper sheet film of 30 μm of thickness by electrolytic copper plating.In addition, for Examples 1 to 6 and comparative example 1~3
Copper sulphate takes the sample of 45g respectively, so that the sample is dissolved in ultra-pure water (resistivity is 15M Ω cm or more) and is made
The copper sulfate solution of 200mL.(ratio of following plating bath, copper sulphate and other liquid is set as identical) then, in the measurement
In method, sulfuric acid copper sample is replaced with into the copper sulfate solution, it is dense to measure the Fe in copper sulfate solution by the method
Degree and organic carbon concentration.It the results are shown in table 2.
Plating bath and plating conditions are as described below.
(plating bath and plating conditions)
Plating bath
As plating bath, the plating bath of consisting of is used.
Copper sulphate (is added, copper in the form of copper sulfate pentahydrate:57.3g/L) concentration:225g/L
Sulfuric acid concentration:55g/L
Chloride ion:60ppm
Polyethylene glycol (average molecular weight 10000) concentration:500mg/L
Bis- (3- sulfopropyls) disulfide (SPS) concentration:20mg/L
Janus green concentration:1mg/L
Solvent uses ultra-pure water (resistivity is 15M Ω cm or more).
Plating conditions
Plating condition is set as:40 DEG C of plating bath, cathode-current density 2.0A/dm2, anodic current density 2.0A/dm2, plating
Apply the time:70~90 minutes.
For the copper sheet film, resistance value is measured by four probe method, thus evaluates plating.About the evaluation of plating,
Resistance value is less than 0.020 × 10-4The case where Ω/cm, is evaluated as ◎, is 0.020 × 10 by resistance value-4Ω/cm or more and small
In 0.040 × 10-4The case where Ω/cm, is evaluated as zero, is 0.040 × 10 by resistance value-4The situation of Ω/cm or more is evaluated as ×.
Show the result in table 2.
About the rate of recovery of copper sulphate, evaluated according to the following contents.
The rate of recovery (%)=(sulphur when copper concentration (g/L)-copper sulphate in the copper sulfate solution of stoste stops being precipitated
Copper concentration (g/L) in sour copper liquor)/stoste copper sulfate solution in copper concentration (g/L)
Show the result in table 1.
[Table 1]
[Table 2]
By when copper sulfate pentahydrate being made to be precipitated from copper sulphate material solution cooling velocity and the rate of recovery be adjusted to suitable
In the Examples 1 to 6 of range, Fe concentration can be reduced to 0.08 mass ppm hereinafter, plating is also good.In addition, passing through
The Fe concentration of copper-bath is set as 0.019 mass ppm or less and then 0.016 mass ppm or less and then 0.012 mass
Ppm is hereinafter, plating is also good.On the other hand, it being cooled in 0 DEG C of comparative example 1 soon in cooling velocity, the rate of recovery is higher,
It is 70% or so, but Fe can not be reduced, plating is also bad.Comparative example 2 is remembered using according to Japanese Patent No. 3987069
Copper sulphate manufactured by the manufacturing method of the high purity copper sulfate of load is formed with copper sheet film under the same conditions as example 1;
Comparative example 3 is using the sulphur manufactured by the manufacturing method according to the high purity copper sulfate recorded in Japanese Patent No. 3943583
Sour copper is formed with copper sheet film under the same conditions as example 1.The concentration of copper sulfate of comparative example 2 and 3 is higher, but with reality
It applies example 1~6 to compare, concentration of iron is high, therefore the resistance value of copper sheet film is got higher, and becomes the plating result poorer than Examples 1 to 6.
In addition it is possible to use the plating solution of the composition, carries out semiconductor wafer, especially has partly leading for perforation silicon hole
The wiring of body chip is formed.In addition, in addition to the composition, can be used for example recorded in Japanese Patent No. 5388191
The plating solution of the existing compositions such as composition forms or is formed on semiconductor circuit base plate circuit to carry out the wiring of semiconductor wafer.
That is, by the plating solution of the composition, the semiconductors such as integrated circuit or the package substrate equipped with the integrated circuit can be formed
Circuit board.
Claims (29)
1. a kind of copper sulphate, a concentration of 0.08 mass ppm or less of Fe.
2. copper sulphate according to claim 1, a concentration of 0.05 mass ppm or less of Fe.
3. copper sulphate according to claim 1 or 2, meet any of (3-1) below~(3-5), two, three
It is a, four or five:
A concentration of 1.0 mass ppm or less of (3-1) In,
A concentration of 0.05 mass ppm or less of (3-2) Tl,
A concentration of 1.0 mass ppm or less of (3-3) Sn,
A concentration of 1.0 mass ppm or less of (3-4) Ag,
A concentration of 0.2 mass ppm or less of (3-5) Al.
4. copper sulphate according to claim 1 or 2, meet any of (4-1) below~(4-5), two, three
It is a, four or five:
A concentration of 0.5 mass ppm or less of (4-1) In,
A concentration of 0.05 mass ppm or less of (4-2) Tl,
A concentration of 0.5 mass ppm or less of (4-3) Sn,
A concentration of 0.8 mass ppm or less of (4-4) Ag,
A concentration of 0.15 mass ppm or less of (4-5) Al.
5. copper sulphate according to claim 1 or 2, meet any of (5-1) below~(5-5), two, three
It is a, four or five:
A concentration of 0.2 mass ppm or less of (5-1) In,
A concentration of 0.05 mass ppm or less of (5-2) Tl,
A concentration of 0.2 mass ppm or less of (5-3) Sn,
A concentration of 0.3 mass ppm or less of (5-4) Ag,
A concentration of 0.1 mass ppm or less of (5-5) Al.
6. copper sulphate according to claim 1 or 2, meet any of (6-1) below~(6-5), two, three
It is a, four or five:
A concentration of 0.2 mass ppm or less of (6-1) In,
A concentration of 0.05 mass ppm or less of (6-2) Tl,
A concentration of 0.2 mass ppm or less of (6-3) Sn,
A concentration of 0.05 mass ppm or less of (6-4) Ag,
A concentration of 0.09 mass ppm or less of (6-5) Al.
7. copper sulphate according to claim 1 or 2, meet any of (7-1) below~(7-5), two, three
It is a, four or five:
A concentration of 0.2 mass ppm or less of (7-1) In,
A concentration of 0.05 mass ppm or less of (7-2) Tl,
A concentration of 0.2 mass ppm or less of (7-3) Sn,
A concentration of 0.045 mass ppm or less of (7-4) Ag,
A concentration of 0.05 mass ppm or less of (7-5) Al.
8. copper sulphate according to any one of claim 1 to 7, wherein a concentration of 99.9 mass % or more of copper sulphate
And 99.999 below mass %.
9. copper sulphate according to claim 8, wherein a concentration of 99.995 mass % or less of copper sulphate.
10. copper sulphate according to any one of claim 1 to 7, wherein a concentration of 99.9 mass % or more of copper sulphate
And 99.992 below mass %.
11. copper sulphate according to any one of claim 1 to 7, wherein a concentration of 99.9 mass % or more of copper sulphate
And 99.99 below mass %.
12. copper sulphate according to any one of claim 1 to 7, wherein a concentration of 99.9 mass % or more of copper sulphate
And 99.99 mass % hereinafter, metal impurities other than Cu add up to a concentration of 30 mass ppm or less.
13. copper sulphate according to any one of claim 1 to 12, organic carbon concentration is 10 mass ppm or less.
14. a kind of copper-bath is to carry out liquid institute using the copper sulphate described in any one of claim 1 to 13
.
15. a kind of copper-bath, a concentration of 0.019 mass ppm or less of Fe.
16. a kind of copper-bath, a concentration of 0.016 mass ppm or less of Fe.
17. a kind of copper-bath, a concentration of 0.012 mass ppm or less of Fe.
18. the copper-bath according to any one of claim 15 to 17, organic carbon concentration is 1.20 mass ppm
Below.
19. a kind of manufacturing method of copper sulphate comprising:The sulfuric acid copper raw material that copper raw material will be made to be dissolved in obtained in the concentrated sulfuric acid
Solution carries out heating concentration, and the copper sulphate material solution after heating is concentrated is cooled down with 15 DEG C/hr or less of cooling velocity, with
Precipitate is recycled in such a way that the rate of recovery for the precipitate that the cooling is precipitated becomes 3~50%.
20. a kind of plating solution, a concentration of 0.018 mass ppm or less of Fe.
21. a kind of plating solution, a concentration of 0.012 mass ppm or less of Fe.
22. the plating solution according to claim 20 or 21 meets any of (8-1) below~(8-5), two
It is a, three, four or five:
A concentration of 0.2 mass ppm or less of (8-1) In,
A concentration of 0.01 mass ppm or less of (8-2) Tl,
A concentration of 0.3 mass ppm or less of (8-3) Sn,
A concentration of 0.4 mass ppm or less of (8-4) Ag,
A concentration of 0.04 mass ppm or less of (8-5) Al.
23. the plating solution according to claim 20 or 21 meets any of (9-1) below~(9-5), two
It is a, three, four or five:
A concentration of 0.13 mass ppm or less of (9-1) In,
A concentration of 0.01 mass ppm or less of (9-2) Tl,
A concentration of 0.2 mass ppm or less of (9-3) Sn,
A concentration of 0.3 mass ppm or less of (9-4) Ag,
A concentration of 0.020 mass ppm or less of (9-5) Al.
24. the plating solution according to claim 20 or 21 meets any of (10-1) below~(10-5), two
It is a, three, four or five:
A concentration of 0.08 mass ppm or less of (10-1) In,
A concentration of 0.01 mass ppm or less of (10-2) Tl,
A concentration of 0.1 mass ppm or less of (10-3) Sn,
A concentration of 0.2 mass ppm or less of (10-4) Ag,
A concentration of 0.013 mass ppm or less of (10-5) Al.
25. the plating solution according to any one of claim 20 to 24, copper concentration is 50~100g/L.
26. the plating solution according to any one of claim 20 to 25, copper concentration is 50~90g/L.
27. the plating solution according to any one of claim 20 to 26, containing a concentration of 99.9 mass % or more and
99.999 quality % copper sulphate below.
28. a kind of manufacturing method of semiconductor circuit base plate comprising:Use the plating described in any one of claim 20 to 27
It applies liquid and carries out copper facing.
29. a kind of manufacturing method of e-machine, using utilizing partly leading manufactured by the manufacturing method described in claim 28
Body circuit board and manufacture e-machine.
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
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JP2017-071474 | 2017-03-31 | ||
JP2017071474 | 2017-03-31 | ||
JP2017076786 | 2017-04-07 | ||
JP2017-076786 | 2017-04-07 | ||
JP2017-090247 | 2017-04-28 | ||
JP2017090247 | 2017-04-28 | ||
JP2018-019614 | 2018-02-06 | ||
JP2018-019613 | 2018-02-06 | ||
JP2018019614A JP2018188348A (en) | 2017-04-28 | 2018-02-06 | Copper sulfate, copper sulfate solution, plating solution, manufacturing method of copper sulfate, manufacturing method of semiconductor circuit board, and manufacturing method of electronic device |
JP2018019613A JP2018172265A (en) | 2017-03-31 | 2018-02-06 | Copper sulfate, copper sulfate solution, plating solution, method for producing copper sulfate, method for producing semiconductor circuit board, and method for producing electronic apparatus |
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Citations (4)
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CN1678532A (en) * | 2002-09-05 | 2005-10-05 | 株式会社日矿材料 | High purity copper sulfate and method for production thereof |
CN1835891A (en) * | 2003-09-04 | 2006-09-20 | 株式会社日矿材料 | High purity copper sulfate and method for production thereof |
TW201134753A (en) * | 2010-02-22 | 2011-10-16 | Jx Nippon Mining & Metals Corp | Highly pure coper sulfonate aqueous solution and method for producing same |
CN102992387A (en) * | 2012-12-20 | 2013-03-27 | 广东光华科技股份有限公司 | Method for removing iron ion impurities in copper salt at high efficiency |
-
2018
- 2018-03-29 CN CN201810269118.2A patent/CN108689426A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1678532A (en) * | 2002-09-05 | 2005-10-05 | 株式会社日矿材料 | High purity copper sulfate and method for production thereof |
CN1835891A (en) * | 2003-09-04 | 2006-09-20 | 株式会社日矿材料 | High purity copper sulfate and method for production thereof |
TW201134753A (en) * | 2010-02-22 | 2011-10-16 | Jx Nippon Mining & Metals Corp | Highly pure coper sulfonate aqueous solution and method for producing same |
CN102992387A (en) * | 2012-12-20 | 2013-03-27 | 广东光华科技股份有限公司 | Method for removing iron ion impurities in copper salt at high efficiency |
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