CN1335419A - Electroplating method using with combination of electroplating liquid vibrating flow and pulse type electroplating current - Google Patents

Abstract

To provide a plating method which is capable of efficiently forming plating films of conductive patterns of micro-structure with good quality at a high speed. While vibrating flow of >=150 mm/sc in three-dimensional flow velocity is generated by vibrating the vane with amplitude 0.1 to 10.0 mm and number of vibration 200 to 800 times/minute, voltage is impressed between the articles to be plated which are arranged in the plating bath as cathodes and a metallic member as an anode. The plating current at this time is impulsive and alternately strikes the first state to sustain the first time T1 at a first value 11 and the second state to sustain the second time T2 at a second value 12. The first value is >=5 times the second value and the first time is >=3 times the second time.

Description

Use the vibrational flow of electroplate liquid and the electro-plating method of pulse type electroplating current combination

The present invention relates to electro-plating method, relate in particular to the electro-plating method of electric condition particular combinations feature with electroplate liquid physical condition and electroplating current.

So far, make the field, be widely used in the plating that forms conductive material membrane on the article surface at article such as electronic units.

Especially, recently for satisfying the demand of electronic unit miniaturization and multifunction, requiring to go up the conductive pattern that forms microtexture at article surface (comprising through-hole inner surface and blind hole internal surface).

For example, corresponding with the narrow chipization of the input/output terminal of the Highgrade integration that is accompanied by semiconductor device, the wiring figure is carried out miniaturization, require through hole and blind hole internal diameter is below the 100 μ m thereupon, especially wants little to 50 μ m, even below the 30 μ m.In addition, the longitudinal mode that also requires through hole and blind hole is more than 5, even is more than 8 than big.

And, for example in the multilayer wiring of semiconductor device, capacity is reduced to purpose between the wiring that is taken place with highly integrated wiring miniaturization to result from, and replaces existing aluminium wiring and utilizes the copper wiring, adopts and utilizes galvanized copper wiring method in order to form such multilayer wiring.This method requires to pile up copper in will be below the internal diameter 1 μ m minimum blind hole.

And, for example, also require on the surface of the chip part of 0.3mm side-to-side dimensions, to form 1 counter electrode film.

The applicant once proposed a kind of effective electro-plating method (opening flat 11-189880 communique with reference to the spy) that is specially adapted to have the article of microtexture part such as minute aperture.This method is vibrational flow to take place in electroplate liquid and make it and the foaming of air bell and usefulness.This method also can be applicable to electroless article effectively except that being used for plating effectively.

Yet this method will be provided with air bell in accommodating the plating tank of electroplate liquid, and the pipeline that imports air to this air bell need be set, therefore, just produce a difficult point, promptly, the size of electroplating liquid measure and plating tank must be done greatlyyer etc., thereby electroplanting device maximizes.

On the other hand, as galvanized power supply, generally adopt direct supply.But, in recent years, a scheme is proposed in order to improve the electroplating film quality, that is, the limit changes the electroplating current cycle, and electroplate on the limit.This method alternately flows the electric current of straight polarity and the electric current of negative polarity, that is to say, its aim is, will be by the straight polarity small protuberance in concavo-convex on the formed coated surface of switching on, dissolve by negative polarity energising concentrated part ground, by carrying out so repeatedly, it is smooth and do not have a high-quality film of defectives such as small cavity to obtain the plane.Yet this method also has disadvantage, that is, owing to removed formed plate surface part, and so improved film forming speed (that is, having improved electroplating processes speed).

Recently, conductive pattern is in the tendency of miniaturization day by day, when forming the electroplating film of such conductive pattern, is easy to take place the even property of defective and non-uniform film thickness, has become difficulty gradually so keep the good quality of electroplating film.

In addition, the applicant also proposed following scheme, promptly, limit vibration is stirred the electroplate liquid limit and is carried out chromed electro-plating method, and is stirred the electroplate liquid limit by galvanized article receiving in the vibration of cylindrical shell inner edge and carry out chromed method (opening flat 7-54192 communique and the spy opens flat 6-330395 communique with reference to the spy) a plurality of.

Yet, in these methods, all use direct current, and for the direction size of crosscut long axis direction, that is, width is below the 5mm as electroplating current, for example the microsize of 0.31-1.0mm is not proposed particularly by being suitable for of electro.Such microsize by electro in cylindrical shell in the electroplating process, in cylindrical shell, overlapped between the electro, electroplate liquid is extremely low to the flowability that required electroplating film forms part.Therefore, so-called amplitude bigger by the occasion of electro, incommensurable technical difficulty is then arranged, thereby on the homogeneity this point of film forming speed and electroplating film thickness, the leeway of improvement is arranged further.

Therefore, one of purpose of the present invention is, a kind of electro-plating method that can zero defect have the even property of non-uniform film thickness etc. and form the microtexture conductive pattern with high quality is provided.

Another object of the present invention then is to provide at a high speed a kind of superior in quality electroplating film of conductive pattern that obtains microtexture.

A further object of the present invention is that then the electricity that can utilize less device to obtain microtexture expeditiously leads the good electroplating film of graphical quality.

According to the present invention, in order to achieve the above object, it is characterized in that, vibration by single hop or multistage fixed vibration blade on the vibrating arm that is connected with the vibration generation part and in electroplate liquid, vibrates, vibrational flow takes place in electroplate liquid, simultaneously with contact with described electroplate liquid dispose made negative electrode by electro, and make anode with the metal parts that contacts configuration with described plating bath, making alive between described negative electrode and anode, be pulse type by electroplate liquid to the electroplating current of cathode flow by described anode this moment, alternately be chosen at the 1st state that the 1st time T 1 of the 1st value I1 continues, and the 2nd state that continues in the 2nd time T 2 with same polar the 2nd value 12 of described the 1st value; Described the 1st value 11 is more than 5 times of described the 2nd value 12; Described the 1st time T 1 is more than 3 ones of described the 2nd time T 2.

In a form of the present invention, the 6-25 that described the 1st value I1 is described the 2nd value I2 doubly; The 4-25 that described the 1st time T 1 is described the 2nd time T 2 doubly.In a form of the present invention, described the 1st time T 1 is 0.01 second-300 seconds.In a form of the present invention, described vibration blade is to vibrate under the condition of amplitude 0.05-10.0mm and vibration number 200-1500 time/minute.In a form of the present invention, the three-dimensional flow of the vibrational flow of described electroplate liquid is that 150mm/ is more than second.In another form of the present invention, described vibration generation part vibrates under the 10-500Hz condition.

In a kind of form of the present invention, under the condition of amplitude 0.05-5.0mm and vibration number 100-300 time/minute, make and describedly vibrated by electro.In a kind of form of the present invention,, shaking width of cloth 10-100mm and shaking to make under several 10-30 time/minute the condition and describedly shaken by electro.In a kind of form of the present invention, the described to-be-electroplated surface that is had the following microtexture of 50 μ m by electro.

In a kind of form of the present invention, a plurality of being remained on by electro kept in the container, this maintenance container has little perforate that can be by electroplate liquid and has owing to make electroplating current flow to this by the used conductive component of electro with described the contact by electro, around the rotation center of non-perpendicular direction, be rotated in described electroplate liquid by this maintenance container, make described a plurality ofly in described retainer, rotated by electro, and make repeatedly described each contacted with described conductive component respectively by electro and break away from.

In a kind of form of the present invention, the width of described plated body product is below the 5mm.

Below accompanying drawing and symbol thereof are done simple declaration.

Fig. 1 implements the sectional view that electroplanting device constitutes for expression electro-plating method embodiment 1 of the present invention.

Fig. 2 implements the sectional view that electroplanting device constitutes for expression electro-plating method embodiment 1 of the present invention.

Fig. 3 implements the vertical view that electroplanting device constitutes for expression electro-plating method embodiment 1 of the present invention.

Fig. 4 is the amplification view of vibration transmission rod to the vibrating mass installation portion.

Fig. 5 is the amplification view of vibration blade installation portion on vibration transmission rod.

Fig. 6 represent vibration blade on vibration transmission rod, install the distortion illustration.

The sectional view of the variation that Fig. 7 is installed on negative busbar by electro for expression.

Fig. 8 passes through by electro mobile electroplating current variation diagram for expression.

Fig. 9 constitutes sectional view for expression electro-plating method embodiment 2 of the present invention implements electroplanting device.

Figure 10 constitutes sectional view for expression electro-plating method embodiment 2 of the present invention implements electroplanting device.

Figure 11 constitutes vertical view for expression electro-plating method embodiment 2 of the present invention implements electroplanting device.

Figure 12 implements the sectional view of the electroplanting device of electro-plating method of the present invention for expression.

Figure 13 is an otch vertical view of the electroplanting device of Figure 12.

The sectional view that the vibrational flow generating unit that Figure 14 implements the employed electroplanting device of electro-plating method of the present invention for expression constitutes is installed on plating tank.

The sectional view that the vibrational flow generating unit that Figure 15 implements the employed electroplanting device of electro-plating method of the present invention for expression constitutes is installed on plating tank.

The vertical view that the vibrational flow generating unit that Figure 16 implements the employed electroplanting device of electro-plating method of the present invention for expression constitutes is installed on plating tank.

Figure 17 is the vertical view of presentation layer zoarium.

Figure 18 is the sectional view of the inaccessible appearance in plating tank top of presentation layer zoarium.

Figure 19 is the fit figure of presentation layer.

Figure 20 passes through by electro mobile electroplating current variation diagram for expression.

Figure 21 is the sectional view of expression vibrational flow generating unit variation.

Figure 22 is the vertical view of expression Figure 21 vibrational flow generating unit.

Figure 23 electroplates with power supply one illustration for indicating impulse.

In above-mentioned accompanying drawing, 1,1 '; 1 "-metal sheet, 2,2 '-rubber plate, 2a, 2c-is a solid rubber layer, 2b-rubber sponge layer, 3-laminate, the 5-communicating pores, 6-opening, 12-plating tank, the 13-supporting base, 14-electroplate liquid, 15-bearer frame, 16-vibrational flow generating unit, the 16a-pedestal, 16b, the 46-disc spring, the 16c-vibrating mass, the 16d-vibrating motor, the 16e-vibration transmission rod, 16f-vibration blade, 16g1,16g2-vibratory stress discrete part, 16h1, the 16h2-pad, 16i1,16i2,16i3,16i4,16m, 16n, the 117-nut, 16j-vibration blade solid components, 16k-shading ring, 16p-elastomeric element thin plate, 20, the 48-oscillating motor, 22-union lever, 24, the 44-rocking frame, the 26-guide rail, 28, the 48-vibrating motor, 30-negative busbar, 32-positive bar, the 34-power source circuit, 40-is by the electro holding member, 40a-top hook portion, hook portion under the 40b-, the 40c-compression spring, the 49-counterweight, 50-cylinder bearing parts, 52-cylindrical shell, the 52a-tube part, 54-negative electrode conductive component, 54 ', the 56-envelope curve that insulate, 56-anode metal parts, the 112-Shockproof rubber, 116,131, the 132-bolt, 118-installation parts, 119-rubber ring, 123-upside guiding parts, 124-downside guiding parts, 136-flexible seal parts, X-is by electro.

The invention embodiment

Following with reference to accompanying drawing, specific embodiments of the invention are described.In addition, in the accompanying drawings all, parts or the part with identical function added identical symbol.

The electroplanting device that Fig. 1 and Fig. 2 implement electro-plating method embodiment 1 of the present invention for expression constitutes sectional view, and Fig. 3 is its vertical view.

In these figure, 12 is plating tank, contains electroplate liquid 14 in this plating tank.16 is the vibrational flow generating unit.This vibrational flow generating unit 16 includes: the pedestal 16a that installs by Shockproof rubber on plating tank 12; At the disc spring 16b of this pedestal lower end fixed as vibration absorption component; At this disc spring upper end fixed vibrating mass 16c; Be installed in the vibrating motor 16d of the vibration generation part on this vibrating mass; On vibrating mass 16c, be installed in the vibration transmission rod 16e of upper end; Be immersed in the vibration blade 16f that installs on the position in the electroplate liquid 14 in this vibration transmission rod Lower Half.In disc spring 16b, Figure 12 is described as described later, and shaft-like guiding parts can be set.

Vibrating motor 16d for example by using Frequency Converter Control at 10-500Hz, is preferably in 20-60Hz, vibrates under the 30-50Hz better condition.The vibration that is taken place by vibrating motor 16d is delivered to vibration blade 16f by vibrating mass 16c and vibration transmission rod 16e.Vibration blade 16f is vibrated by front-end edge with required vibration number in electroplate liquid 14.This vibration is to take place like this,, begins from the mounting portion to vibration transmission rod 16e that ora terminalis forward carries out " soft and crooked " that is.The amplitude of this vibration and vibration number are different with vibrating motor 16d, but can according to the mechanical characteristic of vibration transfer path and with the decisions such as interaction property of electroplate liquid 14, in the present invention, amplitude is 0.05-10.0mm (for example 0.1-10.0mm), vibration number is 200-1500 time/minute (for example 200-800 time/minute), is ideal.

Fig. 4 is according to transmitting bar 16e goes up amplification view from installation portion to vibrating mass 16c.The screw division that forms in vibration transmission rod 16e upper end by vibrating mass 16c up and down two mesh with nut 16i1,16i2,16i3,16i4 by vibratory stress discrete part 16g1,16g2 and pad 16H1,16H2.Vibratory stress discrete part 16g1,16g2 for example are made of rubber.

Fig. 5 is vibration blade 16f goes up an amplification view from installation portion to vibration transmission rod 16e.Up and down vibration blade fixing part 16j is set both sides in each of seven vibration blade 16f.At the shading ring 16k that is provided for by fixing part 16j between the contiguous vibration blade 16f setting between vibration blade 16f at interval.The upside of the vibration blade 16f of topmost and the downside of the vibration blade 16f of foot be provided with vibration transmission rod 16e on the matched nut 16m of screw that forms.

Fig. 6 is the distortion illustration of expression vibration blade 16f to vibration transmission rod 16e installation portion.In this variation, respectively each vibration blade 16f is gone up installation to vibration transmission rod 16e by upside and downside screw 16n.Also have, between vibration blade 16f and fixing part 16j, add the elastomeric element thin slice 16p that constitutes by fluorine resin or viton etc., so just can prevent the breakage of vibration blade 16f.As shown in the figure, the fixing part 16j of upside following (press surface) is the dome tubular, and the fixing part 16j of downside top (press surface) is corresponding recessed round shape.Like this, the part of the vibration blade 16f that is pushed by above-below direction by fixing part 16j bends, and the leading section of vibration blade 16f is angle [alpha] to horizontal plane, and this angle [alpha] for example can be more than-30 ° below 30 °, and is better below 20 ° more than-20 °.Especially, angle [alpha] is more than-30 ° below-5 ° or more than 5 ° below 30 °, preferably-20 ° more than or below-10 °, perhaps more than 10 ° below 20 °.When the press surface with fixing part 16j made single face, angle [alpha] was 0 °.Angle [alpha] is with regard to whole vibration blade 16f, need not be identical, for example shown in Figure 1, with regard to the 1-2 root vibration blade 16f of below, can be used as one value (: be reverse) promptly down with shown in Figure 6, with regard to vibration blade 16f in addition, can be used as+value (promptly up: be direction shown in Figure 6).

As vibration blade 16f, can use resilient metal sheet, synthetic resin board or rubber plate etc.The thickness of vibration blade 16f should be designed to when 16 actions of vibrational flow generating unit, and the front-end edge of this vibration blade 16f partly is flutter phenomenon (being fluctuation status).When vibration blade 16f is made by metal sheets such as stainless steels, its thickness can be made 0.2-2mm.In addition, when vibration blade 16f was made by synthetic resins or rubber, its thickness can make 0.5-10mm.

In Fig. 1-3, oscillating motor is connected with rocking frame 24 by union lever 22.The setting of this rocking frame 24 is, but along continuous straight runs (left and right directions among Fig. 1) is done to come and go mobile on track 24.Vibrating motor 28 is installed on rocking frame 24.On rocking frame 24, negative busbar 30 and positive bar 32 are installed, keep state of insulation with rocking frame 24, they are connected with the negative terminal and the positive terminal of power source circuit 34 respectively.Power source circuit 34 can make square waveform voltage by voltage of alternating current.This power source circuit for example is to have the transistorized rectifying circuit of use, and Pulased power supply unit is a known devices.

In the present invention for AC rectification (comprising additional flip-flop) is exported in the generation employed power source circuit of electroplating current (supply unit) use.As this supply unit or rectifier, can utilize semi-conductor adjustable type power supply, Dropper mode power supply, switch power supply, silicon rectifier, SCR type rectifier, the high-frequency type rectifier, the rectifier of frequency conversion digital control approach (for example Co., Ltd. central authorities make Power Master), the KTS series that Sansha Electric Manufacturing Company, Limited makes, the system RCV of four countries Electric Co., Ltd power supply, switching regulaor formula power supply with make by transistor switch and (be converted to after the direct current for the high frequency switch power of supplier's shape waveform pulse electric current with exchanging by diode by transistor switch open close, by power transistor the high frequency of 20-30KHz is added transformer, take out output) through rectification and smoothing again, PR formula rectifier, the high-frequency impulse PR power supply of high frequency control mode (HiPR series (strain formula pin society thousand generations field) etc. for example.

Below current waveform is described.In order to realize electroplating high speed and the improvement of electroplating overlay film, preferred electroplating current waveform is important.Difference can not stipulate entirely that still, present situation is owing to electroplate the size difference of total class difference or electroplate liquid component or plating tank to electroplate required voltage and current condition: if electroplating voltage is the 2-15V of direct current, and then can be fully to all electroplating.Here, the rated output voltage of electroplating with direct supply is the standard that 6V, 8V, 12V and four kinds of 15V have become the same trade.The following voltage of this voltage rating is adjustable, therefore, preferably has the power supply of the voltage rating in some leeway for desirable magnitude of voltage, is ideal.At industry, the power supply output-current rating has been carried out stdn, reach 500A, 1000A, 2000A-10000A, other adopt the form of customized production.As the best way is kind and surface-area according to electro, as by the needed current density of electro * by the surface-area of electro, the required current capacity of decision power supply, preferably the optimality criterion power supply that matches with it.

Originally, we can say that it is very short that pulse height W compares with period T, still, is imprecise.And, in the pulse wave, do not comprise rectangular wave ripple in addition.The used element responsiveness of pulsing circuit uprises, and the pulse width of cloth also is ns (10 ^-9S) below.Along with the amplitude stenosis of pulse, to keep the sharp waveform of leading edge and trailing edge and become difficult, this may be owing to contain due to the radio-frequency component.

Kind as pulse wave has zigzag wave, light source ripple, choppy sea, complex wave, rectangular wave etc., but in the present invention, especially waits from electrical efficiency and smoothness, and rectangular wave is an ideal.

If pulse plating is shown with power supply one example, then as shown in figure 23, comprise switching regulaor formula direct supply and transistor switch, to disconnect at a high speed and to connect, supply with the square-wave pulse electric current by transistor switch to load.

The top of the electroconductibility holding member 40 that maintenance is used by electro X is carried out machinery with negative busbar 30 and is electrically connected.Be submerged in the electroplate liquid 14 by the bottom of electro holding member 40,, be electrically connected by galvanized article X and be held by anchor clamps etc. in this part.Also have, though also not shown in the drawings, carry out machinery with positive bar 32 and be electrically connected by the anode metal parts of being made by electroplated metal (for example being housed in the form in the plastics system cage).Its underpart is submerged in the electroplate liquid 14.In addition, on negative busbar, install and the method for anode metal parts anode bus installation or the shape and the structure of negative busbar and positive bar, all can use various known technology as electro.

The sectional view of the variation that Fig. 7 is installed on negative electrode by electro for expression.In this example, electroconductibility holding member 40 includes: the hook portion 40a on the top of installing on negative busbar 30; Clamping is by the clamp portion 40b of the bottom of electro X; Make the compression spring 40c of clamping part generation holding force.

In Fig. 1 to Fig. 3, by making oscillating motor 20 action, rocking frame 24 and holding member 40, so installed in the above by electro X, for example shaking width of cloth 10-100mm and shaking under several 10-30 time/minute the condition and shake.In addition, vibrating motor 28 for example by using the control of frequency transformer, at 10-60Hz, preferably vibrates under the 20-35Hz condition.The vibration that is taken place by vibrating motor 28 is delivered to by electro X by vibrating grid 24 and holding member 40, thus, is that 0.05-5.0mm (for example 0.1-5.0mm), vibration number are to vibrate under 100-300 time/minute the condition by electro X at amplitude.

The graphic representation of Fig. 8 for representing to be changed by electro X mobile electroplating current (current density) based on passing through according to power source circuit 34 added voltage between negative busbar 30 and positive bar 32.As shown in the figure, electroplating current the 2nd state that to be the 1st state that continues of the 1st time T 1 of the 1st value I1 continue with the 2nd time T 2 of the 2nd value 12 (＜11) replaces the square topped pulse shape that shows.Here, the 1st value I1 and the 2nd value I2 are identical polars.I1 is more than 5 times of I2 (for example more than 6 times: be 6-25 times as an example), and preferably 8-20 doubly.T1 is more than 3 times of T2 (for example more than 4 times: 4-25 doubly as an example), and preferably 6-20 doubly.Combine by vibrational flow, in fine conductive pattern, also can obtain good quality and high film forming speed the electroplate liquid 14 of such electroplating current and above-mentioned vibrational flow generating unit 16.

The 1st value I1 and the 1st time T 1 are according to the settings aptly such as composition of electroplating kind (for example: plating copper sulfate, plating cupric cyanide, plating tetra-sodium, nickel plating, plating black nickel, plating nickel sulfamic acid, chromium plating, plating zinc cyanide, the no zinc cyanide of plating, plating cash tin, plate acid tin, silver-plated, plating gold tricyanide, the acid gold of plating, copper facing zinc alloy, ferro-nickel alloy, tinlead plating, plating palladium, plate scolding tin etc.) or electroplate liquid, for example, the 1st value I1 can be decided to be 0.01-100 (A/dm ²) scope within; The 1st time T 1 can be decided to be within the scope of 0.01-300 (second) (for example 3-300 second).But, not being only limited to above-mentioned scope, best 11,12, T1, T2 also can change in broad range according to above-mentioned plating kind or electroplate liquid component etc., for example, are accompanied by galvanized carrying out and the electroplate liquid component is changed because of changing.

According to the electroplating film that should form, identical with known electrochemical plating, select electroplate liquid 14.For example when plating copper sulfate,, can use the electroplate liquid of making by following material as through hole liquid:

Copper sulfate 60-100g/L (liter)

Sulfuric acid 170-210g/L

It is an amount of that light is translated agent

Chlorion 30-80mL/L

As common liquid, can use the electroplate liquid of making by following material:

Copper sulfate 180-250g/L

Sulfuric acid 45-60g/L

It is an amount of that light is translated agent

Chlorion 30-80mL/L

Secondly, for example when carrying out nickel plating, can use the electroplate liquid of making by following material as through hole liquid:

Single nickel salt 270g/L

Nickelous chloride 68g/L

Boric acid 40g/L

Sal epsom 225g/L

As common liquid, can use the electroplate liquid of making by following material:

Single nickel salt 150g/L

Ammonium chloride 15g/L

Boric acid 15g/L

As power liquid, can use the electroplate liquid of making by following material:

Single nickel salt 240g/L

Ammonium chloride 45g/L

pH 4-5

Liquid temp 45-55 ℃

Also have, for example when plating acid tin,, can use the electroplate liquid of making by following material as the sulfuric acid saline solution:

Stannous sulfate 50g/L

Sulfuric acid 100g/L

Cresol sulfonic acid 100g/L

Gelatin 2g/L

2-Naphthol 1g/L

As by galvanized article X, can enumerate electronic unit and mechanical part and other etc., but be not particularly limited.What can bring into play speciality of the present invention significantly is the occasion that forms the electroplating film with microtexture., can have been enumerated by the plating example of electro as like this: following (the 20-100 μ m for example of multi-layer wire substrate internal diameter 100 μ m; Perhaps, particularly below the 50 μ m, especially below the 30 μ m, for example 10 μ m, 5 μ m, 3 μ m etc.) small blind hole or the formation of the internal lip-deep plated conductive film of through hole (for example degree of depth 10-100 μ m); Following (the 20-50 μ m for example of square 50 μ m between circuit board; Perhaps, particularly below the 30 μ m, especially below the 20 μ m, for example below the 10 μ m, 5 μ m etc.) the 30 μ m that high-density wiring figure is used are following (particularly below the 20 μ m, especially 10 μ m, 5 μ m for example, 3 μ m etc.) the groove (for example degree of depth 7-70 μ m) of the small width of cloth with the formation of interior conducting film; When semiconductor device is made multilayer wiring with the formation of imbedding conducting film in the internal diameter 0.3 μ m of copper metal line government establishments law or the atomic small blind hole below it or the minimum groove (for example 0.1 μ m, the degree of depth 1.5 μ m's); The formation of the microelectrode bus of semiconductor device arranged in high density etc.When especially, the present invention is applicable to the structure of high aspect ratio (for example more than 3 times, especially more than 5 times) to improve effect very big.

Also have, as by electro X, can use mean diameter to be the minimum article of 5-500 μ m, so-called here mean diameter is meant that cross one another three directions are the mean value of the size of representative.By electro X, can enumerate copper powder and as this through the metal-powder of pre-treatment aluminium powder form and iron powder etc., through synthetic resin powder such as the ABS resin powder of conductor processing with through the ceramic chip of conductor processing etc.In addition, also can enumerate other electronic unit, mechanical part, metal-powder alloy, micropartical is inorganic and pigment dyestuff, Metal Ball etc.

For example,,, on plated nickel film, form copper plating film and silver-plated film again, can form composite film coating as forming plated nickel film above the copper particle by metallics at 300 μ m left and right sides diameters.

Also have, when by electro being electrical insulating property article such as plastics, will carry out the base treatment of electroconductibility as pre-electroplating treatment.But, electroplate under the occasion of face at microtexture, high aspect ratio, handle even carry out conductive substrates, also be difficult to form even good electrical conductivity substrate, thereby be easy to become inhomogeneous by the thickness of electroplating resulting electroplating film by common electroless plating.In order to solve such problem, can handle with reference to adopting sputter or evaporation to carry out conductive substrates, still, in this case, owing to be in reliever, to handle, can not handle in a large number and processed continuously difficult point so have the cost rising that makes treatment unit.To this, use with the identical method of vibrational flow method that is used for used in the present invention when making the treatment solution vibrational flow, conductive substrates to electroless plating etc. is handled, even under the occasion of the plating face of microtexture, high aspect ratio, also can obtain the substrate of homogeneity high conductivity.Thereby, combined by such conductive substrates is handled with electro-plating method of the present invention, can carry out continuously by pre-treatment to electroplating processes, boost productivity expeditiously.

Electro-plating method of the present invention, improved because the vibrational flow that is produced in the electroplate liquid 14 makes the flowing property of electroplate liquid in the microtexture recess by vibrational flow generation part 16, although constitute simultaneously by the 1st state and than the 1st state fully low but for same polarity and than the 1st state very the 2nd state of short period of time carry out the pulse type electric current that electroplating current constituted repeatedly, can improve the homogeneity of film thickness like this, and the non-uniform film thickness that produces of the formation of the electroplating film of concentrating at protuberance and edge part can reduce owing to direct current electrode position the time is even or the generation of defects such as pore of through hole and blind hole, and can obtain high surface light and translate, in addition, also since during the pulse type electroplating current of reversal of poles formed a part of electroplating film do not dissolve thereupon, so can obtain high film forming speed, the formation of manufacturing installation is oversimplified.Thereby, by electro, can form desirable electroplating film at a high speed by high quality and high efficiency for widely.

In addition, in the present invention because the vibrational flow effect that taken place in the electroplate liquid 14, though by the distance of electro X and anode metal parts approaching and improved current density, also be difficult to be short-circuited.This also can think unfavorable condition and can high rate of finished products and form the major cause of Shen plated film at a high speed not take place to burn or burn etc.

In order to obtain such effect better, preferably, the three-dimensional flow of the vibrational flow of electroplate liquid 14 is that 150mm/ is more than second.So high three-dimensional flow can be realized by vibrational flow effectively by electroplate liquid, is difficult to realize by general stirring, even realized, also needs large-scale device to constitute, and this is disadvantageous.

The embodiment of the invention, by rocking frame 24 shake and/or vibrate carry out by electro X shake and/or vibrational energy further improves above-mentioned effect, still, even do not carry out these shaking and vibrating and can obtain good result by electro X.Do not use rocking frame 24, oscillating motor 20 and vibrating motor 28 etc., but, the formation of device is more oversimplified by supporting negative busbar 30, positive bar 32, by electro X and anode metal material etc.Under by the situation of electro X bigger or long size flat plate-like article in overall dimensions such as multi-layer wire substrates, shake by moving along direction in the face of article, can improve effect.

The sectional view that Fig. 9 and Figure 10 constitute for expression electro-plating method embodiment 2 embodiment electroplanting devices of the present invention.Figure 11 is its vertical view.

Present embodiment by the maintenance of electro X and to all different with the illustrated embodiment 1 of above-mentioned Fig. 1-8 by the supply mode of electro X, is the mode that adopts so-called barrel plating (barrel plating).

In Fig. 9-11, vibrating grid 44 is installed on the plating tank 12 by the disc spring 46 as vibration absorption component.Vibrating motor 48 is installed on vibrating grid 44 and takes it and counterweight 49 that weight balancing is used.On vibrating grid 44, cylindrical shell 52 is installed by support unit 50.The installation of this cylindrical shell can be rotated support unit 50, rotates along the direction shown in the arrow among Fig. 9 by not shown drive member.In cylindrical shell 52, contain a plurality of small by electro X.On the periphery of cylindrical shell 52, be formed with prevention by electro X by and a plurality of little perforate that allows the liquid of electroplate liquid 14 to pass through.In cylindrical shell 52, be provided with negative electrode conductive component 54, extend to the bottom of cylindrical shell.This negative electrode conductive component 54 coats the 54 ' rotation center with cylindrical shell 52 that connects up by insulation and is connected with the negative terminal of power source circuit 34 by being installed in the duct member 52 on the cylindrical shell.Even negative electrode conductive component 54 does not rotate when cylindrical shell rotates yet, therefore, along with cylindrical shell rotation rotation carried out repeatedly by electro X with negative electrode conductive component 54 contact and from the disengaging of negative electrode conductive component 54.56 is the anode metal parts at electroplate liquid 14 middle and lower parts dipping.These anode metal parts 56 for example are housed in the plastic cage, and coat wiring 56 ' by insulation and be connected with the positive terminal of power source circuit 34.As shown in Figure 9, anode metal parts 56 are configured in the both sides of cylindrical shell 52.Yet anode metal parts 56 also can only be arranged on a side of cylindrical shell 56.

Vibrating motor 48, for example amplitude and the vibration number with above-mentioned vibrating motor 28 same degree vibrates, and is to vibrate for 100-300 time/minute at amplitude 0.05-5.0mm (for example 0.1-5.0mm), vibration number by electro X.In the present embodiment by carrying out further having been improved effect, can obtain good effect but this is also vibrated also by electro X by the vibration of electro X with the vibration of vibrating grid 44.By not using vibrating grid 24 and vibrating motor 48 etc. to use supporting support unit 50 and cylindrical shell 52, the formation of device is oversimplified more.

In the present embodiment, the setting of electroplating current density is identical with the explanation of above-mentioned Fig. 8.In the present embodiment to each by electro X, with respectively the contacting of negative electrode conductive component 54 time, at the 1st state or the 2nd state, the electroplating current of the change procedure that perhaps between the 1st state and the 2nd state, flowing.But, if the current density continuous representation only will contact the time, then fifty-fifty, as shown in Figure 8, still can obtain the effect identical with the foregoing description 1.

Present embodiment is for a plurality of when being formed following electrode film or electroplating film simultaneously by electro X, the most suitable, promptly, to microsize electro X, the for example formation of the electrode film of the chip parts such as ceramic chip electrical condenser of the size about 0.6mm * 0.3mm * 0.2mm is perhaps to formation of the electroplating film of diameter 0.5mm * length 20mm left and right sides pin etc.Like this, using, wherein be below the 2mm as being of a size of below the width of cloth 5mm by the direction of the crosscut long axis direction of electro, during small article below the 1mm, be big in the homogeneity of electroplating film thickness and the improvement effect of film forming speed.As other by electro X, also can enumerate the metal-powder alloy, micropartical is inorganic and pigment dyestuff and Metal Ball etc.

Before implementing electro-plating method of the present invention, to carry out required pretreatment procedure certainly.For this pretreatment procedure, also can adopt existing known electro-plating method equally.

Also have, in the method for the invention, as in order to occur in the employed vibrational flow generating unit of the required oscillating current of electroplate liquid with vibration blade, can use above-mentioned spy (for example to open the part described in the flat 11-189880 communique aptly, illustrated with reference to Fig. 7 in this communique-8, vibration blade is configured in the plating tank bottom, transmit frame by vibrating motor by vibration vibration is passed to vibration blade, and the vibration blade along continuous straight runs is vibrated), or the described part of in this communique, quoting.

For example, as the vibrational flow generating unit, can use the vibrational flow generating unit shown in Figure 21 and Figure 22.In these figure,, supporting two vibrational flow generating units 16 by being fixed on the resting support 15 on the set supporting base 13 of coating bath 12.In vibrational flow generating unit 16, accepting on the vibrating mass 16 ' e that vibration transmits above-below direction vibration transmission rod 16e to be installed by vibrating motor 16d " the upper end.Vibration transmission rod 16e " in plating tank 12, extend, the end of horizontal direction vibration transmission rod 16e ' is installed in its bottom.Shared two the vibrational flow generating units 16 of this vibration transmission rod 16e ' are equipped with the vibration blade 16f of above-below direction.By vibrating motor 16d by vibrating mass 16c ', vibration transmission rod 16e ", 16e ' is to vibration blade 16f transmitting vibrations, makes the vibration of vibration blade 16f along continuous straight runs.

Figure 12 implements the sectional view of the another kind of embodiment of the employed electroplanting device of electro-plating method of the present invention for expression.Figure 13 is its a part of otch vertical view.This embodiment, the formation of its vibrational flow generating unit 16 is different with the foregoing description.That is, facing to institute's fixed installation parts 118 on the upper end edge portion of plating tank 12, the fixing lower end of disc spring 16b, the downside at the fixed vibrating mass 16c of the upper end of this disc spring 16b institute is equipped with vibrating motor 16d.In addition, in disc spring 16b,, and all dispose each other with proper spacing at the upside guiding parts 123 of the fixing upper end of vibrating mass 16c at the fixing downside guiding parts 124 of lower end of installation parts 118.

The sectional view of the another kind of embodiment that the vibrational flow generating unit that Figure 14 and Figure 15 implement the employed electroplanting device of electro-plating method of the present invention for expression constitutes is installed on plating tank, Figure 16 is its vertical view.Figure 14 and Figure 15 are equivalent to the X-X ' section of Figure 16 and the section of Y-Y ' respectively.Also have, in these figure, all omitted negative electrode and anode and power source circuit etc. that electroplating processes is used.

In such an embodiment, replace above-mentioned disc spring 16b and use rubber plate 2 and metal sheet 1,1 ' laminate 3.Promptly, laminate 3 is to form like this, on the upper end edge portion institute fixed installation parts 118 of plating tank 12, the metal sheet of installing 1 ' is fixing by Shockproof rubber 112 by bolt 131, go up configuration rubber plate 2 at this metal sheet 1 ', configuration metal sheet 1 will make it make integral body by nut 116 and bolt 117 on this sheet rubber 2.

Vibrating motor 16d is fixed on the metal sheet 1 by bolt 132 by support unit 115.In addition, the upper end of vibration transmission rod 16e is installed on the laminate 3 by rubber ring 119, particularly on metal sheet 1 and rubber plate 2.That is, the upside metal sheet is also brought into play the function of the embodiment vibrating mass 16c described in Fig. 1 and other figure; And downside metal sheet 1 ' is also being brought into play the function of the embodiment pedestal 16a described in Fig. 1 and other figure.So, have these metal sheets 1,1 ' laminate 3 (being mainly rubber plate 2) is being brought into play and Fig. 1 and the identical absorption of vibrations function of the described disc spring 16b of other figure.

Figure 17 illustrates the vertical view of laminate 3.With the embodiment of corresponding Figure 17 of Figure 11-16 embodiment (a) in, in laminate 3, be formed with communicating pores 5 by vibration transmission rod 16e.Also have, in the embodiment of Figure 17 (b), laminate 3 is split up into 2 two portions 3a, 3b by the separate line by communicating pores 5 to be formed, can pass through vibration transmission rod 16e easily like this when device is assembled.In addition, in the embodiment of Figure 17 (c), form the annular shape corresponding, form peristome 6 at middle body with the upper end edge portion of plating tank 12.

In the embodiment of above-mentioned Figure 17 (a) and (b), the top of plating tank 12 is stopped up by laminate 3, therefore, in the time of can preventing electroplating processes, is leaked towards periphery by electroplate liquid 14 evaporable gases or the electroplate liquid that disperses.

Figure 18 is stopped up the sectional view of the appearance on (sealing) plating tank top by this laminate 3 for expression.Among the embodiment of Figure 18 (a), rubber plate 2 contacts and seals with vibration transmission rod 16e in communicating pores 5.And among the embodiment of Figure 18 (b), in the peristome 6 of laminate 3, be provided with the flexible seal parts 136 that are installed in laminate 3 and oscillating drive link 16e and stop up the space between them.

Figure 19 illustrates the embodiment as the laminate 3 of absorption of vibrations material.The embodiment of Figure 19 (b) is the embodiment of above-mentioned Figure 14-16.The embodiment of Figure 19 (a) is made by metal sheet 1 and rubber plate 2 for laminate 3.The embodiment of Figure 19 (c) is made by upside metal sheet 1, upside rubber plate 2, upside metal sheet 1 ' and downside rubber plate 2 ' for laminate 3.The embodiment of Figure 19 (d) for laminate 3 by upside metal sheet 1, upside rubber plate 2, intermediate metal plate 1 ", downside rubber plate 2 ', downside metal sheet 1 ' make.The metal sheet of laminate 3 or the number of rubber plate for example, can be decided to be 1-5 and open.In addition, also can only constitute vibration absorption component in the present invention by rubber plate.

As metal sheet 1,1 ', 1 " material, can use stainless steel, iron, copper, aluminium and other suitable alloys.The thickness of metal sheet for example is 10-40mm.But, to the parts beyond the layer alloy body directly fixed metal sheet (for example, above-mentioned intermediate metal plate ") can do thinly, be 0.3-10mm.

As rubber plate 2,2 ' material, that can use synthetic rubber and natural rubber adds the sulphur thing, preferably uses and press the Shockproof rubber that JISK 6386 stipulates, especially uses quiet elasticity of shearing rate 4-22kgf/cm ²Be advisable 5-10kgf/cm ²For better, extensibility is for well more than 250%.Can enumerate neoprene, butadiene-acrylonitrile rubber, vinyl cyanide-neoprene, vinylbenzene-neoprene, acrylonitrile-butadiene rubber, polyisoprene rubber, ethylene-propylene-diene copolymer rubber, expression alcohol as synthetic rubber is that rubber, epoxidation system rubber, fluorine are that rubber, silicon are that rubber, polyurethane series rubber, polysulfide rubber, phosphorus are rubber.The thickness of rubber plate for example is about 5-60mm.

Among the embodiment of Figure 19 (d), laminate 3 is made by upside metal 1, rubber plate 2 and downside metal 1 '; Rubber plate 2 is made by upside solid rubber layer 2a, rubber sponge layer 2b and downside solid rubber layer 2c.Also can remove the arbitrary layer among upper and lower sides solid rubber layer 2a, the 2c, especially, a plurality of solid rubber layer and a plurality of rubber sponge layer can also be carried out the laminated laminate that forms.

Figure 20 represents the graphic representation of variation, and this variation is in the above-described embodiments, according to by power source circuit 34 between negative busbar 30 and positive bar 32 added voltage to by the variation of electro X mobile electroplating current (current density) variation.In this variation, the current density waveform of the 1st state and the 2nd state is not by rectangular wave shown in Figure 8, but produces the ripple of some pulsation.The formation that such pulsation is based on power source circuit 34 produces.Electroplating current also can be such pulsatory current among the present invention.As the current value I 1 of the 1st state and the 2nd state, the peak value that I2 can utilize each state.

Also have, in the present invention, can use circuit as power source circuit 34, also can use the system of output (that is, being equivalent to be used alternatingly two supply units) alternately by these two kinds of systems with voltage plenum system that voltage plenum system that the 1st state uses and the 2nd state use.

More than such electroplate liquid vibrational flow and the combination technique of pulse type electroplating current, equally also be applicable to and utilize in the treatment solution energising to carry out object being treated surface-treated anonizing or electrolytic polishing method or electrolytic degreasing method.Certainly, according to contents processing, object being treated can be configured in anode one side or negative electrode one side.Therefore, can handle the surface of good of carrying out of processed article with microtexture.

Embodiment

Followingly the present invention is described according to embodiment.

Used the illustrated device of relevant Fig. 1-3.Here, use 150W * 200V * 3 φ as vibrating motor 16d, as 300 liters of plating tank 12 use capacity, use central authorities of Co., Ltd. to make made Power Master as power source circuit 34.

As by electro X, use the silicon wafer that carries out 8 inches (diameter 200mm) of given pre-treatment with ordinary method, in blind hole, bury copper and form conducting film, the copper line method that this blind hole adopts in order to form multilayer wiring forms copper layer system.A plurality of blind holes are to form with internal diameter 0.24 μ m at the titanium nitride insulation layer of thickness 0.35 μ m.

As electroplate liquid 14, used the through hole liquid of the plating copper sulfate of making by following material.

Copper sulfate 75g/L

Sulfuric acid 190g/L

It is an amount of that light is translated agent

Chlorion 40mL/L

The vibrating motor 16d of vibration generating unit 16 is vibrated under the 45Hz condition, vibration blade 16f is vibrated under amplitude 0.2mm and 650 times/minute conditions of vibration number in electroplate liquid 14.Vibrating motor 28 is vibrated under the 25Hz condition, in electroplate liquid 14, under amplitude 0.15mm and 200 times/minute conditions of vibration number, vibrated by electro X.Utilize 3 D electromagnetic velocimeter ACM 300-A (Aretsuku Electronics Co., Ltd system) to measure three-dimensional flow in electroplate liquid this moment, be 200mm/ second.

By power source circuit 34,11 shown in Fig. 8,12, T1, T2 are respectively 11=6 (A/Wafer)=3 (A/dm ³), I2=0.6 (A/Wafer), T1=10 (second), T2=1 (second), the square waveform electroplating current flows.

By energising, the result of microscope and other inspections shows, after handling through 10 minutes, forms the electroplating copper film of about 10 μ m thickness, and a plurality of blind holes all are good imbedding.

Comparative example 1-1

Show that by energising, microscope and check result thereof except that T2=0 (second), after other were handled similarly to Example 1, a plurality of blind hole parts (58%) had good copper plating film and are embedded in, remaining does not have good copper plating film to be embedded in.

Comparative example 1-2

Show by energising, microscope and check result thereof, except that not making the action of vibrational flow generating unit, after other were handled similarly to Example 1, a plurality of blind hole parts (10%) had good copper plating film and are embedded in, and remaining does not have good copper plating film to be embedded in.

Embodiment 2

Used device illustrated on Fig. 1-3 (vibrating motor 16d is identical with embodiment 1 with plating tank 12 and power source circuit 34), multi-layer wire substrate as used the A4 version size of having carried out given pre-treatment according to a conventional method by electro X has formed the plated conductive film at through-hole inner surface.A plurality of through holes are that internal diameter is 30 μ m Φ, and aspect ratio is 10.

As electroplate liquid, used the common liquid of the plating copper sulfate of making by following material:

Copper sulfate 200g/L

Sulfuric acid 50g/L

It is an amount of that light is translated agent

Chlorion 60mL/L

The vibrating motor 16d of vibrational flow generating unit 16 is vibrated under the 50Hz condition, vibration blade 16f is vibrated under amplitude 0.2mm and 700 times/minute conditions of vibration number in electroplate liquid 14.In addition, vibrating motor 28 is vibrated under the 25H2 condition, and make by electro X in electroplate liquid 14 to vibrate under amplitude 0.15mm and 200 times/minute conditions of vibration number.Oscillating motor 20 is driven, make and in electroplate liquid 14, shaken width of cloth 30mm by electro X and shake under several 20 times/minute conditions and shake.Utilize 3 D electromagnetic velocimeter ACM 300-A to measure three-dimensional flow in electroplate liquid this moment, be 200mm/ second.

By power source circuit 34, the I1 shown in Fig. 8, I2, T1, T2 become 11=4 (A/dm respectively ²), I2=0.4 (A/dm ²), T1=180 (second), T2=20 (second), the electroplate liquid of the square waveform that flows.

Show that by energising, microscope and other check results after carrying out handling in 10 minutes, 99.9% of a plurality of through holes form good electroplating film.

Comparative example 2-1

Show that by energising, microscope and other check results except that T2=0 (second), other carry out after similarly to Example 2 the processing, the part of a plurality of through holes (50%) all length forms good copper plating film, and remaining does not form good copper plating film.

Comparative example 2-2

Show by energising, microscope and other check results, except that not making 16 actions of vibrational flow generating unit, other carry out after similarly to Example 2 the processing, the part of a plurality of through holes (10%) forms good copper plating film, and remaining does not form good copper plating film (owing to burn or burn etc. produces unfavorable condition).

Embodiment 3

Used device illustrated on Fig. 9-11 (vibrating motor 16d is identical with embodiment 1 with plating tank 12 and power source circuit 34), as by electro X, used and carried out given pre-treatment according to a conventional method, 800 of the ceramic chips of size 0.6mm * 0.3mm * 0.2mm are formed for making the plated nickel film of electrode film in the face at the two ends of relevant its long axis direction and the part at 0.6mm * 0.3mm face (by the zone of both ends of the surface to 0.1mm) that continues.

Electroplate liquid during as nickel plating, use to have the cylindrical shell liquid that following material is made:

Single nickel salt 270g/L

Nickelous chloride 68g/L

Boric acid 40g/L

Sal epsom 225g/L

The vibrating motor 16d of vibrational flow generating unit 16 is vibrated under the 5Hz condition, vibration blade 16f is vibrated under amplitude 0.2mm and 750 times/minute conditions of vibration number in electroplate liquid 14.In addition, make vibrating motor 48 vibration, and make by electro X in electroplate liquid 14 to vibrate under amplitude 0.15mm and 250 times/minute conditions of vibration number.Utilize 3 D electromagnetic velocimeter ACM 300-A to measure three-dimensional flow in electroplate liquid this moment, be 210mm/ second.As cylindrical shell 52 use aperture openings rate 20%, revolution is the cylindrical shell of 10rpm.

By power source circuit 34, the I1 shown in Fig. 8, I2, T1, T2 become I1=0.4 (A/dm respectively ²), I2=0.04 (A/dm ²), T1=20 (second), T2=2 (second), the electroplate liquid of the square waveform that flows.

Show that by energising, microscope and other check results after handling through 30 minutes under 50 ℃, entire chip forms the thick good plated nickel film of about 2 μ m.

Comparative example 3-1

Show that by energising, microscope and other check results except that T2=0 (second), other carry out after similarly to Example 3 the processing, a chip part (12%) forms good plated nickel film, and remaining does not form good plated nickel film.

Comparative example 3-2

Show by energising, microscope and other check results, except that not making 16 actions of vibrational flow generating unit, other carry out after similarly to Example 3 the processing, and the part of a plurality of through holes (60%) forms good plated nickel film, and remaining does not form good plated nickel film.

Embodiment 4

Identical with embodiment 3, replace nickel plating and use zinc-plated.As electroplate liquid 14, used the sulfuric acid saline solution of the acid tin of making by following material of plating;

Stannous sulfate 50g/L

Sulfuric acid 100g/L

Cresol sulfonic acid 100g/L

Gelatin 2g/L

2-Naphthol 1g/L

By power source circuit 34, the I1 shown in Fig. 8, I2, T1, T2 become I1=0.4 (A/dm respectively ²), I2=0.04 (A/dm ²), T1=20 (second), T2=2 (second), the electroplating current of the square waveform that flows.

Show that by energising, microscope and other check results after handling through 60 minutes under 50 ℃, entire chip forms good tin-plated coating film.

Comparative example 4-1

Show that by energising, microscope and other check results except that T2=0 (second), other carry out after similarly to Example 4 the processing, a chip part (10%) forms good tin-plated coating film, and remaining does not form good tin-plated coating film.

Comparative example 4-2

Show by energising, microscope and other check results, except that not making 16 actions of vibrational flow generating unit, other carry out after the processing with embodiment 4 samples, and the part of a plurality of through holes (57%) forms good plated nickel film, and remaining does not form good plated nickel film.

Embodiment 5

Used device illustrated on Fig. 9-11 (vibrating motor 16d is identical with embodiment 1 with plating tank 12 and power source circuit 34), as by electro X, used 30 profile 0.5mm Φ that carried out given pre-treatment according to a conventional method, length 20mm brass pin forms plated nickel film in its outside.

Electroplate liquid 14 during as nickel plating, use to have the cylindrical shell liquid that following material is made:

Single nickel salt 270g/L

Nickelous chloride 68g/L

Boric acid 40g/L

Sal epsom 225g/L

The vibrating motor 16d of vibrational flow generating unit 16 is vibrated under the 45Hz condition, vibration blade 16f is vibrated under amplitude 0.2mm and 500 times/minute conditions of vibration number in electroplate liquid 14.In addition, make vibrating motor 48 vibration, and make by electro X and in electroplate liquid 14, under amplitude 0.15mm and 200 times/minute conditions of vibration number, vibrate.Utilize 3 D electromagnetic velocimeter ACM 300 1 A to measure three-dimensional flow in electroplate liquid this moment, be 200mm/ second.As cylindrical shell 52 use aperture openings rate 20%, revolution is the cylindrical shell of 10rpm.

By power source circuit 34, the I1 shown in Fig. 8, I2, T1, T2 become I1=3 (A/dm respectively ²), I2=0.3 (A/dm ²), T1=30 (second), T2=3 (second), the electroplate liquid of the square waveform that flows.

Show by energising, microscope and other check results, after handling through 20 minutes under 50 ℃, the uniformly good plated nickel film of whole aciculiform film forming thickness.

Comparative example 5-1

Show that by energising, microscope and other check results except that T2=0 (second), other carry out after similarly to Example 5 the processing, the part of pin (17%) forms good plated nickel film, and remaining does not form good plated nickel film.

Comparative example 5-2

Show by energising, microscope and other check results, except that not making 16 actions of vibrational flow generating unit, other carry out after similarly to Example 5 the processing, the part of pin (60%) forms good plated nickel film, and remaining does not form the evenly good plated nickel film of film thickness (producing unfavorable condition owing to burning or burning).

Embodiment 6

Used the illustrated device of Fig. 9-11 (vibrating motor 16d is identical with embodiment 1 with plating tank 12 and power source circuit 34), as by electro X, use forms copper plating film with 30000 of the spheroids of the acrylonitrile-butadiene-styrene copolymer (ABS resin) of the diameter 3mm Φ that carried out given pre-treatment (comprising skimming treatment and Electrostatic Treatment) according to a conventional method in its outside.

Electroplate liquid 14 during as electro-coppering, used the electroplate liquid of being made by following material:

Copper sulfate 200g/L

Sulfuric acid 50g/L

It is an amount of that light is translated agent

Chlorion 60mL/L

The vibrating motor 16d of vibrational flow generating unit 16 is vibrated under the 40Hz condition, vibration blade 16f is vibrated under amplitude 0.2mm and 700 times/minute conditions of vibration number in electroplate liquid 14.Vibrating motor 48 is driven, make by electro X and in electroplate liquid 14, vibrate under amplitude 0.15mm and 250 times/minute conditions of vibration number.Utilize 3 D electromagnetic velocimeter ACM 300-A to measure three-dimensional flow in electroplate liquid this moment, be 210mm/ second.As cylindrical shell use aperture openings rate 20%, revolution is the cylindrical shell of 10rpm.

By power source circuit 34, the I1 shown in Fig. 8, I2, T1, T2 become I1=0.5 (A/dm respectively ²), I2=0.04 (A/dm ²), T1=30 (second), T2=3 (second), the electroplate liquid of the square waveform that flows.

Show that by film thickness determination, energising, microscope and other check results after handling through 30 minutes under 50 ℃, 99.5% of spheroid forms evenly good copper plating film of film thickness.

Comparative example 6-1

Show by film thickness determination, energising, microscope and other check results, except that T2=0 (second), other carry out after similarly to Example 6 the processing, and the part of spheroid (40%) forms good plated nickel film, and remaining does not form evenly good copper plating film of film thickness.

Comparative example 6-2

Show by film thickness determination, energising, microscope and other check results, except that not making 16 actions of vibrational flow generating unit, other carry out after similarly to Example 6 the processing, the part of spheroid (50%) forms good plated nickel film, and remaining does not form evenly good plated nickel film of film thickness.

Embodiment 7

Used the illustrated device of Fig. 1-3.Here use 150W * 200V * 3 Φ, plating tank 12 then to use 300 liters as vibrating motor 16d.Then used central authorities of Co., Ltd. to make made Power Master PMD1 type as power source circuit 34.

As used the silicon wafer that has carried out the 40mm conformality thickness 1mm of given pre-treatment with ordinary method by electro.Form the blind hole of a plurality of internal diameter 20 μ m, the degree of depth 70 μ m on the surface of this silicon wafer.

As electroplate liquid, used the roller acid copper electroplating ventilating hole liquid of making by following material.

Copper sulfate 75g/L

Sulfuric acid 190g/L

Gloss-imparting agent is an amount of

Chlorion 40mL/L

And, configuration pottery system air bell (external diameter 75mm Φ in plating tank 12; Internal diameter 50mm Φ; Length 500mm; Pore footpath 50-60 μ m; Void content 33-38%), make its bubbling in electroplate liquid.

The vibrating motor 16d of vibrational flow generating unit 16 is vibrated under the 40Hz condition, vibration blade 16f is vibrated under amplitude 0.1mm and 650 times/minute conditions of vibration number in electroplate liquid 14.The vibrating motor 28 of 75W * 200V * 3 Φ is vibrated under the 25Hz condition, make by electro X and in electroplate liquid 14, vibrate under amplitude 0.15mm and 200 times/minute conditions of vibration number.Utilize 3 D electromagnetic velocimeter ACM 300-A (Aretsuku Electronics Co., Ltd system) to measure three-dimensional flow in electroplate liquid this moment, be 200mm/ second.

By power source circuit 34, the I1 shown in Fig. 8, I2, T1, T2 become I1=1.5 (A/Wafer), I2=0.1 (A/Wafer), T1=0.08 (second), T2=0.02 (second) respectively, the electroplating current of the square waveform that flows.

Show by energising, microscope and other check results, after 2.5 hours handle, on the whole internal surface of a plurality of blind holes, form the uniform copper plating film of thickness.

Comparative example 7

Show that by energising, microscope and other check results except that T2=0 (second), other carry out after similarly to Example 7 the processing, the blind hole peristome is stopped up by electroplating film.

Embodiment 8

Except the vibrating motor 16d as vibrational flow generating unit 16 uses the high-frequency vibration motor, this motor is vibrated under 150Hz, make vibration blade 16f vibration and will being decided to be in the treatment time outside 1.5 hours under amplitude 0.2mm and 1200 times/minute conditions of vibration number in electroplate liquid 14, other carry out processing similarly to Example 7.Show by energising, microscope and other inspection fruit results, on whole internal surface of a plurality of blind holes, form the copper plating film of about 7 μ m uniform thickness.

Embodiment 9

As by electro X, the epoxy resin board that uses circuit board to use.On the surface of epoxy resin board, form a plurality of internal diameter 15 μ m, the blind hole of the degree of depth 40 μ m.

As galvanized pre-treatment, carried out degreasing → washing → etching → washing → neutralization → washing → catalysis → washing → acceleration (catalysis) → washing → electroless plating copper, give electroconductibility, wash again → activate → wash → strike plating.Same vibrational flow takes place in electroplate liquid by relevant illustrated identical vibration generating unit with Fig. 1-3.

Plating is carried out according to the mode identical with embodiment 7.But, drive oscillating motor 20 again, make and in electroplate liquid 14, shaken width of cloth 30mm by electro X and shake under several 20 times/minute conditions and shake.Utilize 3 D electromagnetic velocimeter ACM 300-A to measure three-dimensional flow in electroplate liquid this moment, be 200mm/ second.

By power source circuit 34, the I1 shown in Fig. 8, I2, T1, T2 become I1=4.5 (A/dm respectively ²), I2=0.4 (A/dm ²), T1=0.08 (second), T2=0.015 (second), the electroplating current of the square waveform that flows.

Show that by energising, microscope and other check results after carrying out processing in 1 hour, the whole of a plurality of blind holes are imbedded well.

Comparative example 8

Show that by energising, microscope and other check results except that T2=0 (second), other carry out after similarly to Example 9 the processing, the peristome of blind hole is stopped up by electroplating film, but the space is left in inside.

As mentioned above, utilize electro-plating method of the present invention,, also can form the uniform high-quality electroplating film of zero defect and film thickness even for fine plated conductive figure.And, utilize the present invention can obtain the high-quality electroplating film of the conductive pattern of microtexture at high speed.In addition, utilize the also available less device of the present invention to constitute the high-quality electroplating film that obtains the microtexture conductive pattern expeditiously.

Claims (11)

1. electro-plating method, it is characterized in that, by making and vibrating that generation part is connected and the vibration of single hop or multistage fixed vibration blade on the vibrating arm of electroplate liquid internal vibration, vibrational flow takes place in electroplate liquid, simultaneously with contact with described electroplate liquid dispose made negative electrode by electro, and make anode with the metal parts that contacts configuration with described plating bath, making alive between described negative electrode and anode, be pulse type by electroplate liquid to the electroplating current of cathode flow by described anode this moment, alternately be chosen at the 1st state that the 1st time T 1 of the 1st value I1 continues, and the 2nd state that continues in the 2nd time T 2 with same polar the 2nd value I2 of described the 1st value; Described the 1st value I1 is more than 5 times of described the 2nd value I2; Described the 1st time T 1 is more than 3 ones of described the 2nd time T 2.

2. electro-plating method according to claim 1 is characterized in that, the 6-25 that described the 1st value I1 is described the 2nd value I2 doubly; The 4-25 that described the 1st time T 1 is described the 2nd time T 2 doubly.

3. according to each described electro-plating method of claim 1-2, it is characterized in that described the 1st time T 1 is 0.01 second-300 seconds.

4. according to each described electro-plating method of claim 1-3, it is characterized in that described vibration blade is to vibrate under the condition of amplitude 0.05-10.0mm and vibration number 200-1500 time/minute.

5. according to each described electro-plating method of claim 1-4, it is characterized in that the three-dimensional flow of the vibrational flow of described electroplate liquid is that 150mm/ is more than second.

6. according to each described electro-plating method of claim 1-5, it is characterized in that described vibration generation part vibrates under the 10-500Hz condition.

7. according to each described electro-plating method of claim 1-6, it is characterized in that, under the condition of amplitude 0.05-5.0mm and vibration number 100-300 time/minute, make and describedly vibrated by electro.

8. according to each described electro-plating method of claim 1-7, it is characterized in that, shaking amplitude 10-100mm and shaking to make under several 10-30 time/minute the condition and describedly shaken by electro.

9. according to each described electro-plating method of claim 1-8, it is characterized in that the described to-be-electroplated surface that is had the following microtexture of 50 μ m by electro.

10. according to each described electro-plating method of claim 1-9, it is characterized in that, a plurality of being remained on by electro kept in the container, this maintenance container has can be by the little perforate of electroplate liquid, and have owing to making electroplating current flow to this by the used conductive component of electro with described the contact by electro, around the rotation center of non-perpendicular direction, be rotated in described electroplate liquid by this maintenance container, make described a plurality ofly in described retainer, rotated by electro, and make repeatedly described each contacted with described conductive component respectively by electro and break away from.

11. electro-plating method according to claim 10 is characterized in that, the width of described plated body product is below the 5mm.

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