US20110056838A1

US20110056838A1 - Method of manufacturing printed wiring board

Info

Publication number: US20110056838A1
Application number: US12/862,331
Authority: US
Inventors: Satoru Kawai
Original assignee: Ibiden Co Ltd
Current assignee: Ibiden Co Ltd
Priority date: 2009-09-04
Filing date: 2010-08-24
Publication date: 2011-03-10
Also published as: TW201132263A; JP2011058093A; CN102014589A; KR20110025612A

Abstract

A printed wiring board is manufactured by a method in which an opening is formed in a substrate, and a seed layer for electrolytic plating is formed on an inner wall of the opening and a surface of the substrate. The substrate with the seed layer is placed in an electrolytic plating solution, and an insulative body is placed in the electrolytic plating solution. The substrate and the insulative body are moved relative to each other to form an electrolytic plated film on the substrate and fill the opening with the electrolytic plated film. A conductive circuit is formed on the substrate. The electrolytic plating solution includes copper sulfate, sulfuric acid, and iron ions.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims the benefit of priority to U.S. Provisional Patent Application No. 61/239,995, filed Sep. 4, 2009, the contents of which are incorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

In connection with methods for manufacturing a printed wiring board, International Publication WO 2006/033315A1 discloses a method for filling penetrating holes and non-penetrating holes with an electrolytic plated film while an insulative body is in contact with the surface to be plated.

BRIEF SUMMARY OF THE INVENTION

In a method for manufacturing a printed wiring board according to one embodiment of the present invention, an opening is formed in a substrate, and a seed layer for electrolytic plating is formed on an inner wall of the opening and a surface of the substrate. The substrate with the seed layer is placed in an electrolytic plating solution, and an insulative body is placed in the electrolytic plating solution. The substrate and the insulative body are moved relative to each other to form an electrolytic plated film on the substrate and fill the opening with the electrolytic plated film. A conductive circuit is formed on the substrate. The electrolytic plating solution includes copper sulfate, sulfuric acid, and iron ions.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:

FIGS. 1A-1E are cross-sectional views showing the steps of a method for manufacturing a multilayer printed wiring board according to one embodiment of the invention.

FIGS. 2A-2E are cross-sectional views showing the steps of a method for manufacturing a multilayer printed wiring board according to one embodiment of the invention.

FIGS. 3A-3D are cross-sectional views showing the steps of a method for manufacturing a multilayer printed wiring board according to one embodiment of the invention.

FIGS. 4A-4C are cross-sectional views showing the steps of a method for manufacturing a multilayer printed wiring board according to one embodiment of the invention.

FIGS. 5A and 5B are cross-sectional views showing the steps of a method for manufacturing a multilayer printed wiring board according to one embodiment of the invention.

FIG. 6 is a cross-sectional view of a multilayer printed wiring board produced by a manufacturing method according to one embodiment of the invention.

FIGS. 7A-7D are cross-sectional views showing the steps of a method for manufacturing a multilayer printed wiring board according to one embodiment of the invention.

FIGS. 8A-8F are cross-sectional views showing the steps of a method for manufacturing a printed wiring board according to one embodiment of the invention.

FIG. 9 is a perspective view schematically showing the structure of a plating apparatus used in a method for manufacturing a printed wiring board according to one embodiment of the invention.

FIG. 10 is a schematic illustration showing the structure of a conveyor mechanism in a plating tank of a plating apparatus used in a method for manufacturing a printed wiring board according to one embodiment of the invention.

FIG. 11 is a schematic illustration showing the structure of a conveyor mechanism in a plating tank of a plating apparatus used in a method for manufacturing a printed wiring board according to one embodiment of the invention.

FIGS. 12A-12E are cross-sectional views showing the steps of a method for manufacturing a multilayer printed wiring board according to one embodiment of the invention.

FIGS. 13A-13F are cross-sectional views showing the steps of a method for manufacturing a multilayer printed wiring board according to one embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The embodiments will now be described with reference to the accompanying drawings, wherein like reference numerals designate corresponding or identical elements throughout the various drawings.

First Embodiment

A plating apparatus used in a method for manufacturing a printed wiring board according to First Embodiment of the present invention is described with reference to FIG. 9. A plating apparatus 10 includes a plating tank 14, a circulation device 16, insulative bodies (20A, 20B), elevator bars 22, and an elevator device 24. The plating tank 14 is filled with a plating solution 12. The circulation device 16 circulates the plating solution 12. The insulative body (20A) is comprised of a porous material such as a porous resin (e.g., sponge). For plating surfaces of a printed wiring board 30, the insulative body (20A) is placed in the plating solution 12 and brought into contact with one of the surfaces to be plated, e.g., a front surface of the printed wiring board 30. The insulative body (20B) is comprised of a porous material such as a porous resin (e.g., sponge). For plating the surface of a printed wiring board 30, the insulative body (20B) is placed in the plating solution 12 and brought into contact with the other surface to be plated (e.g., a back surface) of the printed wiring board 30. The elevator device 24 vertically moves the insulative bodies (20A, 20B) along the printed wiring board 30. The insulative bodies (20A, 20B) are moved by the elevator bars 22 which move vertically by means of the elevator device 24. The printed wiring board 30 is connected to a cathode side. Inside the plating tank 14, an anode not shown in the drawing is provided, and metal sources such as copper balls are stored in the anode. The plating solution 12 contains, e.g., copper sulfate, sulfuric acid and iron ions. The plating solution 12 before the plating is started contains iron(III) ions. As the plating proceeds, iron(II) ions are produced, and thus iron(II) and iron(III) ions exist in the plating solution 12. As for the iron-ion source, iron(II) sulfate is preferred. Hydrates are preferred as iron sulfate; iron sulfate 7-hydrate (FeSO₄.7H₂O) is preferred. By performing dummy plating, the concentration of Fe²⁺ and the concentration of Fe³⁺ can be adjusted.
With reference to FIGS. 13A-13F, the following describes a method that uses the plating apparatus 10 to form an electrolytic plated film for a printed wiring board (substrate) 30. Openings (31 a, 31 b) are formed in the substrate 30 having a first surface (30A) and a second surface (30B) opposite the first surface (30A) (FIG. 13A). The openings (31 a, 31 b) include penetrating holes for through-hole conductors (through-hole conductor openings) and via holes. In this example, the opening (31 a) is a penetrating hole and the opening (31 b) is a non-penetrating hole (via-conductor opening). A seed layer 34 is formed on the first and second surfaces (30A, 30B) of the substrate 30 and the inner walls of the openings (31 a, 31 b) (FIG. 13B). As examples of a seed layer, an electroless plated film, a sputtered film and a vapor-deposited film can be listed. Alternatively, by providing conductive particles such as Pd or C on the inner walls of the through holes and the substrate surfaces, an electrolytic plated film can be formed directly on the substrate surfaces and the inner walls of the openings (31 a, 31 b). In such a case, conductive particles work as a seed layer. The seed layer 34 in this example is an electroless copper-plated film. The substrate 30 with the seed layer 34 is placed in the plating solution 12 to form an electrolytic plated film 36. An example of the composition of the plating solution 12 and the plating conditions are below.


<Composition of Plating Solution 12>

Copper sulfate concentration:	0.8 ± 0.1 mol/L
Sulfuric acid concentration:	0.5 ± 0.15 mol/L
Chloride-ion concentration:	5-100 ppm
Iron-ion concentration:	1 g/L-20 g/L

The iron-ion concentration is the total value of those of iron(II) ions and

iron(III) ions.

The concentration of iron(II) ions:concentration of iron(III) ions = 1:2-1:4

Additive concentration:	5 ± 1 mol/L


<Plating Conditions>

	Current density:	0.5-5 A/dm²

The insulative body (20A) is pressed against the first surface (30A) of the substrate 30, and the insulative body (20B) is pressed against the second surface (30B) of the substrate 30 (FIG. 13C). When the insulative bodies (20A, 20B) contact the substrate 30, the insulative bodies (20A, 20B) are preferably pushed further by, for example, 1.0-15.0 mm into the substrate surfaces after they come in contact with the substrate surfaces (surfaces to be plated). If the amount to be pushed is less than 1.0 mm, the result tends to be the same as plating without using the insulative bodies (20A, 20B). If the amount to be pushed exceeds 15.0 mm, the thickness of the plated film in the openings (31 a, 31 b) tends to vary, since the supply of the plating solution 12 will be hampered. The amount to be pushed is most preferably 2-8 mm. The variation in the plated film on the substrate surfaces and in the openings (31 a, 31 b) will be less. Also, the thickness of the electrolytic plated film formed on the substrate surfaces will be reduced.
While the insulative bodies (20A, 20B) are in contact with the substrate 30, the substrate 30 and the insulative bodies (20A, 20B) move relative to each other (FIG. 13C)). The moving speed of the insulative bodies (20A, 20B) relative to the substrate 30 is preferably 1.0-16.0 m/min. Within such a range, iron ions can be appropriately fed onto the substrate surfaces. As a result, the film thickness of the electrolytic plated film 36 formed on the substrate surfaces can be reduced. In addition, since the plating solution 12 can be fed into the openings (31 a, 31 b) by the insulative bodies (20A, 20B), plating can be filled in the openings (31 a, 31 b).
In the present embodiment, the substrate 30 with seed layers 34 (see FIG. 13B) is placed in the plating solution 12 described above. Then, the insulative bodies (20A, 20B) are pressed against the substrate 30. While the insulative bodies (20A, 20B) are pressed against the substrate 30, the insulative bodies (20A, 20B) and the substrate 30 move relative to each other. While such conditions are sustained, the electrolytic plated film 36 is formed on the surfaces of the substrate 30 and in the openings (31 a, 31 b) (FIG. 13C).
In the embodiment, while the insulative bodies (20A, 20B) are in contact with the substrate 30 in an electrolytic plating solution containing iron ions, the electrolytic plated film 36 is formed on the surfaces of the substrate 30 and in the openings (31 a, 31 b) of the substrate 30. Accordingly, iron(III) ions can be readily fed onto the substrate surfaces that are to be plated. Without wishing to be bound by any theory, it is thought that the following reaction occurs on the surfaces of plated films.
2Fe³⁺+Cu
2Fe²⁺+Cu²⁺ Reaction Formula (1)
If the above reaction occurs, it is thought that deposition and dissolution of the plated film will occur in areas with which the insulative bodies (20A, 20B) are in contact. It is thought that the growth speed of the plated film on the substrate surfaces will slow down. By contrast, since the plated film in the openings (31 a, 31 b) does not make contact with the insulative bodies (20A, 20B) at the initial point of plating, it is thought that the growth of the electrolytic plated film 36 in the openings (31 a, 31 b) will seldom be suppressed by the iron ions. Since iron(III) ions are diffused into the openings (31 a, 31 b) through the concentration gradient, the concentration of iron(III) ions is thought to be low. Thus, in the embodiment, it is thought that the openings (31 a, 31 b) (including penetrating holes and non-penetrating holes (via holes)) can be filled with the electrolytic plated film 36 while the thickness of the electrolytic plated film 36 on the substrate surfaces is relatively small. When the electrolytic plated film 36 in the openings (31 a, 31 b) gradually thickens, the insulative bodies (20A, 20B) come in contact with the surface of the electrolytic plated film 36 that fills the openings (31 a, 31 b). When being in contact with the insulative bodies (20A, 20B), the electrolytic plated film 36 filling the openings (31 a, 31 b) and the electrolytic plated film 36 on the substrate surfaces have growth speeds that are thought to become the same. Accordingly, the electrolytic plated films 36 obtained in the present embodiment are thought to be uniform and thin.
Without wishing to be bound by any theory, an alternative mechanism may be possible in which plating is suppressed from deposition through the following reaction.
Fe³⁺+Cu²⁺+3e ⁻
Fe²⁺+Cu Reaction Formula (2)
In Reaction Formula (2), since electrons for depositing copper-plated film are used to reduce iron(III) ions into iron(II) ions, it is thought that the growth of the plated film is suppressed. In Reaction Formula (2), for the same reason as in Reaction Formula (1), it is thought that plating is filled in the openings (31 a, 31 b), while the thickness of the plated film on the substrate surfaces remains relatively small.
The above reactions (Reaction Formula (1) and Reaction Formula (2)) could occur as well with ions other than iron ions. However, in the embodiment, since it is thought that iron ions are forcibly fed onto the plated-film surface using the insulative bodies (20A, 20B), iron is considered to be preferred as the metal ions added to the plating solution 12. That may be because ionization tendencies of iron and copper are similar. Compared with conventional technology, the method for forming a plated film on the substrate surfaces and in the openings (31 a, 31 b) of the substrate 30 while insulative bodies (20A, 20B) are in contact with the substrate 30 in an electrolytic plating solution containing iron ions is excellent in forming fine wiring, for example. When an electrolytic plated film is formed on a substrate with openings using the embodiment of the present invention and conventional technology, the thickness of electrolytic plated film (the thickness of the plated film formed on the substrate) obtained using the embodiment of the present invention is approximately one-half to one-third of the thickness of the electrolytic plated film (the thickness of the plated film formed on the substrate) obtained using conventional technology. Openings can be filled with plated film in the embodiment of the present invention the same as in conventional technology.
By using the plating method of the embodiment, the openings (31 a, 31 b) can be filled with plating, and the surface of the plated film exposed through the openings (31 a, 31 b) tend to be flat (see FIGS. 13D and 13E). Moreover, the top surface of the plated film exposed through the openings and the top surface of the plated film formed on a substrate surface may be positioned on the same level, and the electrolytic plated film 36 on the substrate surfaces can be formed thinly. According to the plating method of the present embodiment, filling deep openings with plated film and reducing the thickness of the plated film formed on the substrate surfaces can be achieved at the same time. After that, by patterning the thin electrolytic plated film 36 and the seed layer 34 on the substrate surfaces, fine-pitch conductive circuits can be formed (FIG. 13F). At the same time, through-hole conductors 42, via conductors 60 and conductive circuits 58 are completed.
Furthermore, if the insulative bodies (20A, 20B) comprised of a porous resin (e.g., sponge) or a brush are used, iron(III) ions tend to be fed onto the surfaces that are to be plated. This may be because the plating solution 12 is easily fed onto the substrate surfaces through the pores of the porous resin or the spaces between the bristles of the brush. The plated film formed on the substrate surfaces tends to be thin.
In areas with which the insulative bodies (20A, 20B) are in contact, the growth of the electrolytic plated film 36 slows down. Namely, iron ions are forcibly fed by the insulative bodies (20A, 20B) onto plating interfaces, a reaction to reduce iron(III) ions to iron(II) ions occurs, and deposition of copper is suppressed. In the penetrating holes (31 a) with which the insulative bodies (20A, 20B) are not in contact, iron(III) ions are not fed forcibly, but are only diffused by the concentration gradient onto plating interfaces, the degree of reduction reaction of iron(III) ions is low, and the electrolytic plated film 36 grows. Accordingly, the electrolytic plated film 36 on the surface of a core substrate can be formed thinly, while the through-hole conductor 42 is filled.
According to the embodiment of the present invention, not only can the openings be filled with electrolytic plated film, but the electrolytic plated film formed on the substrate surfaces can remain thin. Therefore, the embodiment of the present invention is applicable especially to the procedure for forming an electrolytic plated film by methods (such as the subtractive method and tenting method) where the electrolytic plated film is formed on the entire substrate surfaces, and conductive circuits are formed by etching. Since fine-pitch conductive circuits can be formed, applying the embodiment of the present invention is advantageous for making a highly integrated board.
<Manufacturing Method 1>
A method for manufacturing a multilayer printed wiring board (Manufacturing Method 1) is described with reference to FIGS. 1A-6.
FIG. 6 is a cross-sectional view of a multilayer printed wiring board 100. The multilayer printed wiring board 100 has a core substrate 30, conductive circuits 40, through-hole conductors 42, and interlayer resin insulation layers (50, 150). The core substrate 30 has a first surface (top surface in FIG. 6) and a second surface (bottom surface in FIG. 6) opposite the first surface. The conductive circuits 40 are provided on the first and second surfaces of the core substrate 30. The conductive circuits 40 are connected by the through-hole conductors 42. Formed on the core substrate 30 and the conductive circuits 40 are the interlayer resin insulation layers 50, where via conductors 60 and conductive circuits 58 are formed. The interlayer resin insulation layers 150, where via conductors 160 and conductive circuits 158 are formed, are formed on the interlayer resin insulation layers 50. A solder-resist layer 70 with opening portions 71 is formed on the via conductors 160, conductive circuits 158 and interlayer resin insulation layer 150. Bumps (76U, 76D) are formed on the via conductors 160 and conductive circuits 158 exposed through the opening portions 71 in the solder-resist layer 70.
In the following, the steps for manufacturing the multilayer printed wiring board 100 shown in FIG. 6 are described with reference to FIGS. 1A-5B.
A double-sided copper-clad laminate with a thickness of, for example, 0.8 mm is prepared (FIG. 1A). The core substrate (insulative substrate) 30 of the double-sided copper-clad laminate is made of a glass-epoxy resin or a BT (bismaleimide triazine) resin and a core material such as glass cloth. On the first surface of the core substrate 30 and on the second surface opposite the first surface, copper foils (130A, 130B) are laminated. Penetrating holes 32 for through-hole conductors are formed in the double-sided copper-clad laminate using a drill or a laser (FIG. 1B).
Catalyst nuclei are attached to the surfaces of the double-sided copper-clad laminate and the inner-wall surfaces of the penetrating holes 32 for through-hole conductors (not shown in the drawings). The core substrate 30 with the attached catalyst is immersed in a commercially available electroless copper plating solution (such as THRU-CUP made by C. Uyemura Co., Ltd.) to form an electroless copper-plated film 34 with a thickness of 0.3-3.0 μm on the substrate surfaces and inner walls of the penetrating holes 32 (FIG. 1C).
After being cleansed with 50° C. water to degrease, washed with 25° C. water, and further cleansed with sulfuric acid, the core substrate 30 is immersed in an electrolytic copper plating solution 12 with the following composition. After that, by using the plating apparatus 10 described above with reference to FIG. 9, an electrolytic plated film 36 is formed on both surfaces of the copper-clad laminate and in the penetrating holes under the following conditions (FIG. 1D).


<Composition of Electrolytic Plating Solution 12>

Sulfuric acid	0.5	mol/L
Copper sulfate	0.8	mol/L
Iron sulfate 7-hydrate	5	g/L
(FeSO₄•7H₂O)
Leveling agent	50	mg/L
Polishing agent
50	mg/L

	Fe²⁺:Fe³⁺	1:2-1:4


<Electrolytic Plating Conditions>

	Current density	1 A/dm²
	Time	65 minutes
	Temperature
	22 ± 2° C.

Here, as described above with reference to FIG. 9, the insulative bodies (20A, 20B), using a porous resin, are vertically moved along the surfaces that are to be plated, and the electrolytic copper-plated film 36 is formed on the core substrate 30 while penetrating holes 32 are filled with plating. The penetrating holes 32 are filled with the electrolytic copper-plated film 36. During that time, the moving speed of the insulative bodies (20A, 20B) is 7 m/min., the size of the insulative bodies (20A, 20B) relative to that of the core substrate is 0.80, and the amount that the insulative bodies (20A, 20B) are to be pushed is 8 mm.
Thereafter, an etching resist 38 with a predetermined pattern is formed on the electrolytic plated films 36 (FIG. 1E).
The electrolytic plated film 36, the electroless plated film 34 and the copper foils (130A, 130B) left exposed by the etching resists 38 are removed by etching, and the through-hole conductors 40 and conductive circuits 42 are formed (FIG. 2A).
A roughened surface (40 a) is formed on the entire surfaces of the conductive circuits 40 and the top surfaces of the through-hole conductors 42 (FIG. 2B).
<Forming Built-Up Layers>
On both surfaces of the core substrate 30, a resin film (brand name: ABF-45SH, made by Ajinomoto Fine-Techno Co., Inc.) for interlayer resin insulation layers is laminated. Then, by curing the resin film for interlayer resin insulation layers, the interlayer resin insulation layer 50 is formed on both surfaces of the core substrate 30 (FIG. 2C).
By using a CO₂gas laser, via-conductor openings (50 a) with a diameter of 80 μm are formed in the interlayer resin insulation layers 50 (FIG. 2D).
The substrate 30 with the via-conductor openings (50 a) is immersed for 10 minutes in an 80° C. solution containing 60 g/L of permanganic acid, and the roughened surface (50α) is formed on the surfaces of the interlayer resin insulation layers 50 including the inner walls of the via-conductor openings (50 a) (FIG. 2E).
The substrate 30 is immersed in a neutralizing solution (made by Shipley Company) and then washed with water. Furthermore, catalyst nuclei (not shown in the drawings) are attached to the surfaces of interlayer resin insulation layers 50 and the inner-wall surfaces of via-conductor openings (50 a).
The substrate 30 with attached catalyst is immersed in a commercially available electroless copper plating solution to form an electroless copper-plated film 52 with a thickness of 0.3-3.0 μm on the surfaces of the interlayer resin insulation layers 50 and the inner walls of the via-conductor openings (50 a) (FIG. 3A).
After being cleansed with 50° C. water to degrease, washed with 25° C. water, and further cleansed with sulfuric acid, the substrate 30 with the interlayer resin insulation layers 50 is immersed in the electrolytic copper plating solution 12 having the same composition as above. Using the plating apparatus 10 described above with reference to FIG. 9, under the conditions described above, an electrolytic copper-plated film 56 is formed on the interlayer resin insulation layers 50 and in via-conductor openings (50 a) (FIG. 3B). The via-conductor openings (50 a) are filled with the electrolytic copper-plated film 56.
Here, as described above with reference to FIG. 9, while the insulative bodies (20A, 20B) using a porous resin are vertically moved along the surfaces that are to be plated, plating is filled in the openings (50 a) and the electrolytic copper-plated film 56 with a thickness of 12 μm is also formed on the surfaces of the interlayer resin insulation layers 50. The moving speed of the insulative bodies (20A, 20B) is 7 m/min., the size of the insulative bodies (20A, 20B) relative to that of the core substrate 30 is 0.80, and the amount that the insulative bodies (20A, 20B) are to be pushed is 8 mm.
Thereafter, an etching resist 54 is formed on electroless copper-plated films 56 (FIG. 3C). The electrolytic plated film 56 and electroless plated-film 52 left exposed by the etching resists 54 are removed by etching. Then, by removing the etching resists 54, independent upper-layer conductive circuits 58 and filled vias 60 are formed (FIG. 3D). Roughened surfaces (58α, 60α) are formed on the surfaces of upper-layer conductive circuits 58 and filled vias 60 (FIG. 4A).
By repeating the above steps described with reference to FIGS. 2B-4A, further upper-layer interlayer insulation layers 150, conductive circuits 158 and filled vias 160 are formed, and a multilayer wiring board 300 is obtained (FIG. 4B).
A commercially available solder-resist composition (such as SR 7200 made by Hitachi Chemical Co., Ltd.) 70 is applied on both surfaces of the multilayer wiring board 300 to be 20 μm thick (FIG. 4C), on which a dry treatment is conducted at 70° C. for 20 minutes and at 70° C. for 30 minutes. After that, through exposure and development treatments, openings 71 to expose conductive circuits and filled vias are formed in solder-resist composition (FIG. 5A). Then, by conducting heat treatments under the conditions of 80° C. for an hour, 100° C. for an hour, 120° C. for an hour and 150° C. for three hours respectively, the solder-resist composition is cured, and the solder-resist layer 70 with openings to expose conductive circuits and filled vias is formed on interlayer resin insulation layers. The top surfaces of the conductive circuits and filled vias exposed through the openings in the solder-resist layers work as pads for mounting electronic components and pins.
A nickel layer, a palladium layer and a gold layer are formed in that order on the pads exposed through the openings in the solder-resist layer 70. After that, solder balls are supplied onto the pads and then reflowed. Accordingly solder bumps (solder bodies) (76U, 76D) are formed on the pads. The multilayer printed wiring board 100 having the solder bumps (76U, 76D) is completed (FIG. 6).
<Manufacturing Method 2>
In the following, the manufacturing steps according to Manufacturing Method 2 are described with reference to FIGS. 7A-7D. As illustrated in FIG. 7B, a plating resist 54 is formed on an intermediate substrate which is in the state shown in FIG. 3A. This is different from Method 1 described above with reference to FIGS. 3A-3D where an electrolytic plated film 56 is formed on the entire surface of an electroless plated film 53.
After being cleansed with 50° C. water to degrease, washed with 25° C. water and further cleansed with sulfuric acid, the substrate 30 is immersed in an electrolytic copper plating solution 12 having the same composition described in Method 1. An electrolytic copper-plated film 56 is formed on interlayer resin insulation layers 50 and in the via-conductor openings under the same conditions as above, and via-conductor openings are filled with the electrolytic copper-plated film 56 (FIG. 7C).
Here, as described above with reference to FIG. 9, insulative bodies (20A, 20B) using a porous resin are vertically moved along the surfaces that are to be plated, and the electrolytic copper-plated film 56 is formed on the interlayer resin insulation layers 50 and in the via-conductor openings, while the via-conductor openings are filled with plating. The via-conductor openings are filled with the electrolytic copper-plated film 56. The moving speed of the insulative bodies (20A, 20B) is 7 m/min., the size of the insulative bodies (20A, 20B) relative to that of the core substrate 30 is 0.80, and the amount that the insulative bodies (20A, 20B) are to be pushed is 8 mm.
Plating resists 54 are removed using a 5% KOH solution. After that, by removing the electroless plated film 52 that are not covered by the electrolytic plated film 56, independent upper-layer conductive circuits 58 and filled vias 60 are formed (FIG. 7D). Since the subsequent steps are the same as in Manufacturing Method 1, their descriptions are omitted.
<Manufacturing Method 3>
In the following, the manufacturing steps according to Manufacturing Method 3 are described with reference to FIGS. 8A-8F. This method is an example relating to a method for manufacturing a printed wiring board having hourglass-shaped through-hole conductors. Here, an hourglass-shaped through-hole conductor indicates a through-hole conductor made by filling plating in a penetrating hole which is made up of a first opening tapering from the first surface of core substrate 30 toward the second surface, and of a second opening tapering from the second surface toward the first surface.
A double-sided copper-clad laminate (30C) is prepared, made by laminating copper foils (130A, 130B) on both surfaces of the core substrate 30. The core substrate 30 has a first surface and a second surface opposite the first surface. Copper foil (130A) is formed on the first surface of the core substrate 30 and the copper foil (130B) is formed on the second surface of the core substrate 30 (FIG. 8A).
CO₂laser is applied from the first-surface side of the core substrate 30. A first opening (136A) is formed, penetrating the copper foil (130A) and tapering from the first surface of the core substrate 30 toward the second surface (FIG. 8B). Tapering from the first surface toward the second surface has the diameter of the first opening (136A) gradually becoming smaller from the first surface toward the second surface. Regarding the diameter of the first opening (136A), when the first opening (136A) is sliced by a plane parallel to the first surface, the distance across the cross section is the diameter if the first opening (136A) is a circle, and the major axis if it is an oval.
Then, CO₂laser is applied from the second-surface side of the core substrate 30. The position to be irradiated by a laser is opposite the first opening (136A). A second opening (136B) is formed, penetrating the copper foil (130B) and tapering from the second surface of the core substrate 30 toward the first surface. By forming the second opening (136B), the first and second openings (136A, 136B) are joined inside the core substrate 30, and a penetrating hole 136 comprised of the first and second openings (136A, 136B) is formed in the core substrate 30 (FIG. 8C). Tapering from the second surface toward the first surface has the diameter of the second opening (136B) gradually becoming smaller from the second surface toward the first surface. Regarding the diameter of the second opening, when the second opening is sliced by a plane parallel to the first surface, the distance across the cross section is the diameter if the second opening is a circle, and the major axis if it is an oval.
A seed layer 137 made of a sputtered film is formed on the surfaces of the copper foils (130A, 130B) and the inner walls of the penetrating hole 136. The seed layers 137 are made of copper. Since the first and second openings (136A, 136B) are tapered, the seed layers 137 are easily formed by sputtering. However, the seed layers 137 can be formed by electroless plating.
An electrolytic copper-plated film 134 is formed on the first and second surfaces of the core substrate 39 using the same plating apparatus 10, plating solution 12, plating method and plating conditions as described in Manufacturing Method 1. During that time, penetrating hole 136 is filled with an electrolytic copper-plated film 134 (FIG. 8E). While the penetrating hole 32 in Manufacturing Method 1 is in a substantially straight shape, the penetrating hole 136 in this Manufacturing Method 3 is in an hourglass shape. When forming a penetrating hole in the same core substrate to have the same diameter (the diameter on the front and back surfaces of the core substrate), the volume of an hourglass-shaped penetrating hole is smaller than the volume of a straight-shaped penetrating hole. Due to such a difference, the thickness of the electrolytic plated film on the core substrate in Manufacturing Method 3 tends to be thinner than the thickness of the electrolytic plated film on the substrate in Manufacturing Method 1. As such, fine conductive circuits can be formed by Manufacturing Method 3.
In the same manner as in Manufacturing Method 1, an etching resist is formed on electrolytic copper-plated films 134. After that, the electrolytic plated film 134, sputtered film 137 and copper foils (30A, 30B) left exposed by the etching resists are dissolved and removed. Accordingly, independent conductive circuits (134A) and through-hole conductors 142 are formed (FIG. 8E). Then, built-up layers may be formed on the core substrate in the same manner as in Manufacturing Method 1.

Second Embodiment

A plating apparatus used in a method for manufacturing a printed wiring board according to Second Embodiment of the present invention is described with reference to FIGS. 10 and 11.
FIG. 11 is a schematic illustration showing a side view of a plating apparatus 210, and FIG. 10 is a schematic illustration showing a structure of the conveyor mechanism positioned on one side of the plating tank in the plating apparatus 210. The plating apparatus 210 performs plating on a strip-type substrate for flexible printed wiring boards. In this plating apparatus 210, electrolytic plating is conducted on one surface of a strip substrate (230A) pulled from a reel (298A) on which a 180 mm-wide and 120 m-long strip substrate is wound. Then, the strip-type substrate (230A) will be wound onto a reel (298B). The plating apparatus 210 has insulative cylindrical contact bodies 220 making contact with the surface of the strip substrate (230A) to be plated, a back board 228 to prevent strip substrate (230A) from warping caused by the contact body (insulative body) 220, and an anode 204. In the anode 204, copper balls 206 are accommodated to supplement copper ingredients in the plating solution. A plating tank 212 is a total of 20 m long. Instead of an insulative material for the contact body 220, a semiconductor contact body can also be used. The contact body 220 in Second Embodiment has substantially the same function as that of the insulative bodies (20A, 20B) described in First Embodiment.
The contact body 220 is formed with a cylindrical brush made of PVC (polyvinyl chloride) with a height of 200 mm and a diameter of 100 mm. In the contact body 220, the tip of the brush makes contact with a printed wiring board and bends. The contact body 220 is supported by a support bar (220A) made of stainless steel and is rotated by a gear which is not shown in the drawing.
Forming filled vias and conductive circuits using the plating apparatus 210 is described with reference to FIGS. 12A-12E. FIG. 12A shows a double-sided copper-clad flexible substrate comprised of a substrate 230 and copper foils (33U, 33D). A commercially available dry film is laminated on one surface of the substrate 230, and the copper foil (33U) is etched away using a known photographic method from areas where via-conductor openings 37 will be formed. Using the copper foil (33U) as a mask, via-conductor openings 37 are formed by a carbon-dioxide gas laser (see FIG. 12B). An electroless plated film 34 is formed on the copper foil (33U) and the inner walls of the via-conductor openings 37 (FIG. 12C), and then an electrolytic plated film 36 is formed using the plating apparatus 210 shown in FIG. 10 (FIG. 12D). The plated film 36 is formed while part of the contact body 220 is in contact with at least part of the surface of the printed wiring board. The contact body 220 makes contact with the electroless plated film 34 on the printed wiring board at the initial point of electroplating, and comes in contact with the electrolytic plated film 36 once the electrolytic plated film 36 is formed.
According to Second Embodiment, the plating solution 12 contains copper sulfate, sulfuric acid and iron ions, as in First Embodiment. Since the plating solution 12 contains iron(III) ions, the thickness of the electrolytic plated film 36 formed on substrate surfaces is smaller, compared with that obtained by using plating solutions that do not contain iron(III) ions at a high concentration. In addition, since the plated film 36 is formed using the contact body 220, via-conductor openings can be filled with the electrolytic plated film 36.
The size of a contact body is preferably the same as or greater than the area to be plated on the strip substrate. The amount that a contact body is to be pushed into a printed wiring board (after the tip of a contact body comes in contact with a surface of the printed wiring board, the amount of the tip to be further pushed) is preferably 1.0-15.0 mm into the surface. If the amount is less than 1.0 mm, the result may be the same as that of a plating method without using a contact body. If the amount exceeds 15.0 mm, it is thought that feeding iron(III) ions onto the substrate surface will become difficult. Also, the contact body tends to enter via-conductor openings and through-hole conductor openings, and thus the concentration of iron(III) ions in the openings is thought to rise. The amount to be pushed is preferably 2-8 mm. That is because variations in plated film may seldom occur.
As for a contact body, one selected from among flexible brushes and spatulas can be preferably used. Being flexible, a contact body follows the irregularities on a substrate and can form a plated film with a uniform thickness on the irregular surface.
A resin brush can be used as a contact body. In such a case, the bristle tips make contact with a surface to be plated. Here, the diameter of the bristle is preferably greater than the diameter of an opening, because the bristle tips will not enter the openings and plated film can be filled appropriately in the openings. As for a resin brush, PP, PVC (polyvinyl chloride), PTFE (polytetrafluoroethylene) or the like having tolerance to plating solutions can be used. Also, resin and rubber can be used. Furthermore, as for a bristle tip, resin fabric such as vinyl-chloride woven fabric or non-woven fabric can also be used.
<Manufacturing Method 4>
A method for manufacturing a printed wiring board using a plating apparatus according to Second Embodiment (using, e.g., subtractive method, tenting method) is described with reference to FIGS. 12A-12E. The method is referred to as Manufacturing Method 4 below.
A laminated strip-type substrate (230A) is prepared as a starting material, in which 9 μm copper foil (33U) is laminated on a front surface (first surface) of 25 μm-thick polyimide strip substrate 230, and 12 μm copper foil (33D) is laminated on a back surface (second surface) (FIG. 12A). The copper foil on the second surface is covered with a resist. The thickness of 9 μm copper foil (33U) on the front surface is adjusted by light etching to be 7 μm. After that, a black-oxide treatment is conducted on the copper foil on the first surface. By irradiating a laser from the first-surface side, via-conductor openings 37 are formed which penetrate copper foil (33U) and polyimide strip substrate 30, and reach the back surface of copper foil (33D) (FIG. 12B). Then, a palladium catalyst is attached to the surface of strip substrate (230A) (not shown in the drawing).
The substrate with attached catalyst is immersed in an electroless plating solution (Thru-Cup) made by C. Uyemura Co., Ltd. and 1.0 μm-thick electroless plated film (seed layer) 34 is formed on the first surface of strip substrate (230A) (FIG. 12C).
After being cleansed with 50° C. water to degrease, washed with 25° C. water, and further cleansed with sulfuric acid, the strip substrate (230A) is immersed in a plating tank containing an electrolytic copper plating solution with the following composition. Using plating apparatus 210 described above with reference to FIG. 10, the electrolytic plated film 36 is formed on the seed layer 34 under the following conditions (FIG. 12D).


<Composition of Electrolytic Plating Solution>

Sulfuric acid	0.5	mol/L
Copper sulfate	0.8	mol/L
Iron sulfate 7-hydrate	100	g/L
(FeSO₄•7H₂O)
Leveling agent	50	mg/L
Polishing agent
50	mg/L

	Fe²⁺:Fe³⁺	1:2-1:4


<Electrolytic Plating Conditions>

	Current density	5.0-30 mA/cm²
	Time	10-90 minutes
	Temperature
	22 ± 2° C.

Here, the current density is preferably set at 5.0-30 mA/cm², especially at 10 mA/cm²or greater. Then, by forming a resist with a predetermined pattern on both surfaces of the strip substrate and conducting etching, conductive circuits (42U) and conductive circuits (42D) are formed (FIG. 12E). This is a so-called subtractive method or a tenting method.
<Manufacturing Method 5>
The composition of the electrolytic plating solution in Manufacturing Method 3 is changed to the following composition. The rest is the same as in Manufacturing Method 3.


<Composition of Electrolytic Plating Solution>

Sulfuric acid	0.5	mol/L
Copper sulfate	0.8	mol/L
Iron sulfate 7-hydrate	50	g/L
(FeSO₄•7H₂O)
Leveling agent	50	mg/L
Polishing agent
50	mg/L

	Fe²⁺:Fe³⁺	1:2-1:4

<Manufacturing Method 6>
The composition of the electrolytic plating solution in Manufacturing Method 3 is changed to the following composition. The rest is the same as in Manufacturing Method 3.


<Composition of Electrolytic Plating Solution>

	Fe²⁺:Fe³⁺	1:2-1:4

When Manufacturing Methods 5 and 6 are compared, the plated film exposed through the openings tends to be recessed in Manufacturing Method 6. This is assumed to be because plating growth inside the openings is slow due to a larger amount of iron(III) ions in Manufacturing Method 6. If a concentration of iron ions is 1 g/L-10 g/L, the plated film exposed through the openings will show a higher flatness feature. Thus, an interlayer resin insulation layer may be easily formed on the plated film. The iron ions in the plating solution are iron(II) ions and iron(III) ions. If the ratio of the concentration of iron(II) ions and that of iron(III) ions in an electrolytic plating solution is in the range of 1:2-1:4, plated film will be effectively suppressed from being deposited on a substrate surface. Filling the openings and reducing the film thickness of the plated film on a substrate surface may both tend to be achieved. Iron sulfate 7-hydrate (FeSO₄.7H₂O) is preferably added in the amount of 5-100 g to 1,000 mL of the electrolytic plating solution. If the concentration of iron ions is in the range of 1 g/L-20 g/L, openings may be filled with plating while reducing the thickness of the plated film on a substrate surface.
<Manufacturing Method 7>
The composition of the electrolytic plating solution in the Manufacturing Method 3 is changed to the following composition. The rest is the same as in Manufacturing Method 3.


<Composition of Electrolytic Plating Solution>

Sulfuric acid	0.65	mol/L
Copper sulfate	0.7	mol/L
Iron sulfate 7-hydrate	50	g/L
(FeSO₄•7H₂O)
Leveling agent	50	mg/L
Polishing agent
50	mg/L

	Fe²⁺:Fe³⁺	1:2-1:4

<Manufacturing Method 8>
The composition of the electrolytic plating solution in Manufacturing Method 3 is changed to the following composition. The rest is the same as in Manufacturing Method 3.


<Composition of Electrolytic Plating Solution>

Sulfuric acid	0.35	mol/L
Copper sulfate	0.9	mol/L
Iron sulfate 7-hydrate	50	g/L
(FeSO₄•7H₂O)
Leveling agent	50	mg/L
Polishing agent
50	mg/L

	Fe²⁺:Fe³⁺	1:2-1:4

In the embodiments and examples of the present invention, an insulative body makes contact with a surface to be plated, and electrolytic plating is conducted while moving the insulative body relative to the surface to be plated. On the surface to be plated with which the insulative body makes contact, the growth of plated film slows down. It is thought that iron ions are forcibly fed by an insulative body onto the surface to be plated, causing reduction reactions of iron ions on the surface to be plated. Thus, it is thought that growth of electrolytic plated film will be suppressed. By contrast, in areas with which the insulative body does not make contact, since iron ions are diffused onto the surface to be plated due to a concentration gradient, reduction reactions of iron ions are less likely to occur on the surface to be plated. Thus, it is thought that the growth speed of electrolytic plated film will be faster. Accordingly, the electrolytic plated film grows faster in the via-conductor openings and through-hole conductor openings, but the plated film on the surface to be plated excluding the openings will be suppressed from being too thick. Namely, the via-conductor openings and through-hole conductor openings are surely filled with the electrolytic plated film, and the plated film on the surface to be plated (substrate surface) can be formed to be relatively thin compared with the thickness of the electrolytic plated film formed in the openings, or compared with the film thickness of conductive circuits in conventional technology. In the embodiments and examples of the present invention, since thin plated films are patterned, finer conductive circuits can be formed more easily than in conventional cases.
The order and contents of the procedure in the above embodiment may be modified freely within a scope that will not deviate from the gist of the present invention. Also, some steps may be omitted according to usage requirements or the like. For example, corrections may also be made based on image rendering data other than vector data.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

Claims

What is claimed is:

1. A method for manufacturing a printed wiring board, comprising:

forming an opening in a substrate;

forming a seed layer for electrolytic plating on an inner wall of the opening and a surface of the substrate;

placing the substrate with the seed layer in an electrolytic plating solution;

placing an insulative body in the electrolytic plating solution;

moving the substrate and the insulative body relative to each other to form an electrolytic plated film on the substrate and fill the opening with the electrolytic plated film; and

forming a conductive circuit on the substrate,

wherein the electrolytic plating solution includes copper sulfate, sulfuric acid, and iron ions.

2. The method according to claim 1, wherein a source of the iron ions is iron(II) sulfate.

3. The method according to claim 1, wherein the iron ions include iron(II) ions and iron(III) ions, and a ratio of the iron(II) ions to the iron(III) ions in the electrolytic plating solution is from 1:2 to 1:4.

4. The method according to claim 2, wherein the iron sulfate is FeSO₄.7H₂O included at a concentration of 5-100 g/L.

5. The method according to claim 1, wherein the insulative body comprises a material selected from the group consisting of long fiber, a porous resin, a fibrous resin, and rubber.

6. The method according to claim 1, wherein the insulative body comprises porous ceramic or a porous resin.

7. The method according to claim 1, wherein the insulative body comprises a brush having bristles comprising a resin.

8. The method according to claim 1, wherein the insulative body comprises resin fiber.

9. The method according to claim 1, wherein the iron ions are included at a concentration of 1 g/L-20 g/L.