[0001] 1. Field of the Invention
[0002] The present invention relates to a plating method, and particularly to a plating method using a specific combination of a physical condition of a plating bath and an electric condition of plating current.
[0003] 2. Description of the Related Art
[0004] An electroplating technique of forming a film of electrically conductive material on the surface of an article has been broadly used in the manufacturing industry of articles such as electronic parts, etc. Particularly, in order to satisfy requirements of miniaturization and high functionality to electronic parts, conductive patterns to be formed on the surfaces (containing the inner surface of through hole, the inner surface of blind via hole) of articles have been required to be formed finely.
[0005] For example, the microstructure design of wiring patterns is promoted in connection with decrease of the pitches of input/output terminals due to the high-integration design of semiconductor devices, and in connection with this promotion, it has been required that the through hole and the blind via hole are designed to have an inner diameter of 100 μm or less, further 50 μm or less, still further 30 μm or less. Further, a large aspect ratio of 5 or more, further 8 or more has been required to the through hole and the blind via hole.
[0006] For example, in order to reduce the capacity between wires which occurs due to the microstructure design of wires required in connection with the high-integration design, copper wires are used in place of aluminum wires which have been hitherto used, and a damascene method using electroplating to form copper multi-layered wires has been used. In this method, it has been required to perform copper deposition in very small blind via holes having the inner diameter of 1 μm or less.
[0007] Further, it has been required that a pair of electrode films are formed on the surface of a chip part having a dimension of about 0.3 mm.
[0008] Particularly, the applicant of this application has proposed a plating method that is effectively applicable to articles having microstructured parts such as fine holes, etc. (see JP(A)-11-189880). According to this method, vibrational flow induced in a plating bath and bubbling induced by a diffusing pipe are used in combination. This method is also effectively applicable to electroless plating as well as electroplating.
[0009] However, in this method, it is required to dispose the diffusing pipe in a plating tank in which the plating bath is accommodated, and also it is required to establish an air pipe to the diffusing pipe. Therefore, the amount of the plating bath and the dimension of the plating tank must be relatively increased, so that the plating apparatus itself must be designed in large size.
[0010] Besides, DC power source is generally used as power source for the electroplating. In order to enhance the quality of plating films, there has been proposed a technique of carrying out plating while the plating current is periodically varied. In this method, positive-polarity current and negative-polarity current alternately flows. That is, a plating film is temporarily formed by supplying the positive-polarity current, and then projecting portions of minute uneven portions on the surface of the plating film thus formed are concentratively and partially melted by supplying the negative-polarity current. The above operation is repeated to achieve a high-quality plating film that has a flat surface and no defects such as minute voids or the like. According to this method, however, the surface portion of the plating film which is temporarily formed is removed and thus this method has a disadvantage in enhancement of the film forming speed (that is, the enhancement of the plating treatment speed).
[0011] It is a recent tendency that conductive patterns are designed in a further microstructure design, and when a plating film having such a conductive pattern is formed, defects or unevenness in film thickness is liable to occur. Therefore, it has been more and more difficult to keep the excellent quality of the plating film.
[0012] The applicant of this application has also proposed a plating method of carrying out chrome-plating while vibrationally stirring the plating bath, and a plating method of accommodating many articles to be plated (hereinafter referred to as “plating target articles”) in a barrel and carrying out chrome-plating while vibrationally stirring the plating bath (see JP(A)-7-54192 and JP(A)-6-330395).
[0013] However, these methods use direct current as plating current, and these publications have no specific disclosure on the application of these methods to minute plating target articles such as articles each of which has a width (the dimension in the traverse direction to the longitudinal direction) of 5 mm or less, for example, 0.3 to 1.0 mm. In the barrel plating process for these minute plating target articles, the plating target articles are overlapped with one another in the barrel, and thus the distribution of plating liquid to desired plating film forming portions of the plating target articles is extremely lowered. Therefore, there are a lot of technical difficulty for these minute plating target articles beyond comparison with plating target articles having relatively large widths, and a further improvement must be made in point of the film forming speed and the evenness of film thickness.
[0014] Therefore, an object of the present invention is to provide a plating method which can form a plating film having a microstructured conductive pattern with high quality so that the plating film has no defect and is not uneven in film thickness.
[0015] Another object of the present invention is to provide a plating method which can form a high-quality plating film having a microstructured conductive pattern at high speed.
[0016] Another object of the present invention is to provide a plating method which can efficiently form a high-quality plating film having a microstructured conductive pattern by a relatively small apparatus.
[0017] In order to attain the above objects, according to the present invention, there is provided an electroplating method, characterized in that a plating target article disposed so as to be in contact with plating bath is set as a cathode while a metal member disposed so as to be in contact with the plating bath is set as an anode, and a voltage is applied between the cathode and the anode while vibrational flow is induced by vibrating vibrational vanes which are fixed in one-stage or multi-stage style to a vibrating rod vibrating in the plating bath interlockingly with vibration generating means, wherein plating current flowing from the anode through the plating bath to the cathode is pulsed and alternately set to one of a first state where the plating current keeps a first value I
[0018] In an aspect of the present invention, the first value I
[0019] In an aspect of the present invention, the plating target article is vibrated at an amplitude of 0.05 to 5.0 mm and a vibration frequency of 100 to 300 revolutions per minute. In an aspect of the present invention, the plating target article is swung at a swinging width of 10 to 100 mm and a swinging frequency of 10 to 30 times per minute.
[0020] In an aspect of the present invention, the plating target article has a face to be plated having a microstructure of a dimension of 50 μm or less.
[0021] In an aspect of the present invention, a plurality of plating target articles are accommodated in a holding container, the holding container having small holes through which liquid of the plating bath is allowed to pass and being equipped with an electrically conductive member which is brought into contact with the plating target articles to make current flow through the plating target articles, and wherein the holding container is rotated around the rotational center corresponding to a non-vertical direction in the plating bath to roll the plating target articles in said holding container to thereby repeat the contact and separation between each of the plating target articles and the electrically conductive member.
[0022] In an aspect of the present invention, the width of each of the plating target articles is equal to 5 mm or less.
[0023] According to the electroplating method of the present invention, even when a plating conductive pattern is minute, a plating film having uniformity in thickness and no defect can be formed with high quality. Further, according to the present invention, a high-quality plating film of microstructured conductive pattern can be obtained at high speed. Still further, according to the present invention, a high-quality plating film of microstructured conductive pattern can be efficiently obtained by a relatively small apparatus.
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[0047] Preferred embodiments according to the present invention will be described hereunder with reference to the accompanying drawings. In the figures, the members or portions having the same functions are represented by the same reference numerals.
[0048]
[0049] In these figures, reference numeral
[0050] The vibrating motor
[0051]
[0052]
[0053]
[0054] In this modification, each vibrating vane
[0055] As shown in
[0056] The vibrating vanes
[0057] In FIGS.
[0058] In the present invention, a circuit for rectifying AC current (containing adding DC components) and then outputting the rectified current is used as the power source circuit (power source device) used to generate plating current. As such a power source device or rectifier may be used a transistor adjustment type power source, a dropper type power source, a switching power source, a silicon rectifier, an SCR rectifier, a high-frequency type rectifier, an inverter digital control type rectifier (for example, Power Master produced by Chuo Seisakusho Co., Ltd.), KTS series produced by Sansha Denki Seisakusho Co., Ltd., an RCV power source produced by Shikoku Denki Co., Ltd., a device which comprises a switching regulator type power source and a transistor switch and supplies rectangular pulse current by switching on/off the transistor switch, a high-frequency switching power source (in which AC current is converted to DC current through a diode, then high frequency of 20 to 30 KHz are applied to a transformer to carry out the rectification and smoothing again, and then the output is taken out), a PR type rectifier, a high-frequency control type high-speed pulse PR power source (for example, HiPR series produced by Chiyoda Co., Ltd. or the like.
[0059] Here, the current waveform will be described. In order to implement both the increase in plating speed and the improvement of the characteristics of plating films, it is important to select the wave form of plating current. The voltage and current conditions required for the electroplating are varied in accordance with the type of plating, the composition of plating bath and the dimension of the plating tank, and thus they cannot be sweepingly specified. However, if the plating voltage is set to a DC voltage of 2 to 15V, it can sufficiently cover the whole at present. Therefore, four kinds of rated output voltage of the plating DC current (6V, 8V, 12V, 15V) are standardized in the industry. The voltage below the above rated can be adjusted, and thus a power source for generating a rated voltage which has a slightly extra voltage with respect to a desired voltage value required for plating is preferably selected. In the industry, the rated output current from 500 A, 1000 A till about 2000 A to 10000 A are standardized as the rated output current of the power source, and the other current values are provided in the form of production to order. It is better that the required current capacity of the power source is determined as the desired current density of plating target article x the surface area of the plating target article in accordance with the type and surface area of the plating target article, and a proper standard power source satisfying the above required current capacity is selected.
[0060] The pulse wave is originally defined as a pulse having a sufficiently shorter width w than its period T. However, this definition is not strict. The pulse wave contains waves other than the square wave. The operating speed of elements used in a pulse circuit is increased, and the pulse width of ns (10
[0061] A saw-tooth wave, a ramp wave, a triangular wave, a composite wave, a rectangular wave (square wave), etc. are known as the types of pulse waves, and particularly the present invention preferably uses the rectangular wave in consideration of the efficiency of electricity and smoothing.
[0062]
[0063] The cathode bus bar
[0064]
[0065] In FIGS.
[0066]
[0067] As shown in
[0068] The first value I
[0069] The plating bath
[0070] Copper sulfate: 60 to 100 g/L (liter)
[0071] Sulfuric acid: 170 to 210 g/L
[0072] Brightener: proper amount
[0073] Chlorine ion: 30 to 80 mL/L
[0074] The following may be used as normal bath for the copper sulfate plating:
[0075] Copper sulfate: 180 to 250 g/L
[0076] Sulfuric acid: 45 to 60 g/L
[0077] Brightener: proper amount
[0078] Chlorine ion: 20 to 80 m/L
[0079] Further, in the case of the nickel plating, the following may be used as barrel bath:
[0080] Nickel sulfate: 270 g/L
[0081] Nickel chloride: 68 g/L
[0082] Boric acid: 40 g/L
[0083] Magnesium sulfate: 225 g/L
[0084] The following may be used as normal bath for the nickel plating:
[0085] Nickel sulfate: 150 g/L
[0086] Ammonium chloride: 15 g/L
[0087] Boric acid: 15 g/L
[0088] The following may be used as Watts bath for the nickel plating:
[0089] Nickel sulfate: 240 g/L
[0090] Ammonium chloride: 45 g/L
[0091] pH: 4 to 5
[0092] bath temperature: 45 to 55° C.
[0093] Further, in the case of the acidic tin plating, the following may be used as sulfate bath:
[0094] Stannous sulfate: 50 g/L
[0095] Sulfuric acid: 100 g/L
[0096] Cresolsulfonic acid: 100 g/L
[0097] Gelatin: 2 g/L
[0098] β-naphthol: 1 g/L
[0099] Electronic parts, mechanical parts, etc. may be used as articles X to be plated, and the articles X are not limited to specific ones. The present invention is remarkably effectively applied to a case where a plating film having a microstructure is formed. Particularly, the following cases may be considered as the plating of these articles X: formation of a plating conductive film onto the inner surface of a minute blind via hole or through hole having an inner diameter of 100 μm or less (for example, 20 to 100 μm, or particularly 50 μm or less, further 30 μm or less, e.g. 10 μm, 5 μm, 3 μm, etc.) and having a depth of 10 to 100 μm for example in a multi-layered wiring board; formation of a conductive film in a minute groove to form a high-density wiring pattern having a pitch of 50 μm or less (for example, 20 to 50 μm, or particularly 30 μm or less, further 20 μm or less, e.g. 10 μm, 5 μm, etc.), the minute groove having a width of 30 μm or less (particularly 20 μm or less, further 10 μm or less, e.g. 5 μm, 3 μm, etc.) and depth of 7 to 70 μm for example; formation of an embedded conductive film into an extremely minute blind via hole having an inner diameter of about 0.3 μm or less or into an extremely minute groove having a width of 0.1 μm and depth of 1.5 μm by copper damascene method when multi-layered wires of a semiconductor device are formed; formation of minute electrode bumps disposed in a high-density arrangement in a semiconductor device; etc. The improving effect of the present invention is particularly remarkable when it is applied to the structure having a high aspect ratio, for example 3 or more, especially 5 or more.
[0100] Further, an extremely small article having an average diameter of 5 to 500 μm may be used as the plating target article X. Here, the average diameter is defined as the average value of representative dimensions in the three directions that cross to one another at right angles. As this type of plating target article X may be provided metal powder such as copper powder, pre-treated aluminum powder or iron powder, synthetic resin powder such as ABS resin powder or the like which is treated to have electrical conductivity, ceramic chips which are treated to have electrical conductivity, etc. Further, other electronic parts, mechanical parts, metal powder alloy, minute particulate inorganic/organic pigment, metal balls, etc. may be also provided.
[0101] For example, Ni plating films may be formed on metal particles such as Cu particles each having a diameter of about 300 μm, or an Au plating film or an Ag plating film may be formed on an Ni plating film to form a composite plating film.
[0102] Further, when a plating target article is made of electrically insulating material such as plastic or the like, a conductive base (primer) forming treatment is carried out as a pre-treatment of the electroplating. However, in the case of a microstructured plating face having a high aspect ratio, an uniform and excellent conductive base could not be formed even if the conductive base forming treatment is carried out by normal electroless plating. Therefore, the thickness of the plating film obtained by the electroplating is liable to be non-uniform. In order to avoid this problem, the conductive base forming treatment may be carried out by sputtering or vacuum deposition. However, in this case, since the treatment is carried out in a pressure-reduced apparatus, there occur such difficulties that the cost of the treatment apparatus rises up and a mass-production treatment and a continuous treatment cannot be performed. On the other hand, if the conductive base forming treatment using the electroless plating or the like is carried out while vibrational flow is induced in treatment liquid by using the same means as the vibrational flow generating means used in the present invention, a highly uniform conductive base can be formed on even a microstructured plating face having a high aspect ratio. Accordingly, by combining the conductive base forming treatment and the electroplating method of the present invention, the process from the pre-treatment to the electroplating treatment can be continuously carried out, and thus the productivity can be enhanced more and more.
[0103] According to the plating method of the present invention, the distribution of the plating bath into microstructure recess portions can be enhanced by the vibrational flow which is induced in the plating bath
[0104] Further, according to the present invention, short-circuit can be prevented by the action of the vibrational flow occurring in the plating bath
[0105] In order to attain such an excellent action, it is remarkably preferable that the three-dimensional flow rate of the vibrational flow of the plating bath
[0106] In this embodiment, the effect can be further enhanced by swinging and/or vibrating the plating target article X through the swing and/or vibration of the swinging frame
[0107]
[0108] In FIGS.
[0109] Reference numeral
[0110] The vibrating motor
[0111] In this embodiment, the plating current density is set in the same way as described with reference to
[0112] This embodiment is more effectively applied to a case where formation of electrode films on plating target articles X having extremely small dimensions, for example, chip parts such as ceramic chip capacitors of about 0.6 mm×0.3 mm×0.2 mm in dimension or the like, or formation of plating films on pins of about 0.5 mm in diameter x about 20 mm in length is carried out on a large number of plating target articles at the same time. As described above, when such a minute article that the dimension in the direction traversing the longitudinal direction, that is, the width is equal to 5 mm or less, further 2 mm or less, still further 1 mm or less is used as the plating target article, the improving effect in the uniformity of the plating film thickness and the film forming speed is greater. Besides, metal powder alloy, inorganic/organic pigment particulates, metal balls may be targeted as the plating target articles.
[0113] As a matter of course, a desired pre-treatment is carried out before the electroplating method of the present invention is carried out. The pre-treatment is carried out in the same manner as the well-known electroplating method.
[0114] Further, a vibrational flow generator disclosed in JP(A)-11-189880 (in which vibrating vanes are disposed at the bottom portion of a plating tank, and vibration is transmitted from a vibrating motor through a vibration transmitting frame to the vibrating vanes to vibrate the vibrating vanes in the horizontal direction, as described with reference to
[0115] For example, vibrational flow generators shown in
[0116]
[0117]
[0118] In this embodiment, a laminated member
[0119] A vibrating motor
[0120]
[0121] According to the embodiments of
[0122]
[0123]
[0124] Examples of material of the metal plates
[0125] Material of the rubber plate
[0126] Examples of synthetic rubber are chloroprene rubber, nitrile rubber, nitrile-chloroprene rubber, styrene-chloroprene rubber, acrylonitrile-butadiene rubber, isoprene rubber, ethylene-propylene-diene rubber, epichlorohydrin rubber, alkylene oxide rubber, fluororubber, silicone rubber, urethane rubber, polysulfide rubber, phosphorus rubber (flame-retarded rubber). The thickness of the rubber plate is 5 to 60 mm for example.
[0127] The laminated member
[0128]
[0129] In the present invention, the power source circuit
[0130] The combination technique of the vibrational flow of the plating bath and the pulsed plating current as described above may be applied to an anodizing method, an electrolytic polishing method, an electrolytic degreasing method, etc. in which the surface treatment of target objects is carried out by utilizing current flow in a treatment bath. The target objects are disposed at the anode side or cathode side in accordance with the treatment content. By using this combination technique, the surface treatment on target articles having microstructures can be excellently performed.
[0131] The present invention will be described in more detail with the following examples.
[0132] The apparatus described with reference to FIGS.
[0133] 8-Inch (diameter of 200 mm) silicon wafers which were subjected to a predetermined pre-treatment by the conventional method were used as the plating target articles X, and a process of forming copper-embedded conductive film in blind via holes coated with a copper seed layer in the copper damascene method was carried out. Many blind via holes were formed in a titanium nitride insulation layer of 0.35 μm in thickness to have an inner diameter of 0.24 μm.
[0134] The following through hole bath of copper sulfate plating was used as the plating bath
[0135] Copper sulfate: 75 g/L
[0136] Sulfuric acid: 190 g/L
[0137] Brightener: proper amount
[0138] Chlorine ion: 40 mL/L
[0139] The vibrating motor
[0140] The plating current of rectangular waveform was supplied by the power source circuit
[0141] When the treatment was carried out for 10 minutes, it was found on the basis of a current flowing test, microscopy and other tests that excellent copper plating films of about 10 μm in thickness were formed and embedded in all the blind via holes.
[0142] The same treatment as Example 1, except for the condition: T
[0143] The same treatment as Example 1, except that the vibrational flow generator
[0144] The plating conductive films were formed on the inner surfaces of through holes by using the apparatus described with reference to FIGS.
[0145] The following normal bath of copper sulfate plating was used as the plating bath
[0146] Copper sulfate: 200 g/L
[0147] Sulfuric acid: 50 g/L
[0148] Brightener: proper amount
[0149] Chlorine ion: 60 mL/L
[0150] The vibrating motor
[0151] The plating current of rectangular waveform was supplied by the power source circuit
[0152] When the treatment was carried out for 10 minutes, it was found on the basis of a current flowing test, microscopy and other tests that excellent copper plating films were formed in 99.9% through holes.
[0153] The same treatment as Example 2, except for the condition: T
[0154] The same treatment as Example 2, except that the vibrational flow generator
[0155] The apparatus described with reference to FIGS.
[0156] The following barrel bath was used as the nickel plating bath
[0157] Nickel sulfate: 270 g/L
[0158] Nickel chloride: 68 g/L
[0159] Boric acid: 40 g/L
[0160] Magnesium sulfate: 225 g/L
[0161] The vibrating motor
[0162] The plating current of rectangular waveform was supplied by the power source circuit
[0163] When the treatment was carried out at 50° C. for 30 minutes, it was found on the basis of a current flowing test, microscopy and other tests that excellent nickel plating films of about 2 μm in thickness were formed in all the ceramic chips.
[0164] The same treatment as Example 3, except for the condition: T
[0165] The same treatment as Example 3, except that the vibrational flow generator
[0166] In place of the nickel plating, tin plating was carried out in the same way as Example 3. The following sulfate bath of acidic tin plating was used as the plating bath
[0167] Stannous sulfate: 50 g/L
[0168] Sulfuric acid: 100 g/L
[0169] Cresolsulfonic acid: 100 g/L
[0170] Gelatin: 2 g/L
[0171] β-naphthol 1 g/L
[0172] The plating current of rectangular waveform was supplied by the power source circuit
[0173] When the treatment was carried out at 50° C. for 60 minutes, it was found on the basis of a current flowing test, microscopy and other tests that excellent tin plating films were formed in all the ceramic chips.
[0174] The same treatment as Example 4, except for the condition: T
[0175] The same treatment as Example 4, except that the vibrational flow generator
[0176] The apparatus described with reference to FIGS.
[0177] The following barrel bath was used as the nickel plating bath
[0178] Nickel sulfate: 270 g/L
[0179] Nickel chloride: 68 g/L
[0180] Boric acid: 40 g/L
[0181] Magnesium sulfate: 225 g/L
[0182] The vibrating motor
[0183] The plating current of rectangular waveform was supplied by the power source circuit
[0184] When the treatment was carried out at 50° C. for 20 minutes, it was found on the basis of the measurement of the thickness of the nickel plating films, current flowing test, microscopy and other tests that excellent nickel plating films having excellent uniformity in thickness were formed in all the pins.
[0185] The same treatment as Example 5, except for the condition: T
[0186] The same treatment as Example 5, except that the vibrational flow generator
[0187] The apparatus described with reference to FIGS.
[0188] The following was used as the plating bath
[0189] Copper sulfate: 200 g/L
[0190] Sulfuric acid: 50 g/L
[0191] Brightener: proper amount
[0192] Chlorine ion: 40 mL/L
[0193] The vibrating motor
[0194] The plating current of rectangular waveform was supplied by the power source circuit
[0195] When the treatment was carried out at 50° C. for 30 minutes, it was found on the basis of the measurement of the thickness of the copper plating films, current flowing test, microscopy and other tests that excellent copper plating films having excellent uniformity in thickness were formed in 99.5% spheres.
[0196] The same treatment as Example 6, except for the condition: T
[0197] The same treatment as Example 6, except that the vibrational flow generator
[0198] The apparatus described with reference to FIGS.
[0199] A silicon wafer having a size of 40 mm×40 mm and a thickness of 1 mm which was subjected to a predetermined pre-treatment by the conventional method was used as the plating target article X, on the surface of which many blind via holes each having an inner diameter of 20 μm and a depth of 70 μm were formed.
[0200] The following through hole bath of copper sulfate plating was used as the plating bath
[0201] Copper sulfate: 75 g/L
[0202] Sulfuric acid: 190 g/L
[0203] Brightener: proper amount
[0204] Chlorine ion: 40 mL/L
[0205] In the plating tank
[0206] The vibrating motor
[0207] The plating current of rectangular waveform was supplied by the power source circuit
[0208] When the treatment was carried out for 2.5 hours, it was found on the basis of the current flowing test, microscopy and other tests that copper plating films having a uniform thickness of about 7 μm were formed in all the inner surfaces of the blind via holes.
[0209] The same treatment as Example 7, except for the condition: T
[0210] The same treatment as Example 7, except that a high frequency vibrating motor was used as the vibrating motor
[0211] It was proved from the current flowing test, microscopy and other tests that the copper plating films having a uniform thickness of about 7 μm were formed in all the inner surfaces of the blind via holes.
[0212] An epoxy resin plate for wiring board was used as the plating target article X, on the surface of which many blind via holes each having an inner diameter of 15 μm and a depth of 40 μm were formed.
[0213] As the pre-treatment for the electroplating treatment, degreasing water washing-etching-water washing-neutralizing-water washing-catalyst-water washing-accelarator-water washing-electroless copper plating were conducted to make the plating target article X electically conductive. Furthermore, water washing-activating-water washing strike plating were conducted. In the electroless copper plating and strike plating, the vibrational flow was generated in the plating treatment liquid by means of the same vibrational flow generator as described with reference to FIGS.
[0214] The electroplating treatment was carried out in the same manner as Example 7, except that the swinging motor
[0215] The plating current of rectangular waveform was supplied by the power source circuit
[0216] When the treatment was carried out for 1 hour, it was found on the basis of the current flowing test, microscopy and other tests that copper plating films were excellently formed and embedded in all the blind via holes.
[0217] The same treatment as Example 9, except for the condition: T