CN102127784B - Electroplated Cu laminated film and preparation method thereof - Google Patents

Electroplated Cu laminated film and preparation method thereof Download PDF

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Publication number
CN102127784B
CN102127784B CN201010010156XA CN201010010156A CN102127784B CN 102127784 B CN102127784 B CN 102127784B CN 201010010156X A CN201010010156X A CN 201010010156XA CN 201010010156 A CN201010010156 A CN 201010010156A CN 102127784 B CN102127784 B CN 102127784B
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Prior art keywords
film
stack membrane
ultrasonic
plating
copper
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CN201010010156XA
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CN102127784A (en
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于志明
崔荣洪
牛云松
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Institute of Metal Research of CAS
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Institute of Metal Research of CAS
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Abstract

The invention relates to a preparation technology of a laminated film, in particular to an electroplated Cu laminated film which has high wear resistance and corrosion resistance, has high bonding strength with a matrix material and can suppress production and propagation of cracks and a preparation method thereof, and solves the problem of strong poison pollution caused by plating copper with cyanide in order to improve the bonding strength between a Cu plated layer and the matrix material. A copper laminated plating film is prepared by an electroplating process and an ultrasonic wave intermittently introducing technology; and the preparation method of the film comprises the following steps of: deoiling and purifying a metal matrix material; electroplating a Cu laminated plating film; taking the copper laminated plating film out when the film reaches a required thickness; and cleaning and drying the copper laminated plating film to obtain the prepared electroplated Cu laminated film. The prepared metal copper film has a laminar structure; the thickness of a single copper film layer is in a range of between 0.08 and 2.5 microns, the total thickness is in a range of between 3.2 and 50 microns, and the thicknesses can be adjusted according to actual demands. The method is simple and practicable and is low in cost.

Description

A kind of plating Cu stack membrane and preparation method thereof
Technical field:
The present invention relates to the technology of preparing of stack membrane, be specially a kind of good wear-resisting, corrosion resistance nature that not only has, and high with the body material bonding strength, can suppress the generation of crackle and plating Cu stack membrane of expansion and preparation method thereof.
Background technology:
The history in existing 170 years of electroplating technology development, and copper coating can obtain multicolour with the electrochemical coloring processing.Therefore, be widely used in the decoration of some archaizeding handicrafts, light fixture, toy, button and other small item.In order to guarantee to have good bonding force between copper coating and the metallic matrix, generally must approach copper (about 3 μ m) by elder generation's preplating one deck in cyanide copper plating solution, in hydrosulphate or pyrophosphate plating solution, thicken then.Contain highly toxic substance in the cyanide copper plating solution, not only human body is directly brought harm, and cause environmental pollution easily, also make the coating process more complicated that becomes in addition.
In recent years, have particular performances and obtained application gradually owing to ultrasonic technique in every field.UW strengthens electroplating technology, is do not changing electroplate liquid formulation, do not increasing under the prerequisite of plating bath protection difficulty, changing coating performance and a kind of novel method that improves electroplating velocity significantly.UW electroplate through sound jet strengthened the diffusion mass transfer process of plating bath, reduce concentration polarization, increase substantially the electrodeposition rate of the system that receives the mass transfer diffusion control; The strengthening effect on its cavitation and microjet counter electrode surface can reduce the deposition overpotential, enlarges to allow current density range.To the difficult metal refining of part, can improve its deposition process conditions.The energy benefit that its cavatition produced has reduced electrode surface reduction of metal ion potential energy, has reduced critical nucleus radius, makes nucleation rate improve refinement coating crystal grain; In addition, under cavitation and the effect of HS microjet, deposited to the broken of cathode surface, formed littler nucleus, caused " forming core propagation ", even crystal grain is stripped from cathode surface and is dissolved in the electrolytic solution again than coarse grain.When nucleation rate surpassed grain growth speed, crystal grain had just obtained refinement; Ultrasonic microjet and cavitation effect can in time be driven away the hydrogen of electrode surface absorption, thereby have reduced the hydrogen embrittlement that coating produces because of liberation of hydrogen, phenomenon such as grow dim, and reduce the coating internal stress.The counter electrode surface is constantly cleaned simultaneously, has reduced the deposition of impurity such as oxyhydroxide etc., can get rid of phenomenons such as coating is mingled with effectively.Ultrasonicly constantly clean electrode surface, make electrode surface obtain the successive activation, thereby the carrying out of promote the oxidation-reduction reaction prevents negative electrode and anode passivation towards jet.In composite electrodeposition, its cleanup action has improved the wetting conditions between particle and the solution, has promoted the deposition of particle.In the nano-composite plate preparation, can reduce the reunion of nano particle effectively, nano particle can be disperseed in plating bath effectively, and form even, smooth composite deposite with the metals ion codeposition.
Chinese invention patent (publication number CN1974870A) discloses a kind of method of UW reduction internal stress of electroplated copper film of material technology; The plating tank that fills electroplating solution is positioned in the ultrasonic bath, utilizes ultrasonication can effectively reduce the internal stress of electroplated copper film.Yet its weak point is: ultrasonic mechanism is crystal grain thinning, so just increases substantially the hardness of copper coating, and when dura mater was blocked up, the fragility tendency increased, and is easy to generate tiny crack and crack propagation.
Chinese invention patent (publication number CN1557997A) discloses the ultrasonic of a kind of nano level metal pottery---electro-deposition method, and the nano-particle material that the present invention uses is TiN, TiC, SiN, SiC and Al 2O 3One or more compsns, the nano functional film layer structure of its formation is tight, strength high toughness is good, and is firm with matrix bond, Rockwell hardness can reach more than the HRC60.Yet its weak point is: (1) TiN, TiC, SiN, SiC and Al 2O 3The nanostructure functional membrane coating that constitutes Deng film belongs to dura mater with dura mater is complementary, and the fragility tendency greatly.(2) its TiN, TiC, SiN, SiC and Al 2O 3All belong to the homogeneous dura mater Deng film, be easy to generate tiny crack and crack propagation.
Summary of the invention:
The object of the present invention is to provide a kind of good wear-resisting, corrosion resistance nature that not only has; And with high plating Cu stack membrane of body material bonding strength and preparation method thereof, solve the problems such as generation and expansion that the severe toxicity that produces when adopting cyanide copper plating for the bonding force that improves Cu coating and body material pollutes, simplifies crackle in coating process and the inhibition plated film.
Technical scheme of the present invention is:
A kind of plating Cu stack membrane of high bond strength; This stack membrane is through intermittently introducing ultrasonic signal deposits the Cu plated film on metal base material in the electroplating technology process; The metal copper film that obtains is laminate structure; The thickness in monolayer of copper film is in 0.08~2.5 micrometer range, and total thickness can be adjusted in 3.2 microns~50 micrometer ranges according to the actual requirements.
The preparation method of the plating Cu stack membrane that described and matrix metal material bonding strength is high is substrate with the metallic substance, in the electroplating technology process, through intermittently introducing ultrasonic signal deposition Cu plated film, forms the Cu stack membrane, and concrete steps are following:
(1) greasy dirt on the removal base metal surface cleans in organic solvent for ultrasonic;
(2) acid etching;
(3) washing;
(4) introduce ultrasonic signal, metal refining copper film on base material in the electroplating process discontinuous;
(5) wash and dry up, obtain the stack membrane of Cu.
In the said step (1), the greasy dirt of removing on the base metal surface is workpiece to be immersed in the trieline organic solution scrub;
In the said step (1), cleaning in organic solvent for ultrasonic is to put into trieline organic solution to workpiece to clean 5~10 minutes through Ultrasonic Cleaners, makes workpiece obtain clean surface.
In the said step (2), acid etching is meant for different body materials selects suitable acid solution that the oxide film on the matrix surface is disposed, the visible various plating handbooks of concrete grammar;
In the said step (4), introduce ultrasonic signal in the electroplating process discontinuous and be meant:
At first, be that 100~200mA, ultrasonic frequency are plated film 120~510 seconds under 16.5~55.5kHz at hyperacoustic electric current; Then, with the electric current of ultrasonic generator in 30 seconds by 100~200mA gradually (evenly) be reduced to 0; Then, do not adding under hyperacoustic state plated film 120~510 seconds; Again with the electric current of ultrasonic generator in 30 seconds by 0 gradually (evenly) be elevated to 100~200mA.Constantly repeat aforesaid operations, depositing time is 100~240 minutes, obtains the plating Cu stack membrane that needs.
In the said step (4), the current density of metal refining copper film process is 1~5A/dm on base material 2
Advantage of the present invention and beneficial effect are:
1, the present invention utilizes metal Cu element good electrical conductivity, thermal conductivity and abundant tinctorial property; With the metallic substance is substrate; In the electroplating technology process, deposit the Cu plated film through intermittently introducing ultrasonic signal; Thereby obtain not only to have good wear-resisting, corrosion resistance nature, and high with the body material bonding strength, as can to suppress the generation and the expansion of crackle Cu stack membrane.
2, the present invention electroplates that Cu stack membrane preparation method is simple, cost is lower.
3, adopt the plating Cu stack membrane of the present invention's preparation; Characteristics with laminate structure; The thickness in monolayer of copper film is in 0.08~2.5 micrometer range; Total thickness can be adjusted in 3.2 microns~50 micrometer ranges according to the actual requirements, and the advantage of this structure mainly contains: the bonding strength between (1) plated film and body material, plated film and the plated film is high; (2) wear-resisting, the corrosion resistance and good of plated film; (3) generation and the expansion of crackle be can suppress effectively, conventional ultrasonic electroplating film easy of crack and peeling phenomenon significantly improved.
Description of drawings:
Fig. 1 the present invention electroplates the end face electromicroscopic photograph of Cu stack membrane.
Fig. 2 the present invention electroplates the comparison of Cu stack membrane and the conventional Cu of plating film corrosion resistance nature.
Fig. 3 the present invention electroplates the comparison of Cu stack membrane and the conventional Cu of plating film wear resisting property.
Fig. 4 plated film bonding force is estimated isolated plant.
Among the figure, 1 clamp body; 2 bolts; 3 backing plates; 4 samples (sample).
Embodiment:
Embodiment 1
Through the surface removal greasy dirt; Acid etching and washing are carried out in ultrasonic cleaning after 5 minutes in trieline organic solution; The 304 stainless steel base materials that clean up are connected on the negative electrode of electroplating power supply, and anode adopts fine copper plate (copper content 99.7wt%), starts ultrasonic generator; Adjust its frequency and arrive 24.5kHz, electric current to 100mA; Be suspended to plating piece then and begin in the electroplating solution that is placed in the ultrasonic cleaning tank to electroplate, the electroplating solution prescription is basically identical with the copper plating solution shown in the table 1 with processing parameter, and the current density that is added on the workpiece is 2A/dm 2During plated film to 150 second with the electric current of ultrasonic generator in 30 seconds gradually (evenly) be reduced to 0; Do not adding under the ultransonic state plated film 150 seconds then, subsequently in 30 seconds again with the electric current of ultrasonic generator gradually (evenly) be elevated to 100mA, repeat this technological process; Depositing time 240 minutes, thus deposition obtains the lamination plated copper film.This plated film is laminate structure, about 0.3 micron of present embodiment lamination Cu plated film thickness in monolayer, about 24 microns of plated film total thickness.As shown in Figure 1, can find out that from lamination Cu plated film section microscopic appearance plated film is tangible laminate structure, about 0.3 micron of every layer thickness has good binding between plated film and the plated film.
Table 1 is electroplated Cu solution formula and processing parameter
Component Content (g/L) Processing parameter Technical indicator
CuSO 4·5H 2O 200~250 Current density 1~5A/dm 2
H 2SO 4 50~70 Temperature/℃ 25-30
Glucose 30~40 Ultrasonic power 220V 100~200mA
Water Surplus Ultrasonic frequency 24.5KHz
The present invention has carried out hardness test to the common plating Cu film for preparing with plating Cu stack membrane sample, and concrete testing method is following:
Testing apparatus: Japan makes SHIMAZU M84207 type microhardness tester; Load: 50gf;
Loading time: 15 seconds; Concrete operation method is following: at first with acetone specimen surface is cleaned up, be placed on sample on the sheet glass (measuring towards last) then, confirm between sample and the sheet glass behind the no gap; Be put into together on the Stage microscope, observe specimen surface with 400 power microscopes earlier, confirm to measure the hardness position; Automatically loading 50gf then kept 15 seconds; Demarcate the impression catercorner length, print hardness value, each sample is surveyed at 3 and is averaged.The hardness test result of Cu lamination plated film is 129.8Hv, and the hardness test result of common plating Cu film is 139.1Hv.
The present invention has carried out the polishing machine simultaneous test to the common plating Cu film for preparing with plating Cu stack membrane sample, and concrete experimental technique is following:
Experimental installation: Japan makes NUS-LSO-1 type emery wheel formula wear testing machine; Emery wheel sand paper: No. 1000 silicon carbide papers; Load: 6.4N; Electronic balance measuring accuracy: 0.1mg.Concrete operations are following:
At first with acetone specimen surface is cleaned up, blowing hot wind dries up specimen surface, measures and record sample initial weight.Then, sample is installed begins to carry out wearing test on the worktable, and each 100 change and guarantee that the sample surface of friction contact with fresh coated abrasive surface all the time.After each wearing test, utilize hairbrush to clean up the friction surface cleaning, dry up with specimen surface with acetone again after clean, measure also record sample weight, the weight loss of the weight change before and after the sample wearing test as sample.Successively, each sample may wear to and exposes till the matrix, and per 100 go round and round a millstone the average weight losses after decreasing of materialsing are passed judgment on the quality of plated film wear resisting property, and its weight loss bright plated film wear resisting property of saving your breath more is good more.Wearing test result is shown in Fig. 2, is increased than common electrical deposited copper film by the wear resisting property of scheming visible ultrasonic electroplating Cu stack membrane.
The present invention has carried out the corrosion resistance nature simultaneous test to the common plating Cu film for preparing with plating Cu stack membrane sample, and concrete experimental technique is following:
Adopt three-electrode cell and EG&G 273A potentiostat to measure polarization curve, testing liquid is the NaCl solution of 3.5wt%.Preceding test sample the envelope with epoxy resin of test is coated with, and making exposed area is 1cm 2Working electrode, supporting electrode is the Pt sheet, reference electrode is KCl, sweep velocity is selected 1mv/s.Fig. 3 is a test result; The corrosion potential that can find out ultrasonic acid copper film is obviously than the height of common electrical deposited copper film; From corrosion current be merely the latter less than 1/2, corrosion resisting property of this explanation ultrasonic electroplating Cu stack membrane is greatly improved than common electrical deposited copper film.
The present invention has carried out the bonding force simultaneous test to the common plating Cu film for preparing with plating Cu stack membrane sample, and concrete experimental technique is following:
As shown in Figure 4; Bending plated film bonding force evaluating apparatus mainly comprised clamp body 1, bolt 2 and backing plate 3 about experimental installation adopted, and placed two backing plates 3 between two clamp bodies 1 that are oppositely arranged; Connect through bolt 2 between two clamp bodies 1, two backing plates 3; Leave the gap that is used for plug-in mounting sample 4 between two backing plates 3, backing plate 3 tops are arc surface, and said arc surface diameter is 15 millimeters; The matrix of plated film sample 4 is 304 thick Stainless Steel Bands of 0.1mm, and concrete operations are following:
At first, with acetone that sample 4 surface cleaning are clean, blowing hot wind dries up specimen surface.Then, put into sample 4 between the arc surface of two backing plates 3 and and clamp through bolt 2.Earlier with sample crooked 180 degree of arc surface and tension along the left side; Crooked 180 degree of arc surface and tension along the right again; This operation that circulates, about each bending once as number of bends, till observing that plated film and base material are local and separating (bubbling appears in coated surface).Measure the result and list in table 2, can find out through the data that table 2 is listed, the bonding strength between plating Cu stack membrane and the matrix is compared with the bonding strength between energising plating Cu film and the matrix and has been exceeded several times.
Table 2 bonding force comparative test result
Embodiment 2
Be with embodiment 1 difference:
Through the surface removal greasy dirt; Acid etching and washing are carried out in ultrasonic cleaning after 8 minutes in trieline organic solution; No. 45 steel as matrix material that clean up are connected on the negative electrode of electroplating power supply, and anode adopts fine copper plate (copper content 99.7wt%), starts ultrasonic generator; Adjust its frequency and arrive 16.5kHz, electric current to 150mA; Be suspended to plating piece then and begin in the electroplating solution that is placed in the ultrasonic cleaning tank to electroplate, the electroplating solution prescription is basically identical with the copper plating solution shown in the table 1 with processing parameter, and the current density that is added on the workpiece is 1A/dm 2During plated film to 120 second with the electric current of ultrasonic generator in 30 seconds gradually (evenly) be reduced to 0; Do not adding under the ultransonic state plated film 120 seconds then, subsequently in 30 seconds again with the electric current of ultrasonic generator gradually (evenly) be elevated to 150mA, repeat this technological process; Depositing time 100 minutes, thus deposition obtains the lamination plated copper film.This plated film is laminate structure, about 0.08 micron of present embodiment lamination Cu plated film thickness in monolayer, about 3.2 microns of plated film total thickness.
Present embodiment carries out wear resistance, corrosion resistance nature test to the plating Cu stack membrane for preparing, and has estimated the bonding strength between plated film and the matrix.Test-results shows, electroplates the Cu stack membrane and not only has good wear-resisting, corrosion resistance nature, and present superior film substrate bond strength.
Embodiment 3
Be with embodiment 1 difference:
Through the surface removal greasy dirt; Acid etching and washing are carried out in ultrasonic cleaning after 10 minutes in trieline organic solution; The alloy matrix aluminum material that cleans up is connected on the negative electrode of electroplating power supply, and anode adopts fine copper plate (copper content 99.7wt%), starts ultrasonic generator; Adjust its frequency and arrive 55.5kHz, electric current to 200mA; Be suspended to plating piece then and begin in the electroplating solution that is placed in the ultrasonic cleaning tank to electroplate, the electroplating solution prescription is basically identical with the copper plating solution shown in the table 1 with processing parameter, and the current density that is added on the workpiece is 5A/dm 2During plated film to 510 second with the electric current of ultrasonic generator in 30 seconds gradually (evenly) be reduced to 0; Do not adding under the ultransonic state plated film 510 seconds then, subsequently in 30 seconds again with the electric current of ultrasonic generator gradually (evenly) be elevated to 200mA, repeat this technological process; Depositing time 180 minutes, thus deposition obtains the lamination plated copper film.This plated film is laminate structure, about 2.5 microns of present embodiment lamination Cu plated film thickness in monolayer, about 50 microns of plated film total thickness.
Present embodiment carries out wear resistance, corrosion resistance nature test to the plating Cu stack membrane for preparing, and has estimated the bonding strength between plated film and the matrix.Test-results shows, electroplates the Cu stack membrane and not only has good wear-resisting, corrosion resistance nature, and present superior film substrate bond strength.

Claims (5)

1. preparation method who electroplates the Cu stack membrane is characterized in that: be substrate with the metallic substance, in the electroplating technology process, through intermittently introducing ultrasonic signal deposition Cu plated film, form the Cu stack membrane, concrete steps are following:
(1) greasy dirt on the removal base metal surface cleans in organic solvent for ultrasonic;
(2) acid etching;
(3) washing;
(4) introduce ultrasonic signal, metal refining copper film on base material in the electroplating process discontinuous;
(5) wash and dry up, obtain the stack membrane of Cu;
In the said step (4), introduce ultrasonic signal in the electroplating process discontinuous and be meant:
At first, be that 100~200mA, ultrasonic frequency are plated film 120~510 seconds under 16.5~55.5kHz at the electric current of ultrasonic generator; Then, the electric current with ultrasonic generator was reduced to 0 by 100~200mA gradually in 30 seconds; Then, do not adding under hyperacoustic state plated film 120~510 seconds; Electric current with ultrasonic generator was elevated to 100~200mA by 0 gradually in 30 seconds again; Constantly repeat aforesaid operations, depositing time is 100~240 minutes, obtains the plating Cu stack membrane that needs.
2. according to the preparation method of the described plating of claim 1 Cu stack membrane, it is characterized in that: in the said step (1), the greasy dirt of removing on the base metal surface is workpiece to be immersed in the trieline organic solution scrub.
3. according to the described preparation method who electroplates the Cu stack membrane of claim 1; It is characterized in that: in the said step (1); Cleaning in organic solvent for ultrasonic is to put into trieline organic solution to workpiece to clean 5~10 minutes through Ultrasonic Cleaners, makes workpiece obtain clean surface.
4. according to the preparation method of the described plating of claim 1 Cu stack membrane, it is characterized in that: in the said step (4), the current density of metal refining copper film process is 1~5A/dm on base material 2
5. plating Cu stack membrane with the preparation of the said method of claim 1; It is characterized in that: this stack membrane is through intermittently introducing ultrasonic signal deposits the Cu plated film on metal base material in the electroplating technology process; The metal copper film that obtains is laminate structure; The thickness in monolayer of copper film is in 0.08~2.5 micrometer range, and total thickness is adjusted in 3.2 microns~50 micrometer ranges according to the actual requirements.
CN201010010156XA 2010-01-20 2010-01-20 Electroplated Cu laminated film and preparation method thereof Expired - Fee Related CN102127784B (en)

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CN102147354A (en) * 2010-02-10 2011-08-10 中国科学院金属研究所 Device for evaluating coating binding force
CN104359742B (en) * 2014-10-13 2017-02-22 中车青岛四方机车车辆股份有限公司 Coloring method for wrought aluminum alloy welded joint color metallography
CN109112578A (en) * 2018-09-06 2019-01-01 中国石油天然气集团有限公司 A method of gradient-structure fine metal component is prepared using electroforming process
CN109862710B (en) * 2019-04-08 2021-03-16 四川锐宏电子科技有限公司 Copper deposition process and device for PCB with uniform thickness
CN110184625A (en) * 2019-07-08 2019-08-30 昆明理工大学 A method of improving pure nickel mechanical property
CN111501072B (en) * 2020-05-09 2021-01-05 广东哈福科技有限公司 Copper electroplating solution passivating agent and copper electroplating solution

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Publication number Priority date Publication date Assignee Title
CN1612950A (en) * 2001-09-05 2005-05-04 3M创新有限公司 Ultrasonically-enhanced electroplating apparatus and methods

Non-Patent Citations (1)

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