KR100461908B1 - Electroplating method using combination of vibrational flow of plating bath and plating current of pulse - Google Patents

Abstract

The present invention relates to a plating method capable of forming a high-efficiency and high-speed plated film of a conductive pattern having a fine structure with good quality without defects and non-uniformity of film thickness.

Three-dimensional flow rate 150 mm / sec in the plating bath 14 by vibrating the vibration blade 16f in conjunction with the vibration generating means 16d at an amplitude of 0.1 to 10 mm and a frequency of 200 to 800 times / minute in the plating bath 14. While generating the above-mentioned vibration flow, a voltage was applied between the cathode and the anode by using the plated article X having the microstructure disposed in the plating bath 14 as the cathode and the metal member 56 as the anode. At this time, the plating current flowing from the anode to the cathode with the plating bath 14 interposed therebetween is a first state in which the first current I1 lasts from the first value I1 to the first time T1 in the pulse state and the second of the same polarity as the first value. At a value I2 of the second state T2 alternately taking a second state, the first value I1 is at least five times the second value I2, and the first time T1 is the second time T2. 3 times or more.

Description

Electroplating method using combination of vibrational flow of plating bath and plating current of pulse}

The present invention relates to a plating method, and more particularly to a plating method characterized by a specific combination of the physical conditions of the plating bath and the electrical conditions of the plating current.

BACKGROUND ART Conventionally, in the field of manufacturing articles such as electronic parts, electroplating for forming a film of conductive material on the surface of articles has been widely used.

In particular, in recent years, in order to satisfy the demand for miniaturization and high functionalization of electronic components, fine ones are required with conductive patterns formed on the surface of the article (including the inner surface of the through hole and the inner surface of the blind via hole).

For example, miniaturization of wiring patterns corresponding to pitching of input / output terminals accompanying high integration of semiconductor devices is recommended, and the inner diameters of through-holes and blind via-holes, which are accompanied by this, are less than 100 μm, 50 μm, or 30 μm. Small things are required. In addition, the aspect ratio between the through-hole and the blind bi-hole is also required to be large, such as 5 or more or 8 or more.

For example, in a multilayer wiring in a semiconductor device, copper wiring is used in place of the conventional aluminum wiring for the purpose of reducing the inter-wire capacitance caused by the miniaturization of the wiring accompanying high integration. The damascene method using electroplating is used to form wiring. In this method, deposition of copper in an inside diameter of 1 mu m or less and a very small blind via hole is required.

In addition, for example, it is required to form one electrode film on the surface of the pitch component having a length of about 0.3 mm.

On the other hand, the present applicant is particularly applicable to articles having microstructured parts such as micropores and proposes an effective plating method (see Japanese Patent Application Laid-Open No. 11-189880). In this method, vibration flow is generated in the plating bath, and this and the bubbling by the diffuser are used together. This method is also useful for radio plating in addition to electroplating.

However, in this method, it is necessary to arrange the diffuser in the plating vessel accommodating the plating bath and to provide air piping to the diffuser, so that the amount of the plating bath and the length of the plating vessel must be relatively large. There was a drawback to being large.

On the other hand, as a power source for the electroplating method as described above, a DC power source is generally used. Recently, however, in order to improve the quality of the plating film, it has been proposed to perform plating while periodically changing the plating current. In this method, the positive current and the negative current flow alternately. That is, the iron part is concentrated and partially dissolved in the negative current through the minute unevenness of the surface of the plating film once formed by the positive current, and the surface is flat and defects such as the microcavity are repeated. Aims to obtain high quality plating film. However, this method is disadvantageous in terms of improving the speed at which the film is formed (that is, improving the plating processing speed) because the surface portion of the plated film once formed is removed.

In recent years, the conductive pattern tends to become finer, and when a plated film is formed from such a conductive pattern, defects and film thickness nonuniformity tend to occur, and it is difficult to maintain good quality of the plated film.

In addition, the present applicant proposes a plating method for chromium plating while vibrating a plating bath and a method for chromium plating while vibrating a plating bath by receiving a plurality of plating qualities as a barrel. (See Publication No. 7-54192 and JP 6-330395).

However, in such a method, direct current is used as the plating current, and the length in the direction crossing the rectangular direction, that is, the width is 5 mm or less, for example, to be applied to a small length of the article to be coated, such as 0.3 to 1.0 mm. It is not specifically presented. In barrel plating of such a fine length of the plated article, the flowability of the plating liquid is extremely reduced to the required plating film forming portion while the plated articles overlap with each other in the barrel. Therefore, in the case of a relatively large width to-be-plated article, there exists incomparable technical difficulty, and there exists a room for new improvement by the point of film formation speed and plating film thickness uniformity.

Accordingly, a first object of the present invention is to provide a plating method capable of forming a fine quality conductive film without defects and non-uniformity in film thickness.

Another object of the present invention is to provide a plating method in which a plated film having a good quality of a conductive pattern having a fine structure can be obtained at a high speed.

It is still another object of the present invention to provide a plating method capable of increasing the efficiency of a plated film having a good quality of a microstructure conductive pattern with a relatively small device configuration.

According to the present invention, to achieve the above object,

A plated article arranged to contact the plating bath while generating vibration flow in the plating bath by vibrating a vibrating blade root fixed in one or more stages to a vibrating rod vibrating in the plating bath in conjunction with the vibration generating means. A cathode is used, and a metal member disposed in contact with the plating bath is used as an anode, and a voltage is put between the cathode and the anode, whereby a plating current flowing from the anode to the cathode is pulsed. Exchange a first state that is a state and lasts a first time T1 with a first value I1 and a second state that lasts a second time T2 with a second value I2 of the same value as the first value; The first value I1 is at least five times the second value I2, and the first time T1 is at least three times the second time T2.

In one embodiment of the present invention, the first value I1 is 6-25 times the second value I2, and the first time T1 is 4-25 times the second time T2. In one aspect of this invention, the said 1st time T1 is 0.01 second-300 second. In one embodiment of the present invention, the vibration blade can be oscillated at an amplitude of 0.05 ~ 10.0mm and a frequency of 200 ~ 1500 times / min. In one embodiment of the present invention, the vibration flow of the plating bath has a three-dimensional flow rate of 150 mm / sec or more. In one embodiment of the present invention, the vibration generating means vibrates at 10 to 500 Hz.

In one embodiment of the present invention, the plated article is vibrated at an amplitude of 0.05 to 5.0 mm and a frequency of 100 to 300 times / minute. In one aspect of the present invention, the article to be plated is rocked at a swing width of 10 to 100 mm and a swing width of 10 to 30 times / minute.

In one embodiment of the present invention, the plated article has a plated surface having a microstructure of 50 μm or less in length.

In one embodiment of the present invention, the conductive member has a small hole through which the liquid of the plating bath easily passes, and the conductive member is configured to flow a plating current to the plated article by contacting the plated article. Holding the inside of the holding vessel, and rotating the holding vessel around the center of rotation in the vertical direction in the plating bath to transfer the plurality of plated articles in the holding vessel, The contact and separation of the conductive member is repeated in sequence.

In one embodiment of the present invention, the width of the article to be plated is 5 mm or less.

Figure 1. Sectional drawing which shows the structure of the plating apparatus in which 1st Embodiment of the plating method which concerns on this invention is implemented.

Figure 2. Sectional drawing which shows the structure of the plating apparatus in which 1st Embodiment of the plating method which concerns on this invention is implemented.

Figure 3. The top view which shows the structure of the plating apparatus in which 1st Embodiment of the plating method which concerns on this invention is implemented.

Figure 4. An enlarged sectional view of the mounting portion of the vibration transfer rod to the vibration member.

Figure 5. An enlarged sectional view of the mounting portion of the vibration blades to the vibration transmission rod.

Figure 6. Another embodiment of the installation of the vibration blades to the vibration transmission rod.

Figure 7. A cross-sectional view showing another embodiment of the installation of an article to be plated onto a negative electrode busbar.

Figure 8. A graph showing the change in plating current flowing through an article to be plated.

Figure 9. Sectional drawing which shows the structure of the plating apparatus in which 2nd Embodiment of the plating method which concerns on this invention is implemented.

Figure 10. Sectional drawing which shows the structure of the plating apparatus in which 2nd Embodiment of the plating method which concerns on this invention is implemented.

Figure 11. The top view which shows the structure of the plating apparatus in which 2nd Embodiment of the plating method which concerns on this invention is implemented.

Figure 12. Sectional drawing which shows the plating apparatus used for implementation of the plating method which concerns on this invention.

Figure 13. Partial cut plan view of the plating apparatus of FIG.

Figure 14. Sectional drawing which shows the installation to the plating container of the vibration flow generating part which comprises the plating apparatus used for implementation of the plating method by this invention.

Figure 15. Sectional drawing which shows the installation to the plating container of the vibration flow generating part which comprises the plating apparatus used for implementation of the plating method by this invention.

Figure 16. A plan view showing the installation of the plating vessel of the vibration flow generating portion constituting the plating apparatus used in the implementation of the plating method according to the present invention.

Figure 17. Top view of the laminate.

Figure 18. Sectional drawing which shows the closed aspect of the plating vessel upper part by a laminated body.

Figure 19. The figure which shows a laminated body.

Figure 20. A graph showing the change in plating current flowing through an article to be plated.

Figure 21. Sectional drawing which shows the modification of a vibration flow generating part.

Figure 22. Fig. 21 is a plan view showing the vibration flow generating portion.

Figure 23. A diagram showing an example of a power supply for pulse plating.

<Explanation of symbols for the main parts of the drawings>

1, 1 ', 1 ": Metal plate 2, 2': Rubber plate 2a, 2c: Solid rubber layer

2b: sponge rubber layer 3: laminated body 5: through-hole

6: opening 12: plating vessel 13: support

14 plating bath 15 support needle 16 vibration flow generating part

16a: expectation 16b: coil spring 16c: vibration member

16d: Vibration motor 16e: Vibration transfer rod 16f: Vibration blade

16g1, 16g2: vibration stress dispersion member 16h1, 16h2: washer

16i1, 16i2; 16i3, 16i4: nut 16j: vibrating blade fixing member

16k: Spacing 16m, 16n: Nut 16p: Elastic member sheet

20: rocking motor 22: connecting rod 24: rocking frame

26 rail 28 vibration motor 30 cathode busbar

32: anode busbar 34: power supply circuit 40: plated article holding member

40a: upper hook portion 40b: lower club portion 40c: compression spring

44: vibration frame 46: coil spring 48: vibration motor

49: balance weight 50: barrel 52a: pipe member

54 '56': insulation coating wiring 56: anode metal member 112: dustproof rubber

116: bolt 117: nut 118: mounting member

119: rubber ring 123: upper guide member 124: lower guide member

131,132 bolt 136: prekinbrusil member

X: Plated Goods

Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. In the drawings, the same reference numerals are attached to members or parts having the same shape.

1 and 2 are cross-sectional views showing the configuration of the plating apparatus carried out in the first embodiment of the plating method according to the present invention, and FIG. 3 is a plan view of FIGS.

In these drawings, reference numeral 12 denotes a plating vessel, in which a plating bath 14 is housed. Reference numeral 16 denotes a vibration flow generator. The vibration flow generating unit 16 includes a base 16a provided with a vibration-proof rubber between the plating vessel 12, a coil spring 16b as a vibration absorbing member fixed to a lower end of the base, and an upper end of the coil spring. Plated bath in the lower half of the vibration member 16c fixed to the vibration member, the vibration motor 16d as vibration generating means installed in the vibration member, the vibration transmission rod 16e provided with an upper end mounted on the vibration member 16c, and the vibration transmission rod. It has the vibration blade root 16f provided in the position immersed in 14. In the coil spring 16b, a rod-shaped guide member may be disposed as shown in FIG. 12 to be described later.

The vibration motor 16d vibrates at 10 to 500 Hz, preferably 20 to 60 Hz, more preferably 30 to 50 Hz, for example, by control using an inverter. The vibration generated by the vibration motor 16d is transmitted to the vibration blade root 16f with the vibration member 16c and the vibration transmission rod 16e interposed therebetween. The end portion of the vibrating blade root 16f vibrates at the frequency required in the plating bath 14. This vibration is bent from the portion where the vibration blade root 16f is provided to the vibration transmission rod 16e to the end portion. The amplitude and frequency of this vibration are different from the vibration motor 16d, but are determined in relation to the mechanical characteristics of the vibration transmission path and the interaction with the plating bath 14, and in the present invention, amplitudes of 0.05 to 10.0 mm (for example, , 0.1 to 10.0 mm), the frequency is preferably 200 to 1500 times / minute (for example, 200 to 800 times / minute).

4 is a wide cross-sectional view of the installation portion of the vibration member 16c and the vibration transmission rod 16e. The nut 16i1, 16i2; 16i3, on the male screw portion formed at the upper end of the vibration transfer rod 16e, with the vibration stress dispersing members 16g1, 16g2 and washers 16h1, 16h2 interposed between the upper and lower sides of the vibration member 16c. And 16i4). The vibration stress dispersion members 16g1 and 16g2 originate from rubber, for example.

5 is an enlarged cross-sectional view of a portion in which the vibration blade root 16f is installed as the vibration transmission rod 16e. On the upper and lower sides of each of the seven vibration blades 16f, vibration blade fixing members 16j are disposed. Spacing rings 16k are arranged between the adjacent vibration blades 16f for setting the interval of the vibration blades 16f with the fixing member 16j interposed therebetween. On the upper side of the uppermost vibration blade 16f and the lower side of the lower vibration blade 16f, a nut 16m suitable for a male screw formed on the vibration transfer lot 16e is disposed.

FIG. 6: is a figure which shows the modification of the installed part of the vibration blade | wing 16f to the vibration transmission rod 16e. In this modified example, each vibration blade root 16f is provided on the vibration transmission rod 16e individually by the upper and lower nuts 16n. Furthermore, breakage of the vibration blade 16f is caused by interposing the elastic member sheet 16p originating from the subsequent resin and the subsequent rubber between the vibration blade 16f and the fixing member 16j. Can be prevented. As shown, the lower surface (pressing surface) of the upper fixing member 16j is an iron cylinder, and the upper surface (pressing surface) of the lower fixing member 16j is a corresponding yaw cylinder. It is in a circle. Prior to this, the portion of the vibrating blade root 16f, which is pressed in the vertical direction by the fixing member 16j, is bent, and the end of the vibrating blade root 16f forms an angle α with respect to the horizontal plane. This angle may be, for example, -30 ° or more and 30 ° or less and preferably -20 ° or more and 20 ° or less. In particular, it is preferable that angle (alpha) is -30 degrees or more -5 degrees or less or 5 degrees or more and 30 degrees or less, Preferably it is -20 degrees or more -10 degrees or less, or 10 degrees or more and 20 degrees or less. When the pressing surface of the fixing member 16j is made flat, the angle α is 0 °. The angle α does not need to be the same for all vibration blades 16f, and is, for example, a value of-for lower one or two vibration blades 16f as shown in FIG. It may be set in the reverse direction to that shown in FIG. 6, and may be set to a value of + (that is, upward direction: the direction shown in FIG. 6) for the vibration blades other than this.

As the vibration blade root 16f, an elastic metal plate, a synthetic resin plate, a rubber plate, or the like can be used. The thickness of the vibration blade 16f is set so that, at the time of operation of the vibration flow generating unit 16, the end portion of the vibration blade 16f exhibits a flatter phenomenon (a phenomenon such as a wave wave). The vibration blades may have a thickness of 0.2 to 2 mm when the reference numeral 16f comes from a metal plate such as a stainless steel plate. Moreover, when the vibration blade root 16f originates from a synthetic resin board and a rubber board, the thickness can be 0.5-10 mm.

1 to 3, the swinging motor 20 is in contact with the swinging frame 24 with the connecting rod 22 therebetween. The swing frame 24 is disposed on the rail 26 so as to be reciprocated in a horizontal direction (left and right direction in FIG. 1). The swinging frame 25 is provided with a vibration motor 28. The swing frame 24 is further provided with a negative bus bar 30 and a positive bus bar 32 in an insulated state from the swing frame 24. These are the negative terminal and the positive terminal of the power supply circuit 34, respectively. Is connected to. The power supply circuit 34 can create a rectangular wave state voltage from an alternating voltage, and such a power supply circuit is known as a pulse power supply having a rectifying circuit using a transistor, for example.

As the power supply circuit (power supply device) used to generate the plating current in the present invention, one that rectifies (including addition of a DC component) and outputs AC is used. As such a power supply device or rectifier, a transistor controlled power supply, a dropper power supply, a switching power supply, a silicon rectifier, an SCR type rectifier, a high frequency type rectifier, and an inverter digital control type rectifier (for example, a power master manufactured by Central Manufacturing Co., Ltd.). ), KTS series manufactured by SAMSA ELECTRIC CO., LTD., RCV power supply, switching regulator power supply and transistor switch manufactured by SAKUK ELECTRIC CO., LTD., And the transistor switch is ON-OFF. , Supplying high frequency switching power supply (converting the AC to DC current and then adding a high frequency of 20 ~ 30KHz to the transformer with the transformers to give the rectified and smoothed output once more), PR type A rectifier, a high speed pulse PR power supply (for example, HiPR series Chiyoda Co., Ltd.) and the like can be used.

Here, the current waveform will be described. In order to speed up the plating and to improve the characteristics of the coating film, the selection of the plating current waveform is important. The conditions of voltage and current required for electroplating vary depending on the type of plating, the composition of the plating bath, the length of the plating vessel, etc., and it is difficult to define them as a single concept. It can cover enough. Therefore, four types of rated output of the DC power supply for plating are standardized in the industry, such as 6V, 8V, 12V, and 15V. Since the voltage below this rated voltage can be adjusted, it is preferable to select a power supply of the rated voltage which has some margin with respect to the desired voltage value required for plating. In the industry, the rated output current of the power supply is standardized to 500 A, 1000 A, and 2000 A to 1000 A, and in addition, it takes a custom-made form. For the type and surface layer of the article to be plated, it is preferable to determine the required current density of the plated article x the required current capacity of the power source as the surface layer of the article to be plated, and select a suitable standard power source.

Pulse waves are originally short in width W compared to period T, but this definition is not exact. Pulse waves also include other than square waves. The operation speed of the element used for a pulse circuit became high, and the pulse width also became less than ns (10 ^-9s ). As the width of the pulse becomes narrower, it is difficult to maintain sharp waveforms of the leading and trailing edges. This is because it contains high frequency components.

Examples of the pulse wave include a top wave, a ramp wave, a triangular wave, a compound wave, a rectangular wave (square wave), and the like, and in the present invention, a square wave is particularly preferable in terms of electric efficiency and smoothness.

As an example of the pulse plating power supply, as shown in FIG. 23, a pulse current in a rectangular wave state is obtained as the transistor switch is turned on and off at high speed, including a switching meter type DC power supply and a transistor switch. Supply to the load.

The upper portion of the conductive holding member 40 is mechanically and electrically connected to the negative electrode busbar 30 to hold the article to be plated X. The lower part of the to-be-plated article holding member 40 is immersed in the plating bath 14, The to-be-plated article X is electrically connected to this part, and it is hold | maintained by the crescent. In addition, although not shown in the drawing, the anode busbar 32 is connected to a cathode metal member (for example, a shape accommodated in a plastic bowl) derived from a metal to be plated, and mechanically and electrically connected to a lower portion thereof. It is immersed in the bath (14). Furthermore, various methods known in the art can be used as the method of installing the plated article of the negative electrode busbar, the method of installing the negative electrode metal member of the negative electrode busbar, and the shape and structure of the negative electrode busbar and the positive electrode busbar.

7 is a cross-sectional view showing a modification of the installation of the negative electrode busbar of the article to be plated. In this example, the conductive retaining member 40 includes an upper hook portion 40a provided on the negative electrode busbar 30, a lower crank portion 40b that holds the plated article X, and the corresponding crank. It has the compression spring 40c which produces negative crank force.

1 to 3, as the swinging motor 20 is operated, the swinging frame 24 and the holding member 40 and the plated article X installed thereon are, for example, swinging width of 10 to 00mm and swinging. It can be shaken at several times from 10 to 30 times / minute. In addition, the vibration motor 28 vibrates at 10 to 60 Hz, preferably 20 to 35 Hz, for example, under control using an inverter. The vibration generated by the vibration motor 28 is transmitted to the article to be plated X via the vibration frame 24 and the holding member 40, whereby the article to be plated X has an amplitude of 0.05 to 5.0. It can be vibrated at a frequency of 100 to 300 times / minute in mm (for example, 0.1 ~ 5.0mm).

FIG. 8 shows the plating current (current density) flowing through the object to be plated X based on the voltage applied between the negative electrode busbar 30 and the negative electrode busbar 32 by the power supply circuit 34. Graph showing change. As shown, the plating current is interchanged between a first state that lasts a first time T1 at a first value I1 and a second state that lasts a second time T2 at a second value I2 (<I1). Rectangular pulse state. Here, the first value I1 and the second value I2 are the same. I1 is 5 times or more (for example 6 times or more: 6-25 times as an example) of I2, and 8-20 times is preferable. Moreover, T1 is three times or more (for example, 4 times or more: 4-25 times as an example) of T2, and 6-20 times are preferable. By combining such plating current and vibration flow of the plating bath 14 by the vibration flow generating unit 16, it is possible to obtain good quality and high film formation speed even in the plating of a fine conductive structure pattern.

The first value I1 and the first time T1 are used for plating type (e.g. copper lactic acid plating, copper cyanide plating, copper pyrophosphate plating, nickel plating, graphite nickel plating, nickel sulfate plating, chromium plating, zinc cyanide plating, furnace). Cyan zinc plating, alkaline suzu plating, acid plating, silver plating, cyanide plating, acid plating, copper-zinc alloy plating, nickel-iron alloy plating, suzu-zinc plating, paraplating, lead plating, etc.) or plating bath Although appropriately set for the composition, for example, I1 can be in the range of 0.01 to 100 [A / dm ² ], and T1 is in the range of 0.01 to 300 [sec] (for example, 3 to 300 [sec]). It is possible. But not limited to this. The optimum I1, I2, T1, and T2 vary in the range of the plating type and the plating bath in composition, and the like, for example, in the progress of plating, the composition of the plating bath may change.

The plating bath 14 is selected simultaneously with the known electroplating method for the plating film to be formed. For example, in the case of wire copper plating, through hole bath,

Lactic Acid Copper: 60 ~ 100g / L (Liter)

Heritage: 170-210 g / L

Polishes: Appropriate

Chlorine Ion: 30 ~ 80mL / L

Even though it can be used as a normal bath,

Lactic acid copper: 180 ~ 250g / L

Lactic acid: 45 ~ 60g / L

Polishes: Appropriate

Chlorine Ion: 20 ~ 80mL / L

Although it is possible to use, for example, in the case of nickel plating in a barrel bath,

Nickel Lactic Acid: 270g / L

Nickel Chloride: 68g / L

Boric acid: 40 g / L Magnesium lactate: 225 g / L

You can use what comes from, and as a normal bath,

Nickel Lactic Acid: 150g / L

Ammonium Chloride: 15g / L

Boric acid: 15 g / L

You can use what comes from, as a watt bath,

Nickel Lactic Acid: 240g / L

Ammonium Chloride: 45g / L

pH: 4 ~ 5

Bath temperature: 45 ~ 55 ℃

For example, in the case of acidic suzu plating, as a lactate bath, the first oils: 50g / L lactic acid: 100g / L Crezo-Rusruhonic acid: 100g / L gelatin: 2g / Lβ-naphthal: one derived from 1 g / L can be used.

Examples of the to-be-plated article X include electronic components, mechanical components, and other examples. Although not particularly limited, the feature of the present invention is remarkably exhibited when a plated film having a microstructure is formed. Examples of the plating of such a plated article include a microwire having an inner diameter of 100 µm or less (for example, 20 to 100 µm: or especially 50 µm or less, or 30 µm, for example, 10 µm, 5 µm, 3 µm, etc.) based on a multilayer wiring. Formation of a plated conductive film on the inner surface of one blind via hole and a through hole (for example, having a depth of 10 to 100 μm): wiring-based pitch of 50 μm or less (eg 20 to 50 μm: or especially 30 μm or less) Or a fine width of 30 μm or less (especially 20 μm or less, or 10 μm or less, for example 5 μm or 3 μm) for a high-density wiring pattern of 20 μm or less, for example, 10 μm, 5 μm, or the like. Formation of conductive film in (for example, 7 ~ 70㎛ depth): Dongmama when forming multilayer wiring of semiconductor device In the method, a conductive film is formed by digging into a very small blind via hole having a diameter of about 0.3 µm or less or a very small gap (for example, 0.1 µm in width and 1.5 µm in depth). Forming banff; And the like can be exemplified. In particular, the present invention has a large improvement effect when applied to a structure having a high aspect ratio (for example, 3 times or more, especially 5 times or more).

Moreover, as the to-be-plated article X, the thing with the average diameter of 5-500 micrometers can be used. Here, an average diameter shall mean the average value of the typical length of three directions orthogonal to each other. Examples of the article to be plated (X) include copper powder, metal powder such as pre-treated aluminum powder and iron powder, synthetic resin powder such as conductive ABS resin powder, conductive ceramic chip, and the like. have. In addition, electronic parts, mechanical parts, metal powder alloys, particulate inorganic and organic pigments, and metal balls may be mentioned.

For example, a nickel (Ni) plated film is formed on metal particles having a diameter of about 300 μm, for example, copper (Cu) particles, or a gold (Au) plated film and a silver (Ag) plated film are formed on the nickel plated film. A composite plating film can be formed.

In the case where the article to be plated is electrically insulating such as plastic, the conductive base is treated as a pretreatment for electroplating, but in the case of a plated surface having a high aspect ratio with a fine structure, it is usually conducted by electroless plating. Even if the base imparting treatment is performed, it is difficult to form a uniform and good conductive base, and therefore, the thickness of the plated film that can be obtained by electroplating tends to be uneven. In order to solve such a problem, it is conceivable to impart conductivity to the substrate by sputtering or vacuum deposition. However, in this case, since the processing is performed in the pressure reducing device, the cost of the processing device increases, so that the mass processing or the continuous processing is performed. There is a difficulty that cannot be. On the contrary, in the case of plating surface having a high aspect ratio with a fine structure by conducting electroconductive base imparting treatment such as electroless plating while vibrating the processing liquid using the same means as the means for vibration flow used in the present invention. Even if it is high in uniformity, it is possible to provide a conductive sheet. Therefore, by combining such electroconductive base treatment with the electroplating method of the present invention, it is possible to continuously carry out the pretreatment to the electroplating treatment, and the productivity is dramatically improved.

In the plating method of the present invention, as the flowability of the plating bath is improved in the uneven portion of the microstructure due to the vibration flow generated in the plating bath 14 by the vibration flow generating unit 16, the plating current density is set to 1st. It is low enough depending on the state and the corresponding first state, but it is pulsed while repeating with the second state for a short time by the first state at the same time with the value of the same, and can improve the film thickness uniformity. It is possible to reduce film thickness unevenness and defects such as gas pits into through holes and via holes due to the formation of a concentrated plating film on the same iron part and the most branch part, and to obtain high surface gloss and polarity. Since it is not accompanied by partial dissolution of the plated film once formed as in the case of the inverted pulsed plating current, a high film formation speed can be obtained, and the configuration of the manufacturing apparatus can be simplified. Therefore, with respect to a wide range of plated articles, it is possible to form a desired plating film with high quality, efficiently and at high speed.

In addition, in the present invention, due to the action of the vibrating flow generated in the plating bath 14, the distance between the plated article X and the anode metal member is shortened to increase the current density, making it difficult to generate short circuits. This also can be considered as a factor capable of forming a plated film at a high rate without causing side effects such as soot and pressing.

In order to obtain such an operation satisfactorily, it is very preferable that the three-dimensional flow rate of the vibration flow of the plating bath 14 is 150 mm / sec or more. Such a high three-dimensional flow rate is effectively realized by vibrating the plating bath, and there is a disadvantage in that an extremely large device configuration is required even if it is difficult to realize and usually realized by stirring.

In the present embodiment, the above effect is further improved by oscillating and / or vibrating the to-be-plated article X due to the rocking and / or oscillation of the rocking frame 24. However, the rocking and the vibration of these to-be-plated articles X are improved. Even if it does not, a favorable effect can be obtained. Supporting the negative electrode busbar 30, the positive electrode busbar 32, the plated article (X) and the positive metal member without using the swinging frame 24, the swinging motor 20 and the vibration motor 28, etc. As a result, the device configuration is further simplified. The fluctuation has a different effect on the movement of the plated article X according to its in-plane direction when the overall length of the plated article X is a relatively long length or a long flat plate.

9 and 10 are cross-sectional views showing the configuration of a plating apparatus in which a second embodiment of the plating method according to the present invention is implemented, and FIG. 11 is a plan view thereof.

This embodiment differs from that of the first embodiment described above with reference to FIGS. 1 to 8 in that the maintenance of the plated article X and the joining to the plated article are different from those of the first embodiment described above with reference to FIGS. 1 to 8. will be.

9 to 11, a vibration frame 44 is provided in the plating vessel 12 with the coil spring 46 serving as the vibration absorbing member interposed therebetween. The vibration frame 44 is provided with a vibration weight 48 and a balance weight 49 to balance the weight thereof. The vibrating frame 44 is provided with a barrel 52 with a supporting member 50 interposed therebetween. The barrel is rotatably provided with respect to the support member 50, and is rotated in the direction indicated by the arrow in FIG. 9 by a driving means (not shown). In the barrel 52, a large number of minute to-be-plated articles X are accommodated. On the outer circumferential surface of the barrel 52, a large number of small holes are formed, which block passage of the article to be plated X and allow passage of the liquid of the plating bath 14. In the barrel 52, a negative electrode conductive member 54 extending to the lower portion thereof is disposed. The negative electrode conductive member 54 is connected to the negative terminal of the power supply circuit 34 by passing through the inside of the pipe member 52a provided in the barrel with the barrel 52 as the rotation center via the insulating coating line 54. It is. The negative electrode conductive member 54 does not rotate even when the barrel rotates, and thus, the electrically conductive plated article X accompanying the barrel rotation contacts the negative electrode conductive member 54 and is isolated from the negative electrode conductive member 54. Repeat. Reference numeral 56 denotes an anode metal member in which a lower portion is immersed in the plating bath 14. The positive electrode metal member 56 is housed in a plastic container, for example, and is connected to the positive terminal of the power supply circuit 34 with the insulating coating wiring 56 therebetween. As shown in FIG. 9, the anode metal member 56 is disposed on both sides of the barrel 52. However, the anode metal member 56 may be disposed only on one side.

The vibration motor 48 vibrates, for example, at the same amplitude and frequency as the vibration motor 28, and the article to be plated X has a frequency of 0.05 to 5.0 mm (for example, 0.1 to 5.0 mm). Vibrate at 100 ~ 300 times / min. Even in this embodiment, even if the object to be plated X caused by the vibration of the vibration frame 44 does not vibrate, a good effect can be obtained. By supporting the support member 50 and the barrel 52 without using the vibration frame 44, the vibration motor 48, or the like, the device configuration is further simplified.

In this embodiment, the plating current density is set similarly to that described with reference to FIG. 8 above. In the present embodiment, each of the articles to be plated X has a plating current in a process of changing between the first conductive state or the second state or between the first state and the second state at each contact with the negative electrode conductive member 54. However, if only the current density at the time of contact is continuously displayed, it becomes as shown in FIG. 8 on average, and also the effect similar to the said 1st Embodiment can be acquired.

In this embodiment, the formation of an electrode film and a diameter of about 0.5 mm by about 20 mm in length in particular for a chip component such as a ceramic chip capacitor having a length of about 0.6 mm × 0.3 mm × 0.2 mm It is suitable when the formation of a plated film or the like on the pin of is performed simultaneously with respect to the plurality of plated articles X. As described above, in the case of using a fine material having a length, i.e., 5 mm or less, particularly 2 mm or less and 1 mm or less, in the direction transverse to the rectangular direction as the article to be plated, in terms of plating film thickness uniformity and film formation speed, The improvement effect is great. In addition, examples of the plated article (X) include metal powder alloys, organic pigments, and metal balls.

It is a matter of course that the necessary pretreatment step is performed prior to the implementation of the electroplating method according to the present invention. These pretreatments may be the same as in the case of a conventionally known electroplating method.

In addition, in the method of the present invention, the vibration flow generating unit having the vibration blades used to generate the vibration flow required in the plating bath is disclosed in Japanese Patent Application Laid-Open No. 11-189880 (for example, FIGS. Arrange the vibrating roots in the lower part of the plating vessel as described with reference to 8, transmit the vibrations to the vibrating blades with the vibration transmission needle in the vibration motor, and vibrate the vibrating blades in the horizontal direction. ) And those listed in the publications cited in the publication may be used as appropriate.

For example, as the vibration flow generating unit, those shown in Figs. 21 and 22 can be used. In these figures, two vibration flow generating portions 16 are supported by a support needle 15 fixed to a support 13 on which a plating vessel 12 is provided. In the vibration flow generating unit 16, the vibration member 16c 'is provided at the upper end portion of the vibration transmission rod 16e "in the up and down direction to receive the vibration transmission from the vibration motor 16d. Vibration transmission rod 16e". Extends into the plating vessel 12, and an end portion of the horizontal vibration transfer rod 16e 'is provided at the lower end thereof. This vibration transmission rod 16e 'is shared by two vibration flow generating units 16, and an oscillation blade root 16f in the vertical direction is provided. The vibration motor 16d transmits the vibration to the vibration blade 16f via the vibration member 16c 'and the vibration transmission rod 16e', thereby vibrating the vibration blade 16f in the horizontal direction.

Fig. 12 is a sectional view showing another embodiment of the plating apparatus used in the implementation of the plating method according to the present invention, and Fig. 13 is a plan view cut a part thereof. In this embodiment, the configuration of the vibration flow generating unit 16 differs from the above embodiment. That is, the lower end of the coil spring 16b is fixed to the installation member 118 fixed to the upper end of the plating vessel 12, and the upper end of the coil manne 16b of the vibration member 16c is fixed. The vibration motor 16d is installed in the lower part. In addition, in the coil spring 16b, the lower guide member 124 fixed at the lower end to the installation member 118 and the upper guide member 123 fixed at the upper end to the vibration member 16c are disposed at appropriate intervals. It is.

14 and 15 are cross-sectional views showing another embodiment of the installation in the plating vessel of the vibration flow generating unit constituting the plating apparatus used in the implementation of the plating method according to the present invention, and Fig. 16 is a plan view thereof. 14 and 15 correspond to X-X 'cross section and Y-Y' cross section of FIG. Further, in these drawings, the cathode anode, the power supply circuit, and the like for the plating process are not shown.

In this embodiment, the laminate 3 of the rubber plate 2 and the metal plates 1 and 1 'is used in place of the coil spring 16b as the vibration absorbing member. That is, the laminate 3 is fixed to the bolt 131 to the metal plate (1 ') installed through the vibration-proof rubber 112 to the mounting member 118 fixed to the upper end of the plating vessel 12 and the corresponding The rubber plate 2 is arrange | positioned on the metal plate 1 ', the metal plate 1 is arrange | positioned on this rubber plate 2, and it is formed by integrating this by the bolt 116 and the nut 117. As shown in FIG.

The vibration motor 16d is fixed to the metal plate 1 by the bolt 132 with the support member 115 interposed therebetween. The upper end of the vibration transfer rod 16e is provided on the laminate 3, particularly the metal plate 1 and the rubber plate 2, with the rubber ring 119 interposed therebetween. That is, the upper metal plate 1 exhibits the function of the vibrating member 16c of the embodiment described in FIG. 1 and the like, and the lower metal plate 1 'shows the base 16a of the embodiment described in FIG. ) Will function. And the laminated body 3 (mainly the rubber plate 2) containing these metal plates 1 and 1 'exhibits the vibration absorption function similar to the coil spring 16b described in FIG.

17 shows a plan view of the laminate 3. In the example of FIG. 17A corresponding to the embodiment of FIGS. 11 to 16, the through-hole 5 is formed in the laminate 3 so as to pass through the vibration transfer rod 16e. In addition, in the example of Fig. 17 (b), the stack 3 comes from two parts 3a and 3b bisected by a dividing line passing through the through hole 5, whereby the vibration transfer rod when the device is assembled. It can easily pass through 16e. In addition, in the example of FIG. 17 (c), the laminated body 3 has the ring shape corresponding to the upper end part of the plating container 12, and the opening 6 is formed in the center part.

In the example of FIGS. 17A and 17B, the upper part of the plating vessel 12 is blocked by the laminate 3, so that the gas volatilized in the plating bath 14 and the plating liquid scattering when the plating process is carried out to the surroundings. Can prevent leakage.

FIG. 18 is a cross-sectional view showing a state where the plating vessel is closed by the laminate 3. In the form of FIG. 18A, the rubber plate 2 abuts against the vibration transfer rod 16e in the through hole 5 and closes. In addition, in the form of FIG. 18 (b), the prekinin chamber member 136 provided in the stack 3 and the vibration transfer rod 16e in the opening 6 of the stack 3 to close the gap therebetween. ) Is installed.

An example of the laminated body 3 as a vibration absorbing member is shown in FIG. An example of FIG. 19B is the embodiment of FIGS. 14 to 16 above. In the example of FIG. 19A, the laminate 3 is derived from the metal plate 1 and the rubber plate 2. In the example of FIG. 19C, the laminate 3 comes from the upper metal plate 1, the upper rubber plate 2, the lower metal plate 1 ′ and the lower rubber plate 2 ′. In the example of FIG. 19 (d), the laminate 3 comes from the upper metal plate 1, the upper rubber plate 2, the intermediate metal plate 1 ″, the lower rubber plate 2 ′ and the lower metal plate 1 ′. The number of metal plates and rubber plates in the sieve 3 may be, for example, 1 to 5. Further, in the present invention, the vibration absorbing member may be constituted only by the rubber plates.

As the material of the metal plates 1, 1 ', 1 ", stainless steel, steel, copper aluminum, and other suitable alloys can be used. The thickness of the metal plate is, for example, 10 to 40 mm. The metal plate (for example, the intermediate metal plate 1 ") that is not directly fixed to the plate may be thinned to 0.3 to 10 mm.

As the material of the rubber plates 2 and 2 ', vulcanizates of synthetic rubber or natural rubber can be used, and dustproof rubber prescribed in JISK6386 is preferable, and in particular, the static modulus of 4 to 22 Kgf / cm 2, preferably 5 to 10 Kgf / Cm 2, elongation of at least 250% is preferred. As the synthetic rubber, chloroprene rubber, nitrile rubber, nitrile chloroprene rubber, styrene chloroprene rubber, acrylonitrile butadiene rubber, inprene rubber, ethylene propylene ethylene copolymer alloy rubber, epicronpyrine rubber, alkyrene An orchid seed type | system | group rubber, a subseries rubber | gum, a silicone type rubber, a urethane-based rubber, a sulfonated rubber, and a popofin rubber can be illustrated. The thickness of the rubber sheet is, for example, 5 to 60 mm.

In the example of FIG. 19 (d), the laminated body 3 consists of the upper metal plate 1, the rubber plate 2, and the lower metal plate 1 ', and the rubber plate 2 is the upper solid rubber layer 2a and the sponge It consists of the rubber layer 2b and the lower solid rubber layer 2c. One of the lower solid rubber layers 2a and 2c may be removed, or a plurality of solid rubber layers and a plurality of sponge rubber layers may be laminated.

FIG. 20 shows the flow of the plated article X therebetween based on the voltage applied between the negative electrode busbar 30 and the negative electrode busbar 32 in the power supply circuit 34 in the above embodiment. It is a graph which shows the modification of the change of plating current (current density). In this modification, the current density waveforms of the first and second states are not rectangular, as shown in Fig. 8, but some pulsation occurs. Such pulsation is based on the configuration of the power supply circuit 34. In the present invention, the plating current may be based on such a pulsation current. It is also possible to use the peak value as the current value I1 I2f in the first state and the second state, respectively.

Furthermore, in the present invention, using the power supply circuit 34 having a voltage supply system for the first state and a voltage supply system for the second state, the two circuits output each other (that is, two power sources). You can also change the device and disconnect it.

As described above, the combination technique of the vibration flow of the plating bath and the plating current of the pulse phase can be similarly applied to the anodizing method, the electropolishing method, and the electrolytic degreasing method, which surface-treat the surface of the surface treatment by applying electricity in the treatment bath. have. Of course, for the contents of the treatment, the surface treatment is disposed on the anode side or the tone side. Thereby, the surface treatment of the surface treatment article which has a microstructure can be performed favorably.

Hereinafter, the present invention will be described according to the examples.

Example 1

The apparatus described with respect to FIGS. 1 to 3 was used. Here, a 150W x 200V x 3Φ thing was used as the vibration motor 16d, and 300 liters of capacity was used as the plating vessel 12, and a power production circuit 34 was used as a power master circuit.

As an article to be plated (X), an 8-inch (200 mm diameter) silicon wafer was subjected to a predetermined pretreatment according to a conventional rule, and filled with copper of a blind via hole in which a simultaneous layer was applied in the copper damascene method for multilayer wiring. A conductive film was formed. Many blind via holes have an inner diameter of 24 mu m in a titanium nitride insulating layer having a thickness of 0.35 mu m.

As the plating bath (1), through-hole bath of lactic acid copper plating

Lactic acid copper: 75g / L

Legacy: 190 g / L

Polish: Appropriate

Chlorine ion: 40ml / l

Was used.

The vibration motor 16d of the vibration flow generating unit 16 was vibrated at 45 Hz to vibrate the vibration blade 16f in the plating bath 14 at an amplitude of 0.2 mm and a frequency of 650 times / minute. In addition, the vibration motor 28 was vibrated at 25 Hz and the plated article X was vibrated at an amplitude of 0.15 mm and a frequency of 200 times / minute in the plating bath 14. At this time, the three-dimensional flow rate in the plating bath was measured by a three-dimensional electrode flowmeter ACM-300A (manufactured by Alec Electronics Co., Ltd.), and the result was 200 mm / second.

Shown in Figure 8 by the power supply circuit (34) I1, I2, T1 , respectively T2 is I1 = 6 [A / ^{wafer] = 3 [A / dm 2} ], I2 = 0.6 [A / wafer], T1 = 10 [Seconds] and a plating current of rectangular waves were flowed as T2 = 1 [seconds].

After 10 minutes of treatment, a copper plated film having a thickness of about 10 µm was formed, and it was found that all of the blind via holes were satisfactorily made by conduction and microscopic examination.

Comparative Example 1-1 :

The same treatment as in Example 1 was performed except that T2 = 0 [seconds]. Some of the blind via holes (58%) had a good copper plating treatment, but the rest did not have a good copper plating treatment. The result of the inspection was confirmed by the energizing microscope and the like.

Comparative Example 1-2 :

The same treatment as in Example 1 was conducted except that the vibration flow generating unit 16 was not operated. Some of the blind via holes (10%) had a good copper plating treatment, but the rest did not have a good copper plating treatment. No electricity (such as soot or depressed) was found to have been checked by energization, microscopy and other tests.

Example 2

The apparatus described above with reference to FIGS. 1 to 3 (vibration motor 16d, plating vessel 12, and power supply circuit 34 are the same as in Example 1), and the article to be plated is prescribed according to general rules. A plated conductive film on the inner surface of the through hole was formed by using a multi-layered wiring board of A4 piece length pretreated. Many through holes had an aspect ratio of 10 with an inner diameter of 30 µm.

As the plating bath 14, the common bath of lactic acid copper plating,

Lactic acid copper: 200g / L

Lactic acid: 50g / L

Polishes: Apply

Chlorine Ion: 60mL / L

Was used.

The vibration motor 16d of the vibration flow generating unit 16 was vibrated at 50 Hz, and the vibration blade 16 was vibrated in the plating bath 14 at an amplitude of 0.2 mm and a frequency of 700 times / minute. In addition, the vibration motor 28 was vibrated at 25 Hz, and the plated article X was vibrated in the plating bath 14 with an amplitude of 0.15 mm and a frequency of 200 times / minute. In addition, the swinging motor 20 was driven to vibrate the article to be plated X in the plating bath 14 at a vibration width of 30 mm and a swing rate of 20 times / minute. It was 399 mm / sec when the three-dimensional flow velocity in the plating bath at this time was measured with the three-dimensional electrode flowmeter ACM300-A.

By the power supply circuit 34, I1, I2, T1, and T2 shown in FIG. 8 are I1 = 4 [A / dm ² ], I2 = 0.4 [A / dm ² ], and T1 = 180 [sec], respectively. It became like T2 = 20 [sec], and the plating current of the rectangular wave state flowed.

After 10 minutes of treatment, it was found that a good copper plating film was formed for 99.9% of the large number of through holes.

Comparative Example 2-1 :

The same treatment as in Example 2 was performed except that T2 = 0 [seconds]. A good copper plating film was formed over the entire length in a part (50%) of the plurality of through holes, but a good copper plating film was not formed in the rest. It turned out that it did not carry out electricity, the microscope and other inspection results.

Comparative Example 2-2 :

The same process as in Example 2 was conducted except that the vibration flow generating unit 16 was not operated. A good copper plating film was formed in a part (10%) of the plurality of through holes, but the good copper plating film was not formed in the rest. (Defects such as soot and squeeze), energization, microscopy and other tests were found.

Example 3 :

Using the apparatus described above with reference to Figs. 9 to 11 (the vibration motor 16d, the plating vessel 12, and the power supply circuit 34 are the same as those in the first embodiment), the article to be plated is prescribed by a general rule. Using 800 ceramic chips with a length of 0.6 mm × 0.3 mm × 0.2 mm, the surface of both ends in the rectangular direction and a portion of the surface of 0.6 mm × 0.3 mm (following 0.1 mm from both ends) Nickel plated film was formed to form an electrode film.

The plating bath 14 at the time of nickel plating is a barrel bath

Nickel Lactic Acid: 270g / L

Nickel Chloride: 68g / L

Boric acid: 40 g / L

Magnesium Lactate: 225g / L

Was used.

The vibration motor 16d of the vibration flow generating unit 16 was vibrated at 55 Hz, and the vibration blade 16f was vibrated at an amplitude of 0.2 mm and a frequency of 750 times / minute in the plating bath 14. In addition, the vibration motor 48 was vibrated to cause the plated article X to vibrate in the plating bath 14 at 0.12 mm and a frequency of 250 times / minute. At this time, the three-dimensional flow rate in the plating bath was 210 mm / sec as defined by the three-dimensional electrode flowmeter ACM300-A. As the barrel 52, a mesh opening 20% was used, and the barrel rotation speed was 10 rpm.

Power supply circuit 34, the I1, I2, T1, T2, which, indicated in Figure 8 by each of ^{I1 = 0.4 [A / dm 2} ], I2 = 0.04 [A / dm 2], I2 = 0.04 [A / dm 2 ], T1 = 20 [sec], T2 = 2 [sec], and the plating current of a rectangular wave was sent.

After 30 minutes of treatment at 50 ° C, it was found that a good nickel plated film having a thickness of about 2 µm was formed on all the chips, as a result of current and microscopic examination.

Comparative Example 3-1 :

Except for setting T2 = 0 [seconds], the same treatment as in Example 3 was carried out. Part of the chip (12%) had a good nickel plated film, but the rest of the chip did not have a good nickel plated film. Other test results proved.

Comparative Example 3-2 :

The same process as in Example 3 except that the vibration flow generating unit 16 was not operated, a good nickel plated film was formed in a part (60%) of the plurality of through holes, but a good nickel plated film was not formed in the rest. It turned out that it did not carry out electricity, the microscope and other inspection results.

Example 4 :

Suzu plating was performed instead of nickel plating as in Example 3. As the plating bath 14, an acidic suzu plating lactate bath,

Lactose First: 50g / L

Lactic acid: 100g / L

Cresol's mixed acid: 100 g / L

Gelatin: 2 g / L

β-naphthal: 1 g / L

Was used.

The I1, I2, T1, T2 shown in Figure 8 by the power supply circuit (34) I1 = 0.4, respectively ^{[A / dm 2], I2} = 0.04 [A / dm 2], T1 = 20 [A / dm 2] The plating power source of rectangular wave state was flowed so that T2 = 2 [second].

After 60 minutes of treatment at 50 ° C, it was found that a good Suzu plating film was formed on all the chips.

Comparative Example 4-1 :

Except for setting T2 = 0 [seconds], the same process as in Example 4 was performed, and a good nickel plated film was formed on a portion (10%) of the chip, but the good nickel plated film was not formed. In addition, examination results other than the microscope were found.

Comparative Example 4-2 :

The same process as in Example 3 is performed except that the vibration flow generating unit 16 is not operated. Some of the through holes (57%) had a good nickel plated film, but the rest of them did not form a good nickel plated film.

Example 5 :

Using the apparatus described above with reference to FIGS. 9 to 11 (the vibration motor 16d, the plating 12, and the power supply circuit 34 are the same as those in the first embodiment), the article to be plated is prescribed by a general rule. The nickel plated film was formed on the other surface using the 30 mm 20 mm elongation pin which preformed the external processing of 0.5 mm phi.

As the plating bath 14 at the time of nickel plating, it is a barrel bath

Nickel Lactic Acid: 270g / L

Nickel Chloride: 68g / L

Boric acid: 40 g / L

Magnesium Lactate: 225g / L

Was used.

The vibration motor 16d of the vibration flow generating unit 16 was vibrated at 45 Hz, and the vibration blade 16f was vibrated in the plating bath 14 at an amplitude of 0.2 mm and a frequency of 500 times / minute. Further, the vibration motor 48 was vibrated, and the plated article X was vibrated in the plating bath 14 at an amplitude of 0.15 mm and a frequency of 200 times / minute. At this time, the three-dimensional flow rate of the plating bath was 200 mm / sec as measured by the three-dimensional electrode flowmeter ACM300-A. As the barrel 52, a mesh opening 20% was used, and the barrel rotation speed was 10 rpm.

By power supply circuit 34, I1, I2, T1 and T2 shown in FIG. 8 are respectively represented by I1 = 3 [A / dm ² ], I2 = 0.3 [A / dm ² ], T1 = 30 [sec], T2 = As shown in 3 [sec], the plating current of rectangular wave state is used.

20 minutes at 50 ℃. It was found that a nickel plated film having good film uniformity was formed over the entire fin, as a result of the film thickness measurement, energization, and inspection other than the microscope.

Comparative Example 5-1 :

The same treatment as in Example 5 was performed except that T2 = 0 [sec], and a good nickel plated film was formed on a part of the fin (17%), but the nickel plated film was not formed. It was found that the result of the film thickness measurement, the energization, and the inspection of the microscope and the like.

Comparative Example 5-2 :

The same process as in Example 5 was conducted except that the vibration flow generating unit 16 was not operated. A good nickel plated film was not formed on a part (60%) of the fins, but the nickel plated film had a good uniformity in film thickness. It was found that it was not formed (defects such as soot and squeeze) were measured by film thickness measurement, energization, and inspection other than a microscope.

Example 6 :

Using the apparatus described with reference to Figs. 1 to 9 (vibration motor 16d and plating vessel 12 and power supply circuit 34 are the same as in Example 1), the general rule as the article to be plated X is applied. Thus, about 30000 spheres of 3 mm diameter chloronitrile and butadiene styrene polymer (ABS resin) subjected to a predetermined pretreatment (including degreasing treatment and charging) were used, and copper plating films were formed on the other surfaces.

In the plating bath 14 at the time of copper plating,

Lactic acid copper: 200g / L

Lactic acid: 50g / L

Polishes: Apply

Chlorine Ion: 40mL / L

Was used.

The vibration motor 16d of the vibration generating unit 16 was vibrated at 40 Hz, and the vibration blade 16f was vibrated in the plating bath 14 at an amplitude of 0.2 mm and a frequency of 700 times / minute. In addition, the vibration motor 48 was vibrated to cause the plated article X to vibrate in the plating bath 14 at an amplitude of 0.15 mm and a frequency of 250 times / minute. At this time, the three-dimensional flow rate of the plating bath was measured by a three-dimensional electrode flowmeter ACM300-A, and it was 210 mm / sec. As barrel 52, the thing of mesh opening 20% was used, and barrel rotation speed was 10 rpm.

The I1, I2, T1, T2, which, indicated in Figure 8 by the power supply circuit 34, respectively, ^{I1 = 0.5 [A / dm 2} ], I2 = 0.04 [A / dm 2], T1 = 30 [ seconds], T2 The plating current of rectangular wave state was flowed so that it might be set to = 3 [sec].

After 30 minutes of treatment at 50 DEG C, it was found that 99.5% of the spheres had a copper-plated film having good uniformity in film thickness.

Comparative Example 6-1 :

The same processing as in Example 6 was performed except that T2 = 0 [sec]. Part of the spheres (40%) had a good nickel plated film, but the remainder was not formed with a copper plated film having good film thickness uniformity.

Comparative Example 6-2 :

The same treatment as in Example 6 was conducted except that the vibration motor generator 16 was not operated. Part of the spheres (50%) had a good nickel plated film formed thereon, but the remaining nickel plated had good uniformity in film thickness. It was found that no film was formed, as a result of film thickness measurement, energization, microscopy and other inspection results.

Example 7 :

The apparatus described with respect to FIGS. 1 to 3 was used. Here, a 150 W x 200 V x 3 Φ thing was used as the vibration motor 16d, and a capacity of 300 liters was used as the plating vessel 12. As the power supply circuit 34, a power master PMDI type manufactured by Joongang Co., Ltd. was used.

As the object to be plated (X), a silicon wafer having a thickness of 1 mm was used at a 40 mm angle subjected to a predetermined pretreatment by a rule. On the surface of this silicon wafer, a large number of blind via holes having an inner diameter of 20 mu m and a depth of 70 mu m are formed.

The plating bath 14 is a through-hole bath of lactic acid copper plating,

Lactic acid copper: 75g / L

Heritage: 190g / L

Polishes: Apply

Chlorine Ion: 40mL / L

Was used.

Furthermore, a ceramic antacid engine (outer diameter 75 mm Φ: inner diameter 50 mm Φ: length 500 mm: pore diameter 50 to 60 mu m: pore ratio 33 to 38%) is placed in the plating vessel 12, and bubbles are placed in the plating bath 14. Generated.

The vibration motor 16d of the vibration flow generating unit 16 was vibrated at 40 Hz, so that the vibration blade root 16f was vibrated in the plating bath 14 at an amplitude of 0.1 mm and a frequency of 650 times / minute. Moreover, the vibration motor 28 of 75Wx200Vx3Φ was vibrated at 25Hz, and the to-be-plated article X was vibrated in the plating bath 14 at the amplitude of 0.15 mm and the frequency 200 times / min. At this time, the three-dimensional flow rate of the plating bath was determined to be cmr by using an electric flowmeter ACM300-A (manufactured by Alec Electronics Co., Ltd.), which was three orders of magnitude, and was 200 mm / sec.

By the power supply circuit 34, each of I1, I2, T1, and T2 shown in FIG. 8, I1 = 1.5 [A / wafer], I2 = 0.1 [A / wafer], T1 = 0.08 [sec], T2 = 0.02 [sec The plating current of rectangular wave state was sent so that it might become].

After 2.5 hours of treatment, a copper plating film having a uniform thickness of about 7 μm was formed on the inner surface of all the blind via holes.

Comparative Example 7 :

The same processing as in Example 7 was carried out except that T2 = 0 [sec]. Closing the opening of the blind via hole with the plating film was found to be the result of inspection other than energization and a microscope.

Example 8

Using the high frequency vibration motor as the vibration motor 16d of the vibration flow generating unit 16, it was vibrated at 150 Hz, so that the vibration blade root 16f was subjected to an amplitude of 0.2 mm and a frequency of 1200 times / min in the plating bath 14. The same treatment as in Example 7 was repeated except that the treatment time was about 1.5 hours. As a result, it turned out that the copper plating film of uniform thickness of about 7 micrometers is formed in the inner surface of many blind via holes by the inspection results other than an electricity supply and a microscope.

Example 9 :

The epochine resin board for wiring boards was used as the to-be-plated article (X). A large number of blind via holes having an inner diameter of 15 μm and a depth of 40 μm are formed on the surface of the epochine resin plate.

Electroplating was performed by degreasing-washing-etching-washing-neutralizing-washing-catalyst-washing-axeretta-washing-electroless copper plating to give electroconductivity, and further, washing, activating, washing-strike-plating. In the electroless copper plating and the strike plating, as described with reference to FIGS. 1 to 3, the same vibration flow was generated in the plating treatment liquid by the vibration flow generating unit.

Electroplating was carried out as in Example 7. However, the swinging motor 20 was driven to swing the article to be plated X in the plating bath 14 at a swing width of 30 mm and a number of swings of 20 times / minute. At this time, the three-dimensional flow rate of the plating bath was measured by the three-dimensional electrode flowmeter ACM300-A, and the result was 200 mm / sec.

Power supply circuit 34 by, respectively, I1, I2, T1, T2 shown in Fig. 8 I1 = 4.5 [A / dm 2], I2 = 0.4 [A / dm 2], T1 = 0.08 [ sec], T2 The plating current of a rectangular wave state was sent as it is set to 0.015 [second].

After one hour of treatment, it was confirmed that currents and microscopic examinations showed good results in all the blind via holes.

Comparative Example 8 :

The same processing as in Example 9 was carried out except that T2 = 0 [sec]. Although the opening of the blind via hole was closed by the plating film, it was confirmed that the electric current and other inspections showed that the gap remained in the corner part.

As described above, according to the electroplating method of the present invention, even if the plated film conductive pattern is fine, it is possible to form the plated film with good quality without defects and film thickness nonuniformity. Moreover, according to this invention, the plating film of the favorable quality of the conductive pattern of a microstructure can be obtained at high speed. Furthermore, according to the present invention, a plated film of good quality of a conductive pattern of fine structure can be obtained with high efficiency with a relatively small device configuration.

Claims (11)

Contacting with the plating bath while generating a vibration flow of three-dimensional flow rate of 150 mm / sec or more in the plating bath by vibrating the oscillation blade fixed in one or multiple stages to the vibration rod vibrating in the plating bath in conjunction with the vibration generating means. A plated article disposed as a cathode and a metal part arranged to contact the plating bath at the same time as an anode, and a voltage is put between the cathode and the above-described anode, wherein the plating bath is And the plating current flowing to the cathode is in a pulse and lasts for a first time T1 at a first value I1 and lasts for a second time T2 at a second value I2 of the same polarity as the first value. Exchanging a second state (alternatively), wherein the first value I1 is 5-25 times the second value I2, the first time T1 is 0.01-300 seconds, and the second time T2 Characterized by 3 to 25 times Electroplating method. delete delete The electroplating method according to claim 1, wherein the vibrating blade root vibrates finely at an amplitude of 0.05 to 10.0 mm and a frequency of 200 to 1500 times / minute. delete The electroplating method of claim 1, wherein the vibration generating means vibrates at 10 to 500 Hz. The electroplating method according to claim 1, wherein the article to be plated is vibrated at an amplitude of 0.05 to 5.0 mm and a frequency of 100 to 300 revolutions per minute. The electroplating method according to claim 1, wherein the article to be plated is rocked at a swing width of 10 to 100 mm and a swing number of 10 to 30 times / minute. The electroplating method according to any one of claims 1 to 8, wherein the article to be plated has a plated surface having a fine structure of 50 µm or less. 9. The plated article according to any one of claims 1 to 8, wherein the plurality of plated articles are plated on the plated article by contacting the plated article with a small hole for allowing the liquid of the plating bath to pass therethrough. By holding a conductive member through which a current flows in a holding container, and rotating the holding container around the center of rotation in a non-vertical direction in the plating bath, the various to-be-plated articles are driven in the holding container, and the article to be plated. Electroplating method, characterized in that to repeat the contact and spacing of each and the conductive member in sequence. The electroplating method according to claim 10, wherein the width of the article to be plated is 5 mm or less.