Patent Application
20120067628
This invention relates to a printed wiring board suitable for use as a package substrate, and particularly relates to a printed wiring board having a solder bump formed in each opening of an organic resin insulating layer (a solder resist layer), a printed wiring board having a BGA (ball grid array) connected to each opening through a solder, and a printed wiring board having a conductive connect ion pin attached, through a conductive adhesive, to a conductor circuit opened and exposed.
A printed wiring board employed as a package substrate is manufactured by a method disclosed in, for example, JP H0 9-130050 A. Electroless plating or etching is conducted on the surface of a conductor circuit for a printed wiring board, thereby forming a roughened layer. Thereafter, the roughened layer is coated with interlayer insulating resin, exposed, and developed by a roll coater and printed to form via hole opening portions for interlayer continuity, and UV hardening and actual hardening are conducted to the resultant layer, thereby forming an interlayer resin insulating layer. Further, the interlayer insulating layer is subjected to a roughening treatment with acid or oxidizer, and a catalyst such as palladium is put on the roughened surface of the layer. A thin electroless plated film is formed and, a pattern is formed on the plated film by a dry film, a thick plated layer is plated by electroplating, the dry film is peeled off with alkali, and the thin film and the thick layer are etched to form a conductor circuit. By repeating this process, a buildup multi layer printed wiring board is obtained. In addition, a solder resist layer is formed as the outermost layer of the printed wiring board so as to protect the conductor circuit.
As shown in
The printed wiring board employed as an IC chip package substrate is required to improve frequency characteristics. On the printed wiring board constituted as stated above with reference to
Further, if the opening size of the nickel layer becomes smaller, plating-based precipitation tends to be adversely influenced by the smaller size. In addition, the nickel layer 372 pushes up the printed wiring board manufacturing cost. Besides, since the nickel layer 372 is high in electric resistance, the electric properties of the printed wiring board are lowered. If a connected wiring is a power supply layer and the frequency thereof exceeds 1 GHz in a high frequency range, then the quantity of the supply of power to the IC chip increases. Since a large capacity of power should be supplied momentarily, the transmission of the power is hampered by the nickel layer.
On the other hand, as shown in
As described above, the printed wiring board employed as an IC chip package substrate is required to improve frequency characteristics. On the printed wiring board constituted as stated above with reference to
The present invention has been made to solve the above-stated problems, and the first object of the present invention is to provide a printed wiring board which includes solder pads excellent in high frequency characteristic and a printed wiring board manufacturing method.
It is the second object of the present invention to provide a printed wiring board which includes BGAs excellent in high frequency characteristic and a printed wiring board manufacturing method.
It is the third object of the present invention to provide a printed wiring board which includes conductive connection pins and has an excellent high frequency characteristic and a printed wiring board manufacturing method.
In order to achieve the first object of the present invention, according to the first invention, a printed wiring board having a solder bump provided on a conductor circuit having a part of an organic resin insulating layer exposed and opened, is characterized in that a single metal layer of tin or noble metal is provided on said exposed conductor circuit, and said solder bump is provided.
According to the first invention, a solder bump is formed by providing a single metal layer on a conductor circuit. Due to this, a signal propagation rate can be increased, as compared with the printed wiring board of the prior art on which the two metal layers are formed. In addition, due to a lack of the nickel layer, manufacturing cost can be decreased and electric characteristics can be enhanced. Further, as for the supply of power to IC chip, the power supply is not hampered and desired power is, therefore, supplied to the IC chip. It is possible to suppress malfunction, delay and the like in initial operation. It is also possible to improve adhesion between the conductor circuit and the solder.
The printed wiring board according to the present invention is constituted so that via holes which are non-penetrating holes are formed in an interlayer resin insulating layer which is not impregnated with a reinforcement core material on a resin substrate having a thickness of about 30 μm, serving as a core substrate, having a thickness of about 0.4 to 1 mm and impregnated with a reinforcement core material, solder bumps made of C4 are formed on the interlayer resin insulating layer, and a flip-chip is mounted on the resultant printed wiring board. In addition, the printed wiring board is connected to an external substrate such as a daughter board through pins or BGAs serving as external terminals. During mounting, the IC chip for the flip-chip is superposed on the solder bumps, and reflow is conducted to thereby melt the solder and, at the same time, connect the solder to the IC chip. As a result, the printed wiring board is electrically connected to the IC chip.
According to the second invention, since noble metal is gold, silver, platinum or palladium, the noble metal is excellent in corrosion resistance and it is difficult to oxidize and degenerate the surface of the noble metal. Further, if the metal is formed on the roughened conductor circuit, the electric characteristic of the board such as resistance is improved, as compared with the board of the two-layer structure (nickel-gold) of the prior art. The reason is considered to be lack of a nickel layer which hampers the improvement of the electric characteristic.
By forming gold on each conductor circuit having a part of an organic resin insulating layer exposed, it is possible to not only obtain the conductor circuit excellent in corrosion resistance or a solder bump formation pad, but also to decrease metal resistance on the IC chip—the solder bump—the conductor layer. Impediment of power supply hardly occur. It is possible to decrease the voltage drop quantity of the power supply. Further, if the solder which is molten by reflow is solidified again, it is possible to improve the adhesion and bonding property of the solder to the pad. Due to this, even if a reliability test is conducted, decrease in tensile strength is small.
By forming silver on each conductor circuit having a part of an organic resin insulating layer exposed, it is possible to not only obtain the conductor circuit excellent in corrosion resistance or a solder bump formation pad, but also to decrease metal resistance on the IC chip—the solder bump—the conductor layer because silver itself is excellent in electric conductivity. Impediment of power supply hardly occur. It is possible to decrease the voltage drop quantity of the power supply. Further, if the solder which is molten by reflow is solidified again, it is possible to improve the adhesion and bonding property of the solder to the pad. Due to this, even if a reliability test is conducted, decrease in tensile strength is small.
By forming tin on each conductor circuit having a part of an organic resin insulating layer exposed, it is possible to not only obtain the conductor circuit excellent in corrosion resistance or a solder bump formation pad, but also to decrease metal resistance on the IC chip—the solder bump—the conductor layer. Impediment of power supply hardly occur. It is possible to decrease the voltage drop quantity of the power supply. Further, if the solder which is molten by reflow is solidified again, it is possible to improve the adhesion and bonding property of the solder to the pad. Due to this, even if a reliability test is conducted, decrease in tensile strength is small. If the solder containing tin is used, in particular, an alloy of the bump and the pad is formed during reflow crystallization, thus making it possible to improve tensile strength.
According to the third invention, the thickness of a metal layer is 0.01 to 3.0 μm. If the thickness is less than 0.01 μm, portions which cannot completely cover the conductor circuit are generated, adversely influencing strength and corrosion resistance. In particular, it is because the roughened surface is exposed, as the conductive circuit having roughened layers formed is provided with metal layers. Besides, no improvement in electric characteristic and strength is seen. Conversely, if the thickness exceeds 3.0 μm, the corrosion resistance and the strength are not improved and the metal becomes too expensive, adversely influencing cost-effectiveness. In addition, a fluctuation in thickness tends to occur, and the characteristic of the respective pads differ, which sometimes adversely influences the electric characteristic. The thickness is preferably 0.05 to 1 μm, more preferably 0.1 to 0.5 μm. In this range, no problem occurs even if there is somewhat a fluctuation in thickness.
According to the fourth invention, roughened layers are formed on the surface and sides of each conductor circuit. This can ensure high adhesion between the conductor circuit and the organic resin insulating layer. The solder bump preferably comprises of eutectic metals of one of Sn/Pb, Sn/Sb, Sn/Ag, Sn/Ag/Cu, and Sn/Cu. Further, the solder bump melting point is preferably between 180 and 280° C. In such a temperature range, even if reflow is conducted, the melting of the resin substrate by the temperature does not occur. If such the solder is used, good adhesion between the solder and the metal layer is ensured. When the solder is solidified again after being molten, an alloy of the solder and the single metal layer is surely formed, thus preventing the deterioration of the strength. Problems concerning to mechanical connection and electric connection hardly occur. With the nickel-gold layers of the prior art, when the nickel layer is defectively formed, the defective layer effects quality of the gold layer thereon, with the result that the formation of an alloy between the metal layer and the solder is hampered. Due to this, bonding strength is deteriorated.
According to the sixth invention, the solder bump comprises of eutectic metals of one of Sn/Pb, Sn/Sb, Sn/Ag, and Sn/Ag/Cu and contains tin, thus ensuring high adhesion to the metal layer (solder pad) comprising of tin.
According to the seventh invention, the solder bump comprises of eutectic metals of one of Sn/Ag and Sn/Ag/Cu and contains silver, thus ensuring high adhesion to the metal layer (solder pad) comprising of silver.
According to the eighth invention, a printed wiring board manufacturing method is characterized by providing a single metal layer on a conductor circuit mainly comprising of copper and having a part of an organic resin insulating layer exposed and opened to form a solder pad by executing at least steps (a) to (c):
(a) the step of immersing the printed wiring board having said conductor circuit exposed from the organic resin insulating layer in an etchant of one of sulfuric acid—hydrogen peroxide, cuprous chloride and ferrous chloride;
(b) the activation step using acid; and
(c) the step of providing said single metal layer on said conductor circuit by tin or noble metal substitutional plating.
According to the eighth invention, the conductor circuit mainly comprising of copper is etched and activated by acid. It is, therefore, possible to form a uniformly thin single-layer metal film comprising of tin or noble metal by substitutional plating, regardless of the form and size of the conductor circuit.
According to the ninth invention, noble metal constituting the metal layer is soft metal. It is, therefore, possible to form a single-layer metal film on the conductor circuit without nickel intervening and without diffusing the gold layer to copper. Namely, according to the prior art, hard gold which enables wire bonding to gold wires is continuously used as gold at the time of establishing connection by the solder pad. Since the hard gold is diffused into the conductor circuit made of copper by electroless plating, a film cannot be formed unless the nickel layer intervenes. In addition, it is necessary to ensure strength for the bonding. According to the ninth invention, in contrast, it is possible to directly form the film on the conductor circuit made of copper.
In order to achieve the second object of the present invention, according to the first invention, a printed wiring board having a BGA (ball grid array) provided on a conductor circuit having a part of an organic resin insulating layer exposed and opened, is characterized in that a single metal layer of tin or noble metal is provided on said exposed conductor circuit, and said BGA is provided.
According to the first invention, a BGA is formed by providing a single metal layer on a conductor circuit. Due to this, a signal propagation rate can be increased, as compared with the prior art of the printed wiring board on which the two metal layers are formed. In addition, due to lack of the nickel layer, manufacturing cost can be decreased and electric characteristics can be enhanced. Further, as for the supply of power to IC chip, the power supply is not hampered and desired power is, therefore, supplied to the IC chip. It is possible to suppress malfunction, delay and the like in initial operation. It is also possible to improve adhesion between the conductor circuit and the solder.
According to the second invention, since noble metal is gold, silver, platinum or palladium, the noble metal is excellent in corrosion resistance and it is difficult to oxidize and degenerate the surface of the noble metal. Further, if the metal is formed on the roughened conductor circuit, the electric characteristic of the board such as resistance is improved, as compared with the board of the two-layer structure (nickel-gold) of the prior art. The reason is considered to be lack of a nickel layer which hampers the improvement of the electric characteristic.
By forming gold on each conductor circuit having a part of an organic resin insulating layer exposed, it is possible to not only obtain the conductor circuit excellent in corrosion resistance or a BGA formation pad, but also to decrease metal resistance on the IC chip—the BGA—the conductor layer. Impediment of power supply hardly occur. It is possible to decrease the voltage drop quantity of the power supply. Further, if the solder which is molten by reflow is solidified again, it is possible to improve the adhesion and bonding property of the solder to the pad. Due to this, even if a reliability test is conducted, decrease in tensile strength is small.
By forming silver on each conductor circuit having a part of an organic resin insulating layer exposed, it is possible to not only obtain the conductor circuit excellent in corrosion resistance or a BGA formation pad, but also to decrease metal resistance on the daughter board—the BGA—the conductor layer because silver itself is excellent in electric conductivity. Impediment of power supply hardly occur. It is possible to decrease the voltage drop quantity of the power supply. Further, if the solder which is molten by reflow is solidified again, it is possible to improve the adhesion and bonding property of the solder to the pad. Due to this, even if a reliability test is conducted, decrease in tensile strength is small.
By forming tin on each conductor circuit having a part of an organic resin insulating layer exposed, it is possible to not only obtain the conductor circuit excellent in corrosion resistance or a BGA formation pad, but also to decrease metal resistance on the daughter board—the BGA—the conductor layer. Impediment of power supply hardly occur. It is possible to decrease the voltage drop quantity of the power supply. Further, if the solder which is molten by reflow is solidified again, it is possible to improve the adhesion and bonding property of the solder to the pad. Due to this, even if a reliability test is conducted, decrease in tensile strength is small. If the solder containing tin is used, in particular, an alloy of the BGA and the pad is formed during reflow crystallization, thus making it possible to improve tensile strength.
According to the third invention, the thickness of a metal layer is 0.01 to 3.0 μm. If the thickness is less than 0.01 μm, portions which cannot completely cover the conductor circuit are generated, adversely influencing strength and corrosion resistance. In particular, it is because the roughened surface is exposed, the conductive circuit having roughened layers formed is provided with metal layers. Besides, no improvement in electric characteristic and strength is seen. Conversely, if the thickness exceeds 3.0 μm, the corrosion resistance and the strength are not improved and the metal becomes too expensive, adversely influencing cost-effectiveness. In addition, a fluctuation in thickness tends to occur, and the characteristic of the respective pads differ, which sometimes adversely influences the electric characteristic. The thickness is preferably 0.05 to 1 μm, more preferably 0.1 to 0.5 μm. In this range, no problem occurs even if there is somewhat a fluctuation in thickness.
According to the fourth invention, roughened layers are formed on the surface and sides of each conductor circuit. This can ensure high adhesion between the conductor circuit and the organic resin insulating layer.
The conductive adhesive for connecting the solders or BGAs which constitute the BGAs preferably comprises of eutectic metals of one of Sn/Pb, Sn/Sb, Sn/Ag, Sn/Ag/Cu, and Sn/Cu. Further, the solder bump melting point is preferably between 180 and 280° C. Within such a temperature range, even if reflow is conducted, the melting of the resin substrate by the temperature does not occur. If such a solder is used, good adhesion between the solder and the metal layer is ensured. When the solder is solidified again after being molten, an alloy of the solder and the single metal layer is surely formed, thus preventing the deterioration of the strength. Problems concerning to mechanical connection and electric connection hardly occur. With the prior art of the nickel-gold layers, when the nickel layer is defectively formed, the defective layer effects the quality of the gold layer thereon, with the result that the formation of an alloy between the metal layer and the solder is hampered. Due to this, bonding strength is deteriorated. Furthermore, the same result can be obtained even if the eutectic metals of Sn/Cu are used.
According to the fifth invention, the conductive adhesive for connecting the solders or BGAs which constitute the BGAs is made of eutectic metals of Sn/Pb, Sn/Sb, Sn/Ag, Sn/Ag/Cu and contains tin, thus ensuring high adhesion of the adhesive to the metal layer (solder pad) comprising of tin.
According to the sixth invention, the conductive adhesive for connecting the solders or BGAs which constitute the BGAs is made of eutectic metals of Sn/Ag, Sn/Ag/Cu and contains silver, thus ensuring high adhesion of the adhesive to the metal layer (solder pad) comprising of silver.
According to the seventh invention, the conductive adhesive for connecting the solders or BGAs which constitute the BGAs is made of eutectic metals of Sn/Pb, Sn/Sb, Sn/Ag, Sn/Ag/Cu and contains gold, thus ensuring high adhesion of the adhesive to the metal layer (solder pad) comprising of gold.
According to the eighth invention, a printed wiring board manufacturing method is characterized by providing a single metal layer on a conductor circuit mainly comprising of copper and having a part of an organic resin insulating layer exposed and opened to form a BGA (ball grid array) comprising of a solder bump by executing at least steps (a) to (c):
(a) the step of immersing the printed wiring board having said conductor circuit exposed from the organic resin insulating layer in an etchant of one of sulfuric acid—hydrogen peroxide, cuprous chloride and ferrous chloride;
(b) the activation step using acid; and
(c) the step of providing said single metal layer on said conductor circuit by tin or noble metal substitutional plating.
According to the eighth invention, the conductor circuit mainly comprising of copper is etched and activated by acid. It is, therefore, possible to form a uniformly thin single-layer metal film comprising of tin or noble metal by substitutional plating, regardless of the form and size of the conductor circuit.
According to the ninth invention, noble metal constituting the metal layer is soft metal. It is, therefore, possible to form a single-layer metal film on the conductor circuit without nickel intervening and without diffusing the gold layer to copper. Namely, according to the prior art, hard gold which enables wire bonding to gold wires is continuously used as gold at the time of establishing connection by the solder pad. Since the hard gold is diffused into the conductor circuit made of copper by electroless plating, a film cannot be formed unless the nickel layer intervenes. In addition, it is necessary to ensure strength for the bonding. According to the ninth invention, in contrast, it is possible to directly form the film on the conductor circuit made of copper.
In order to achieve the third object of the present invention, according to the first invention, a printed wiring board having a conductive connection pin attached to a conductor circuit having a part of an organic resin insulating layer exposed and opened, with a conductive adhesive intervening between the conductive connection pin and the conductor circuit is characterized in that a single metal layer of tin or noble metal is provided on said exposed conductor circuit, and the conductive connection pin is attached to the conductor circuit with the conductive adhesive intervening between the conductive connection pin and the conductor circuit.
According to the first invention, the conductive connection pin is attached to the conductor circuit with the conductive adhesive intervening between the conductive connection pin and the conductor circuit by providing a single metal layer on a conductor circuit. Due to this, a signal propagation rate can be increased, as compared with the printed wiring board of the prior art on which the two metal layers are formed. In addition, due to lack of the nickel layer, manufacturing cost can be decreased and electric characteristics can be enhanced. Further, as for the supply of power to an external substrate such as a daughter board, the power supply is not hampered and desired power is, therefore, supplied to the daughter board. It is possible to suppress malfunction, delay and the like in initial operation. It is also possible to improve adhesion between the conductor circuit and the solder.
The printed wiring board according to the present invention is constituted so that via holes which are non-penetrating holes are formed in an interlayer resin insulating layer which is not impregnated with a reinforcement core material on a resin substrate having a thickness of about 30 μm, serving as a core substrate, having a thickness of about 0.4 to 1 mm and impregnated with a reinforcement core material, solder bumps made of C4 are formed on the interlayer resin insulating layer, and a flip-chip is mounted on the resultant printed wiring board. In addition, the printed wiring board is connected to an external substrate such as a daughter board through conductive connection pins serving as external terminals.
According to the second invention, since noble metal is gold, silver, platinum or palladium, the noble metal is excellent in corrosion resistance and it is difficult to oxidize and degenerate the surface of the noble metal. Further, if the metal is formed on the roughened conductor circuit, the electric characteristic of the board such as resistance is improved, as compared with the board of the two-layer structure (nickel-gold) of the prior art. The reason is considered to be lack of a nickel layer which hampers the improvement of the electric characteristic.
By forming gold on each conductor circuit having a part of an organic resin insulating layer exposed, it is possible to not only obtain the conductor circuit excellent in corrosion resistance or a conductive connection pin attachment pad, but also to decrease metal resistance on the daughter board—the conductive connection pin—the conductor layer. Impediment of power supply hardly occur. It is possible to decrease the voltage drop quantity of the power supply. Further, if the solder which is molten by reflow is solidified again, it is possible to improve the adhesion and bonding property of the solder to the pad. Due to this, even if a reliability test is conducted, decrease in tensile strength is small.
By forming silver on each conductor circuit having a part of an organic resin insulating layer exposed, it is possible to not only obtain the conductor circuit excellent in corrosion resistance or a conductive connection pin attachment pad, but also to decrease metal resistance on the daughter board—the conductive connection pin—the conductor layer because silver itself is excellent in electric conductivity. Impediment of power supply hardly occur. It is possible to decrease the voltage drop quantity of the power supply. Further, if the solder which is molten by reflow is solidified again, it is possible to improve the adhesion and bonding property of the solder to the pad. Due to this, even if a reliability test is conducted, decrease in tensile strength is small.
By forming tin on each conductor circuit having a part of an organic resin insulating layer exposed, it is possible to not only obtain the conductor circuit excellent in corrosion resistance or a conductive connection pin attachment pad, but also to decrease metal resistance on the daughter board—the conductive connection pin—the conductor layer. Impediment of power supply hardly occur. It is possible to decrease the voltage drop quantity of the power supply. Further, if the solder which is molten by reflow is solidified again, it is possible to improve the adhesion and bonding property of the solder to the pad. Due to this, even if a reliability test is conducted, decrease in tensile strength is small. If the solder containing tin is used, in particular, an alloy of the bump and the pad is formed during reflow crystallization, thus making it possible to improve tensile strength.
According to the third invention, the thickness of a metal layer is 0.01 to 3.0 μm. If the thickness is less than 0.01 μm, portions which cannot completely cover the conductor circuit are generated, adversely influencing strength and corrosion resistance. In particular, it is because the roughened surface is exposed, as the conductive circuit having roughened layers formed is provided with metal layers. Besides, no improvement in electric characteristic and strength is seen. Conversely, if the thickness exceeds 3.0 μm, the corrosion resistance and the strength are not improved and the metal becomes too expensive, adversely influencing cost-effectiveness. In addition, a fluctuation in thickness tends to occur, and the characteristic of the respective pads differ, which sometimes adversely influences the electric characteristic. The thickness is preferably 0.05 to 1 μm, more preferably 0.1 to 0.5 μm. In this range, no problem occurs even if there is somewhat a fluctuation in thickness.
According to the fourth invention, roughened layers are formed on the surface and sides of each conductor circuit. This can ensure high adhesion between the conductor circuit and the organic resin insulating layer. The conductive adhesive preferably comprises of eutectic metals of one of Sn/Pb, Sn/Sb, Sn/Ag, and Sn/Ag/Cu. Further, the conductive adhesive melting point is preferably between 180 and 280° C. Within such a temperature range, even if reflow is conducted, the melting of the resin substrate by the temperature does not occur. If such a solder is used, good adhesion between the solder and the metal layer is ensured. When the solder is solidified again after being molten, an alloy of the solder and the single metal layer is surely formed, thus preventing the deterioration of the strength. Problems concerning to mechanical connection and electric connection hardly occur. With the prior art of the nickel-gold layers, when the nickel layer is defectively formed, the defective layer effects the quality of the gold layer thereon, with the result that the formation of an ally between the metal layer and the solder is hampered. Due to this, bonding strength is deteriorated. Furthermore, the same result can be obtained even if the eutectic metals of Sn/Cu are used.
According to the fifth invention, the conductive adhesive comprises of eutectic metals of one of Sn/Pb, Sn/Sb, Sn/Ag, and Sn/Ag/Cu and contains tin, thus ensuring high adhesion to the metal layer (solder pad) comprising of tin.
According to the sixth invention, a printed wiring board manufacturing method is characterized by providing a single metal layer on a conductor circuit mainly comprising of copper and having a part of an organic resin insulating layer exposed and opened to attach a conductive connection pin with a conductive adhesive by executing at least steps (a) to (c):
(a) the step of immersing the printed wiring board having said conductor circuit exposed from the organic resin insulating layer in an etchant of one of sulfuric acid—hydrogen peroxide, cuprous chloride and ferrous chloride;
(b) the activation step using acid; and
(c) the step of providing said single metal layer on said conductor circuit by tin or noble metal substitutional plating.
According to the sixth invention, the conductor circuit mainly comprising of copper is etched and activated by acid. It is, therefore, possible to form a uniformly thin single-layer metal film comprising of tin or noble metal by substitutional plating, regardless of the form and size of the conductor circuit.
According to the seventh invention, noble metal constituting the metal layer is soft metal. It is, therefore, possible to form a single-layer metal film on the conductor circuit without nickel intervening and without diffusing the gold layer to copper. Namely, according to the prior art, hard gold which enables wire bonding to gold wires is continuously used as gold at the time of establishing connection by the conductive connection pin. Since the hard gold is diffused into the conductor circuit made of copper by electroless plating, a film cannot be formed unless the nickel layer intervenes. In addition, it is necessary to ensure strength for the bonding. According to the seventh invention, by contrast, it is possible to directly form the film on the conductor circuit made of copper.
A conductive connection pin comprises of a columnar connection portion and a plate fixed portion, and made of metal selecting from a group comprising of copper, copper alloy, nickel, tin, zinc, aluminum and noble metal.
The configuration of a printed wiring board according to the first embodiment of the present invention will first be described with reference to
As shown in
As shown in
As shown in
On the printed wiring board 10 in the first embodiment, since the single tin layer 74 is provided on each of the conductor circuits 158 and vias 160 and the solder pad 73 is formed thereon, a signal propagation rate can be increased, as compared with the printed wiring board of the prior art on which the two metal layers are formed as described above with reference to
The thickness of the tin layer 74 is preferably 0.01 to 3.0 μm. If the thickness is less than 0.01 μm, portions which cannot completely cover the conductor circuit 158 or via 160 are generated, adversely influencing strength and corrosion resistance. Conversely, if the thickness exceeds 3.0 μm, the corrosion resistance and the strength are not improved. Besides, it is difficult to form a tin layer of not less than 3.0 μm by substitutional plating. Further, with such a thickness, peeling occurs in the film, thus deteriorating the strength. The thickness is more preferably 0.03 to 0.5 μm. In this range, no problem occurs even if there is somewhat a fluctuation in thickness.
On the printed wiring board 10 in this embodiment, a roughened layer 158α is formed on the surface of each of the conductor circuits 158 and vias 160 as shown in
Furthermore, in the first embodiment, a conductive adhesive for connecting the solder or BGA which constitutes the solder bump 76U or the BGA 76D, respectively is an eutectic metal of Sn/Pb, Sn/Sb, Sn/Ag or Sn/Ag/Cu. Since the conductive adhesive contains tin, the adhesive strongly adheres to the solder pad 73 which includes the tin layer 74.
Now, a method for manufacturing the printed wiring board stated above with reference to
The viscosity is measured by using No. 4 rotor of a B-type viscometer (DVL-B type, manufactured by Tokyo Keiki) when the velocity is 60 rpm, and using No. 3 rotor thereof when the velocity is 6 rpm.
Next, the mounting of the IC chip to the printed wiring board 10 completed through the above-stated steps, and the attachment of the printed wiring board 10 to the daughter board will be described with reference to
In the first embodiment stated above, cycloolefin-based resin is used for the interlayer resin insulating layers 50 and 150. Alternatively, epoxy-based resin can be used in place of the cycloolefin-based resin. The epoxy-based resin contains refractory resin, soluble particles, a hardening agent and other components. These materials will be described below one by one.
The epoxy-based resin which is applicable to the manufacturing method of the present invention has a structure in which particles soluble in acid or oxidizer (which particles will be referred to as “soluble particles” hereinafter) are dispersed into resin refractory with respect to acid or oxidizer (which resin will be referred to as “refractory resin” hereinafter).
The expressions “refractory” and “soluble” will now be described. When materials are immersed in solution composed of the same acid or the same oxidizers for the same time, a material of a type which is dissolved at a relatively high dissolving rate is called a “soluble” material for convenience. A material of a type which is dissolved at a relatively slow dissolving rate is called a “refractory material” for convenience.
The soluble particles are exemplified by resin particles which are soluble in acid or an oxidizer (hereinafter called “soluble resin particles”), inorganic particles which are soluble in acid or an oxidizer (hereinafter called “inorganic soluble particles”) and metal particles which are soluble in acid or an oxidizer (hereinafter called “soluble metal particles”). The foregoing soluble particles may be employed solely or two or more particles may be employed.
The shape of each of the soluble particles is not limited. The shape may be a spherical shape or a pulverized shape. It is preferable that the particles have a uniform shape. The reason for this lies in that a rough surface having uniformly rough pits and projections can be formed.
It is preferable that the mean particle size of the soluble particles is 0.1 μm to 10 μm. When the particles have the diameters satisfying the foregoing range, particles having two or more particle sizes may be employed. That is, soluble particles having a mean particle size of 0.1 μm to 0.5 μm and soluble particles having a mean particle size of 1 μm to 3 μmm may be mixed. Thus, a more complicated rough surface can be formed. Moreover, the adhesiveness with the conductor circuit can be improved. In the present invention, the particle size of the soluble particles is the length of a longest portion of each of the soluble particles.
The soluble resin particles may be particles constituted by thermosetting resin or thermoplastic resin. When the particles are immersed in solution composed of acid or an oxidizer, the particles must exhibit dissolving rate higher than that of the foregoing refractory resin.
Specifically, the soluble resin particles are exemplified by particles constituted by epoxy resin, phenol resin, polyimide resin, polyphenylene resin, polyolefin resin or fluorine resin. The foregoing material may be employed solely or two or more materials may be mixed.
The soluble resin particles may be resin particles constituted by rubber. The rubber above is exemplified by polybutadiene rubber, a variety of denatured polybutadiene rubber, such as denatured epoxy rubber, denatured urethane rubber or denatured (metha)acrylonitrile rubber, and (metha)acrylonitrile butadiene rubber containing a carboxylic group. When the foregoing rubber material is employed, the soluble resin particles can easily be dissolved in acid or an oxidizer. That is, when the soluble resin particles are dissolved with acid, dissolution is permitted with acid except for strong acid. When the soluble resin particles are dissolved, dissolution is permitted with permanganate which has a relatively weak oxidizing power. When chromic acid is employed, dissolution is permitted even at a low concentration. Therefore, retention of the acid or the oxidizer on the surface of the resin can be prevented. When a catalyst, such as palladium chloride, is supplied after the rough surface has been formed as described later, inhibition of supply of the catalyst and oxidation of the catalyst can be prevented.
The inorganic soluble particles are exemplified by particles made of at least a material selected from a group comprising of an aluminum compound, a calcium compound, a potassium compound, a magnesium compound and a silicon compound.
The aluminum compound is exemplified by alumina and aluminum hydroxide. The calcium compound is exemplified by calcium carbonate and calcium hydroxide. The potassium compound is exemplified by potassium carbonate. The magnesium compound is exemplified by magnesia, dolomite and basic magnesium carbonate. The silicon compound is exemplified by silica and zeolite. The foregoing material may be employed solely or two or more materials may be mixed.
The soluble metal particles are exemplified by particles constituted by at least one material selected from a group comprising of copper, nickel, iron, zinc, lead, gold, silver, aluminum, magnesium, potassium and silicon. The soluble metal particles may have surfaces coated with resin or the like in order to maintain an insulating characteristic.
When two or more types of the soluble particles are mixed, it is preferable that the combination of the two types of soluble particles is a combination of resin particles and inorganic particles. Since each of the particles has low conductivity, an insulating characteristic with the resin film can be maintained. Moreover, the thermal expansion can easily be adjusted with the refractory resin. Thus, occurrence of a crack of the interlayer resin insulating layer constituted by the resin film can be prevented. Thus, separation between the interlayer resin insulating layer and the conductor circuit can be prevented.
The refractory resin is not limited when the resin is able to maintain the shape of the rough surface when the rough surface is formed on the interlayer resin insulating layer by using acid or oxidizer. The refractory resin is exemplified by thermosetting resin, thermoplastic resin and their composite material. As an alternative to this, the foregoing photosensitive resin of a type having photosensitive characteristic imparted thereto may be employed. When the photosensitive resin is employed, exposure and development processes of the interlayer resin insulating layers can be performed to form the openings for the via holes.
In particular, it is preferable that the resin containing thermosetting resin is employed. In the foregoing case, the shape of the rough surface can be maintained against plating solution and when a variety of heating processes are performed.
The refractory resin is exemplified by epoxy resin, phenol resin, polyimide resin, polyphenylene resin, polyolefin resin and fluorine resin. The foregoing material may be employed solely or two or more types of the materials may be mixed.
It is preferable that epoxy resin having two or more epoxy groups in one molecule thereof is employed. The reason for this lies in that the foregoing rough surface can be formed. Moreover, excellent heat resistance and the like can be obtained. Thus, concentration of stress onto the metal layer can be prevented even under a heat cycle condition. Thus, occurrence of separation of the metal layer can be prevented.
The epoxy resin is exemplified by cresol novolac epoxy resin, bisphenol-A epoxy resin, bisphenol-F epoxy resin, phenol novolac epoxy resin, alkylphenol novolac epoxy resin, biphenol-F epoxy resin, naphthalene epoxy resin, dicyclopentadiene epoxy resin, an epoxy material constituted by a condensation material of phenol and an aromatic aldehyde having a phenol hydroxyl group, triglycidyl isocyanurate and alicyclic epoxy resin. The foregoing materials maybe employed solely or two or more material may be mixed. Thus, excellent heat resistance can be realized.
It is preferable that the soluble particles in the resin film according to the present invention are substantially uniformly dispersed in the refractory resin. The reason for this lies in that a rough surface having uniform pits and projections can be formed. When via holes and through holes are formed in the resin film, adhesiveness with the metal layer of the conductor circuit can be maintained. As an alternative to this, a resin film containing soluble particles in only the surface on which the rough surface is formed may be employed. Thus, the portions of the resin film except for the surface is not exposed to acid or the oxidizer. Therefore, the insulating characteristic between conductor circuits through the interlayer resin insulating layer can reliably be maintained.
It is preferable that the amount of the soluble particles which are dispersed in the refractory resin is 3 wt % to 40 wt % with respect to the resin film. When the amount of mixture of the soluble particles is lower than 3 wt %, the rough surface having required pits and projections cannot be formed. When the amount is higher than 40 wt %, deep portions of the resin film are undesirably dissolved when the soluble particles are dissolved by using acid or the oxidizer. Thus, the insulating characteristic between the conductor circuits through the interlayer resin insulating layer constituted by the resin film cannot be maintained. Thus, short circuit is sometimes incidentally caused.
It is preferable that the resin film contains a hardening agent and other components as well as the refractory resin.
The hardening agent is exemplified by an imidazole hardening agent, an amine hardening agent, a guanidine hardening agent, an epoxy adduct of each of the foregoing hardening agents, a microcapsule of each of the foregoing hardening agents and an organic phosphine compound, such as triphenylphosphine or tetraphenyl phosphonium tetraphenyl borate.
It is preferable that the content of the hardening agent is 0.05 wt % to 10 wt % with respect to the resin film. When the content is lower than 0.05 wt %, the resin film cannot sufficiently be hardened. Thus, introduction of acid and the oxidizer into the resin film occurs greatly. In the foregoing case, the insulating characteristic of the resin film sometimes deteriorates. When the content is higher than 10 wt %, an excessively large quantity of the hardening agent component sometimes denatures the composition of the resin. In the foregoing case, the reliability sometimes deteriorates.
The other components are exemplified by an inorganic compound which does not exert an influence on the formation of the rough surface and a filler constituted by resin. The inorganic compound is exemplified by silica, alumina and dolomite. The resin is exemplified by polyimide resin, polyacrylic resin, polyamideimide resin, polyphenylene resin, melanine resin and olefin resin. When any one of the foregoing fillers is contained, conformity of the thermal expansion coefficients can be established. Moreover, heat resistance and chemical resistance can be improved. As a result, the performance of the printed circuit board can be improved.
The resin film may contain solvent. The solvent is exemplified by ketone, such as acetone, methylethylketone or cyclohexane; aromatic hydrocarbon, such as ethyl acetate, butyl acetate, cellosolve acetate, toluene or xylene. The foregoing material may be employed solely or two or more materials may be mixed.
A printed wiring board 110 according to the first modification of the present invention will next be described with reference to
The thickness of the gold layer 174 is desirably 0.01 to 3 μm. If the thickness is less than 0.01 μm, portions which cannot completely cover the conductor circuit 158 or via 160 are generated, adversely influencing strength and corrosion resistance. Conversely, if the thickness exceeds 3 μm, the corrosion resistance is not improved, electronic characteristic is often deteriorated, and peeling occurs in the films. In addition, the gold layers become too expensive, adversely influencing cost-effectiveness. The thickness of the gold layer 174 is preferably 0.05 to 2 μm. Preferably, the thickness is 0.05 to 2 μm. More preferably, the thickness is in a range of 0.1 to 1 μm. In this range, no problem occurs even if there is a fluctuation in thickness.
Next, A. an interlayer resin insulating layer resin film, and B. resin filler used in a method for manufacturing the printed wiring board according to the first modification of the present invention will be described.
30 parts by weight of bisphenol A epoxy resin (epoxy equivalent: 469, Epicoat 1001 manufactured by Yuka Shell), 40 parts by weight of cresol novolac type epoxy resin (epoxy equivalent: 215, manufactured by Dainippon Ink and Chemicals, EpiclonN-673) and 30 parts by weight of phenol novolac resin including a triazine structure (phenol hydroxyl group equivalent: 120, manufactured by Dainippon Ink and Chemicals, PhenoliteKA-7052) are heated and molten while being agitated with 20 parts by weight of ethyl diglycol acetate and 20 parts by weight of solvent naphtha, and 15 parts by weight of terminally epoxidized polybutadiene rubber (manufactured by Nagase Chemicals Ltd., DenalexR-45EPT) and 1.5 parts by weight of crushed product of 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 2 parts by weight of pulverized silica and 0.5 parts by weight of silicon-based defoaming agent are added, thereby preparing the epoxy resin composition. The obtained epoxy resin composition is coated on a PET film having a thickness of 38 μm so as to have a thickness of 50 μm after being dried by the roll coater, and dried for 10 minutes at 80 to 120° C., thereby manufacturing the interlayer resin insulating layer resin film.
100 parts by weight of bisphenol F type epoxy monomer (manufactured by Yuka Shell, molecular weight: 310, YL983U), 170 parts by weight of SiO2 spheroidal particles having a silane coupling agent coated on surfaces thereof, a mean particle size of 1.6 μm, and a largest particle diameter of not more than 15 μm (manufactured by ADTEC, CRS 1101-CE) and 1.5 parts by weight of leveling agent (manufactured by San Nopco Ltd., PelenolS4) are input in the container, and agitated and mixed therein, thereby preparing resin filler having a viscosity of 45 to 49 Pa·s at 23±1° C. As hardening agent, 6.5 parts by weight of imidazole hardening agent (manufactured by Shikoku Chemicals, 2E4MZ-CN) is used.
A method for manufacturing the printed wiring board stated above with reference to
As the etchant, etchant (manufactured by Mech, Mech-Etch Bond) comprising of 10 parts by weight of an imidazole copper (II) complex, 7 parts by weight of glycolic acid and 5 parts by weight of potassium chloride is used.
Solution temperature of 35° C. for 40 minutes.
The viscosity is measured by using No. 4 rotor of a B-type viscometer (DVL-B type, manufactured by Tokyo Keiki) when the velocity is 60 rpm, and using No. 3 rotor thereof when the velocity is 6 rpm.
Further, heat treatments are conducted for 1 hour at 80° C., 1 hour at 100° C., for 1 hour at 120° C., and for 3 hours at 150° C., respectively, to harden the solder resist layers compositions, thus forming solder resist layers 70 each having the opening portions 71 and a thickness of 20 μm (see
In the first modification, since the noble metal constituting the gold layer 174 is soft gold, it is possible to form single-layer gold films 174 on the conductor circuits 158 and the vias 160 without making nickel intervene and diffusing the gold layers to copper. Namely, according to the prior art, hard gold which enables wire bonding to gold wires is continuously used as gold at the time of establishing connection by the solder pads. Since the hard gold is diffused into the conductor circuits made of copper by electroless plating, films cannot be formed unless the nickel layers intervene. In the first modification, by contrast, it is possible to directly form films on the conductor circuits 158 made of copper and the vias 160. While gold is used herein, platinum or palladium can be used.
A printed wiring board 210 according to the second modification of the present invention will be described with reference to
Manufacturing steps of the printed wiring board in the second modification will be described. Manufacturing steps (1) to (17) of this second modification are equal to those of the first modification described above with reference to
Further, in the second modification, the conductive adhesive for connecting the solders or BGAs which constitute the solder bumps 76U or BGAs 76D is made of eutectic metals of Sn/Ag or Sn/Ag/Cu and contains silver, thus ensuring high adhesion of the adhesive to the solder pads 73 each including the silver layer 274. The second modification is congenital to the solders which do not contain lead (Sn/Ag, Sn/Ag/Cu, and Sn/Cu), so that these solders can be suitably used in this modification.
In the first to second modifications stated above, the metal layer of each solder pad is formed by substitutional plating. Alternatively, it can be formed by electroless plating with catalyst intervening. The electroless plating is less expensive. However, without the catalyst, non-reaction tends to occur. Besides, it is difficult to control film thickness.
As the first comparison, a gold layer (thickness of 0.3 μm) is formed on a nickel layer (thickness of 5 μm) as a metal pad for each of the exposed conductor layers almost similar to those in the first embodiment.
The tensile strength of the solder bumps in the first embodiment, the first modification, the second modification, and the first comparison are measured before and after reliability tests, respectively. Dummy IC's are packaged and the voltage drop quantity of power supplies is determined. The results are compared as shown in
The tensile strength is measured when melting each solder bump formed, burying the tip end portion of a peel measurement equipment, stretching the resultant molten bump in a vertical direction to break the bump.
As a result, in the embodiment, no problems occur to the tensile strength, operation test and the voltage drop quantity at the test, irrespective of the compositions of the solder.
The voltage drop will be described with reference to
Further, the drop quantity of the tensile strength after the reliability test is 2 to 3%. Therefore, no problem occurs with respect to the strength.
In the comparison, by contrast, the tensile strength is lower than that in the embodiment and the drop quantity after the reliability test is 12 to 14%. This shows that there is a problem with the adhesion strength of the adhesion of a solder bump to a solder pad. The voltage drop quantity sometimes exceeds 0.1(V), thus often causing malfunction.
The tensile strength of the BGAs in the first embodiment, the first modification, the second modification, and the first comparison are measured before and after reliability tests, respectively. Dummy IC's are packaged and the voltage drop quantity of power supplies are determined. The results are compared as shown in
The tensile strength is measured when directly pinching each BGA, stretching the BGA in a vertical direction to break the BGA.
As a result, in the first embodiment, the first modification and the second modification, no problems occur to the tensile strength, operation test and the voltage drop quantity at the test, irrespective of the compositions of the solder. In addition, a voltage drop of 0.1(V) or more at which malfunction possibly occurs does not appear, so that it is determined that no malfunction occurs.
Further, the drop quantity of the tensile strength after the reliability test is 2 to 3%. Therefore, no problem occurs with respect to the strength.
In the first comparison, by contrast, the tensile strength is lower than that in the embodiment and the drop quantity after the reliability test is about 12%. This shows that there is a problem with the adhesion strength of the adhesion of a BGA to a solder pad. The voltage drop quantity sometimes exceeds 0.1(V), thus often causing malfunction.
The second embodiment of the present invention will be described hereinafter with reference to the drawings.
The configuration of a printed wiring board according to the second embodiment of the present invention will first be described with reference to
As shown in
As shown in
As shown in
On the printed wiring board 10 in the second embodiment, since the single tin layer 74 is provided on each of the conductor circuits 158 and vias 160 and the conductive adhesive 75 is formed thereon, a signal propagation rate can be increased, as compared with the printed wiring board of the prior art on which the two metal layers are formed as described above with reference to
The thickness of the tin layer 74 is preferably 0.01 to 3.0 μm. If the thickness is less than 0.01 μm, portions which cannot completely cover the conductor circuit 158 or via 160 are generated, adversely influencing strength and corrosion resistance. Conversely, if the thickness exceeds 3.0 μm, the corrosion resistance is not improved. Further, with such a thickness, peeling occurs in the film, thus deteriorating the strength. Besides, it is difficult to form a tin layer of not less than 1.0 μm by substitutional plating. The thickness is more preferably 0.05 to 0.5 μm. In this range, no problem occurs even if there is somewhat a fluctuation in thickness.
On the printed wiring board 10 in this embodiment, a roughened layer 158α is formed on the surface of each of the conductor circuits 158 and vias 160 as shown in
Furthermore, in the second embodiment, the solder bumps 76 and the conductive adhesive 75 are eutectic metals of Sn/Pb, Sn/Sb, Sn/Ag or Sn/Ag/Cu. Since they contain tin, they strongly adhere to the solder pads 73 each of which includes the tin layer 74.
Now, a method for manufacturing the printed wiring board stated above with reference to
Next, the IC chip 90 is mounted on the printed wiring board 10 so that the solder pads 92 of the IC chip 90 correspond to the respective solder bumps 76 of the upper openings 71U of the print wiring board 10, and reflow is conducted, thereby attaching the IC chip 90 onto the printed wiring board 10 (see
In the embodiment stated above, cycloolefin-based resin is used for the interlayer resin insulating layers 50 and 150. Alternatively, epoxy-based resin can be used in place of the cycloolefin-based resin similarly to the first embodiment.
A printed wiring board 110 according to the third modification of the present invention will next be described with reference to
A. an interlayer resin insulating layer resin film, and B. resin filler used in a method for manufacturing the printed wiring board according to the third modification of the present invention are the same as those of the first modification.
A method for manufacturing the printed wiring board stated above with reference to
As the etchant, etchant (manufactured by Mech, Mech-Etch Bond) comprising of 10 parts by weight of an imidazole copper (II) complex, 7 parts by weight of glycolic acid and 5 parts by weight of potassium chloride is used.
Further, heat treatments are conducted for 1 hour at 80° C., for 1 hour at 100° C., for 1 hour at 120° C., and for 3 hours at 150° C., respectively, to harden the solder resist layer's compositions, thus forming solder resist layers 70 each having the opening portions 71U and 71D and a thickness of 20 μm (see
In the third modification, since the noble metal constituting the gold layer 174 is soft gold, it is possible to form single-layer gold films 174 on the conductor circuits 158 and the vias 160 without making nickel intervene and diffusing the gold layers to copper. Namely, according to the prior art, hard gold which enables wire bonding to gold wires is continuously used as gold at the time of establishing connection by the conductive connection pins. Since the hard gold is diffused into the conductor circuits made of copper by electroless plating, films cannot be formed unless the nickel layers intervene. In the third modification, by contrast, it is possible to directly form films on the conductor circuits 158 made of copper and the vias 160. While gold is used herein, platinum or palladium can be used.
A printed wiring board 210 according to the fourth modification of the present invention will be described with reference to
Manufacturing steps of the printed wiring board in the fourth modification will be described. Manufacturing steps (1) to (17) of this fourth modification are equal to those of the third modification described above with reference to
Further, in the fourth modification, the solder bumps 76 and the conductive adhesives 75 are made of eutectic metals of Sn/Ag, Sn/Ag/Cu or Sn/Cn and contain silver, thus ensuring high adhesion to the solder pads 73 each including the silver layer 274. The fourth modification is congenital to the solders which do not contain lead (Sn/Ag and Sn/Ag/Cu), so that these solders can be suitably used in this modification.
In the second embodiment, the third modification, and the fourth modification stated above, the metal layer of each solder pad is formed by substitutional plating. Alternatively, it can be formed by electroless plating with catalyst intervening. The electroless plating is less expensive. However, without the catalyst, non-reaction tends to occur. Besides, it is difficult to control film thickness.
As the second comparison, a gold layer (thickness of 0.3 μm) is formed on a nickel layer (thickness of 5 μm) as a metal pad for each of the exposed conductor layers almost similar to those in the second embodiment.
The tensile strength of the conductive connection pins in the second embodiment, the third modification, the fourth modification, and the second comparison are measured before and after reliability tests, respectively. Dummy IC's are packaged and the voltage drop quantity of power supplies are determined. The results are compared as shown in
The tensile strength is measured when directly pinching the tip end portion of each conductive connection pin, stretching the pin in a vertical direction to break the pin.
As a result, in the embodiment and the modifications, no problems occur to the tensile strength, operation test and the voltage drop quantity at the test, irrespective of the compositions of the solder. In addition, a voltage drop of 0.1(V) or more at which malfunction possibly occurs does not appear, so that it is determined that no malfunction occurs.
Further, the drop quantity of the tensile strength after the reliability test is 2 to 4%. Therefore, no problem occurs in respect of the strength.
In the second comparison, by contrast, the tensile strength is lower than that in the embodiment and the drop quantity after the reliability test is about 12%. This shows that there is a problem with the adhesion strength of the adhesion of a pin to a solder pad. The voltage drop quantity sometimes exceeds 0.1(V), thus often causing malfunction.
As described so far, according to the present invention, the single metal layer is provided on each conductor circuit and the solder pad is formed. Due to this, a signal propagation rate can be increased, as compared with the printed wiring board of the prior art on which the two metal layers are formed. In addition, due to lack of the nickel layers, manufacturing cost can be decreased and electric characteristics can be enhanced.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2001/299668 | Sep 2001 | JP | national |
| 2001/299669 | Sep 2001 | JP | national |
| 2001/299670 | Sep 2001 | JP | national |
This application is a continuation of U.S. Ser. No. 12/261,517 filed Oct. 30, 2008, the entire content of which is incorporated herein by reference. U.S. Ser. No. 12/261,517 is a divisional of U.S. Ser. No. 11/200,077 filed Aug. 10, 2005 which is a divisional of U.S. Ser. No. 10/432,640 filed Jun. 10, 2003, which is a National Stage of PCT/JP02/10144 filed Sep. 30, 2002 and claims priority to 35 U.S.C. §119 to Japanese Application Nos. 2001-299668, 2001-299669 and 2001-299670 filed Sep. 28, 2001.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11200077 | Aug 2005 | US |
| Child | 12261517 | US | |
| Parent | 10432640 | Jun 2003 | US |
| Child | 11200077 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12261517 | Oct 2008 | US |
| Child | 13213240 | US |
