Wiring substrate for bonding using solder having a low melting point and method for manufacturing same

Abstract

There is provided a wiring substrate including an electrode including Cu or a Cu alloy, a plating film having a film including at least Pd, formed on the electrode, and a solder which is bonded onto the plating film by heating, has a melting point of lower than 140 C., and includes Pd dissolved therein, a Pd concentrated layer being absent between the solder and the electrode.

Claims

1. A method for manufacturing a wiring substrate comprising: forming a plating film comprising a film comprising at least Pd on an electrode comprising Cu or a Cu alloy; forming a solder resist layer protecting a portion of the electrode outside of a bonding site of a solder, the solder resist fully covering all side surfaces of the electrode; and bonding, onto the plating film, the solder having a melting point of lower than 140 C. onto the plating film by heating, to uniformly dissolve the Pd in the solder and remove the Pd from the plating film, the bonding the solder onto the plating film by heating being performed under one of the following predetermined thermal conditions: (1) reflow treatment at a time of bonding the solder is performed one to five times under a condition where a peak temperature is 139 C. or higher and 169 C. or lower, a time of maintaining a temperature at 139 C. or higher and 169 C. or lower is shorter than 90 seconds, and a total time of heating treatment including reflow is 300 seconds or shorter, (2) after bonding the solder, a heating treatment of maintaining the temperature at 139 C. or higher and 169 C. or lower for 90 seconds or longer is performed, and (3) reflow treatment at the time of bonding the solder is performed one to five times under a condition where a peak temperature is 139 C. or higher and 169 C. or lower, a total time of heating treatment including reflow is 300 seconds or shorter, and the time of maintaining the temperature at 139 C. or higher and 169 C. or lower is 90seconds or longer.

2. The method for manufacturing a wiring substrate according to claim 1, wherein when the plating film is formed, a thickness of the film comprising Pd is 0.01 m or more and 5 m or less.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a sectional view of a pre-substrate used for the manufacture of a wiring substrate that is related to an exemplary embodiment of the present invention.

(2) FIG. 2 is an enlarged view of the main part of FIG. 1.

(3) FIG. 3 is a sectional view of the periphery of the plating film in the wiring substrate of FIG. 1 where the solder is mounted on the pre-substrate.

(4) FIG. 4 shows images of element mapping of each element of the portion between the electrode and the solder after solder mounting and reflected electron images thereof, in wiring substrates of Examples of the present invention and Comparative Examples.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(5) Basic Structure of Wiring Substrate

(6) A wiring substrate of the present exemplary embodiment is suitable for bonding using solder with a low melting point and is manufactured using a pre-substrate provided with an electrode including Cu or a Cu alloy and a plating film formed on the electrode. The plating film, which has various aspects, may be any one of a multilayer film provided with a Ni plating film, a Pd plating film and a Au plating film, a multilayer film provided with a Pd plating film and a Au plating film, a multilayer film provided with a Ni plating film and a Pd plating film, and a single layer film provided with a Pd plating film.

(7) Also, in the wiring substrate of the present exemplary embodiment, solder (for example, solder layer) including at least Sn and Bi is bonded onto the electrode having the plating film, with a melting point of lower than 140 C. Here, the thickness of the Pd plating film to be stacked and the reflow condition are controlled so as to not form a Pd concentrated layer, which will be described later, between the electrode and the solder, caused by reflow treatment during solder bonding and another heating treatment after thermal bonding by reflow treatment.

(8) Particularly, according to the wiring substrate of the present exemplary embodiment, it is controlled not to form a Pd concentrated layer between the electrode and the solder by any one of the following (1) to (3). (1) Reflow treatment at the time of bonding the solder is performed under a condition where the peak temperature is 139 C. or higher and the time of maintaining the temperature at 139 C. or higher is less than 90 seconds, and the reflow treatment is performed at least once under the same condition. (2) In (1), after bonding the solder, heating treatment of maintaining the temperature at 139 C. or higher for 90 seconds or longer is performed. (3) Reflow treatment at the time of bonding the solder is performed at least once under a condition where a peak temperature is 139 C. or higher and the time of maintaining the temperature at 139 C. or higher is 90 seconds or longer.

(9) The term Pd concentrated layer refers to a layer-shaped aggregate of Pd remaining on the interface between a plating film and an intermetallic compound layer formed by solder bonding, because not all Pd is dissolved in a solder when the solder is bonded onto a single layer plating film or a multilayer plating film including a Pd plating film. When a Pd concentrated layer is formed between an electrode and a solder, the Pd concentrated layer may become a cracking point upon impact, and this may degrade reliability of mounting.

(10) The present application provides a thermal condition where the Pd concentrated layer is not formed in a solder bonding process. Particularly, reflow treatment is performed at least once under a condition where a peak temperature is 139 C. or higher and the time of maintaining the temperature at 139 C. or higher is less than 90 seconds. Alternatively. Pd in the plating film is uniformly dissolved in a solder bulk and is removed by heating treatment where the time of maintaining the temperature at 139 C. or higher is 90 seconds or longer, performed after solder bonding. Alternatively, if the reflow treatment during solder bonding is performed under a condition where a peak temperature is 139 C. or higher and the time of maintaining the temperature at 139 C. or higher is 90 seconds or longer, Pd in the plating film may be uniformly dissolved in a solder bulk even by one reflow, so that no Pd concentrated layer may be formed.

(11) No formation of a Pd concentrated layer allows stable bonding between an electrode and a solder, and this improves reliability of solder mounting.

(12) Hereinafter, one example of the wiring substrate of the present exemplary embodiment will be described in detail.

(13) FIG. 1 is a sectional view of a pre-substrate 1a used for the manufacture of a wiring substrate of the present exemplary embodiment. The pre-substrate 1a is a substrate for electroless plating.

(14) The pre-substrate 1a, as illustrated in FIG. 1, includes an insulating resin substrate 10, an electrode 12 formed on the insulating resin substrate 10, a plating film 14 formed on the electrode 12, and a solder resist layer 16 protecting the electrode 12.

(15) The plating film 14 is formed on the surface of a pad 24 that is a solder bonding site in the electrode 12. In the present exemplary embodiment, as illustrated in FIG. 2, the plating film 14 is a multilayer film which includes a Ni plating film 18, a Pd plating film 20, and a Au plating film 22 layered on the electrode 12. As described above, the plating film may have various aspects. For example, when constituting the plating film with two layers of a Pd plating film and a Au plating film, the Pd plating film 20 and the Au plating film 22 are layered on the electrode 12. When constituting the plating film with only a single layer of a Pd plating film, only the Pd plating film 20 is formed on the electrode 12. In any case, in the present exemplary embodiment, the plating film 14 is configured to include the Pd plating film 20.

(16) When solder 26 (see FIG. 3) is bonded by heating, which will be described later, onto the plating film 14 in the pre-substrate 1a, the Pd plating film 20 and the Au plating film 22 are dissolved in the solder 26. On the bonding interface between the Ni plating film 18 and the solder 26, an intermetallic compound layer 28 is formed as illustrated in FIG. 3.

(17) Examples of an insulating resin constituting the insulating resin substrate 10 may include a glass epoxy resin, a paper epoxy resin, a paper phenol resin, a polyimide film, a polyester film, and the like.

(18) The electrode 12 includes Cu or a Cu alloy. Examples of the Cu alloy that forms a predetermined electric circuit may include an alloy of Cu with Zn, Ni, Sn, Fe, Cr, Mg, Si, P, and the like.

(19) The electrode 12 may be formed by a known process such as subtractive process, semi additive process, additive process, and the like.

(20) Further, the portion of the electrode 12 out of the pad 24 that is the solder bonding site is protected by the solder resist layer 16. The solder resist layer 16 may be formed by a known process such as screen printing process, photolithography process, and the like.

(21) In addition, in the case of a wiring substrate for an electrolytic plating process, an electrode under an insulating resin layer is not independent and is configured to be conductive.

(22) For the Ni plating film 18, either an electroless plating film or an electrolytic plating film may be used. For an electroless Ni plating film, any one in which the eutectoid substance of the plating film includes Pb, S and P; Bi, S and P; or S and P may be used. The electroless Ni plating film including Bi, S and P may be formed using a lead-free electroless Ni plating bath, and the electroless Ni plating film including S and P may be formed using a heavy metal free Ni electroless plating bath. Its eutectoid substances are not limited to Pb, Bi, S, and P, but may include B, C, and H, or any one of Pb, Bi, S, P, B, C, and H. The concentration of each component in the film is not particularly defined.

(23) For an electrolytic Ni plating film, any one of a non-bright plating film, a semi-bright plating film, and a bright plating film may be used. The plating film may be formed using any one of a Watt bath, Weisberg nickel plating bath, black coloring nickel plating bath, strike nickel plating bath, and nickel sulphamate plating bath, as a base.

(24) The thickness of the Ni plating film 18 is preferably 0.5 m or greater, more preferably 3 m to 5 m.

(25) As long as the thickness of the Ni plating film 18 is the lower limit or greater, the thickness of the plating film 14 to be formed tends to be more uniform. Thereby, the thickness of the intermetallic compound layer 28 that is formed on the bonding interface between the plating film and the solder tends to be more uniform, and impact resistance is improved. Setting the thickness of the Ni plating film to 3 m to 5 m may achieve a greater effect. Further, setting the thickness of the Ni plating film 18 to 5 m or thinner may shorten the plating time.

(26) For the Pd plating film 20, either an electroless plating film or an electrolytic plating film may be used. For an electroless Pd plating film, for example, either a known electroless PdP plating film or an electroless pure Pd plating film may be used, and for example, other elements than P may be included therein.

(27) For an electrolytic Pd plating film, any one of a non-bright plating film, a semi-bright plating film, and a bright plating film may be used, and PdNi, PdCo, PdCu and PdIn plating films that are formed with metals different from the eutectoid may be used.

(28) The thickness of the Pd plating film 20 is preferably 0.01 m or greater and 5 m or less, more preferably 0.05 m or greater and 1 m or less. When the thickness of the Pd plating film is less than 0.01 m, a Ni/Pd/Au plating film is formed on an electrode including Cu, and by reflow, solder having a melting point lower than 140 C. and configured to include at least Sn and Bi is bonded by heating under a reflow condition such that the temperature of 139 C. or higher lasts shorter than 90 seconds. In this case, when the Pd plating film is completely dissolved in the solder during the heat bonding process, a large amount of Ni under the Pd plating film is brought into dissolution reaction because the Pd plating film is thin. Here, when the Ni plating film is, for example, an electroless Ni plating film constituted with P as eutectoid, a P-rich layer is formed on the bonding interface between the Ni plating film and the solder, and this degrades reliability of mounting. Thus, this case is not preferable.

(29) On the other hand, when the thickness of the Pd plating film 20 is greater than 5 m, an excessive thermal condition may be required in order to prevent the presence of a Pd concentrated layer.

(30) For the Au plating film 22, either an electroless plating film or an electrolytic plating film may be used. For an electroless Au plating film, a plating film formed by a process, such as displacement Au plating, displacement reduction Au plating, and reduction Au plating, may be used.

(31) For an electrolytic Au plating film, any one of a non-bright plating film, a semi-bright plating film, and a bright plating film may be used.

(32) The thickness of the Au plating film 22 is preferably 0.5 m or less, more preferably 0.05 m or less, in order to obtain sufficient solderability. As long as the thickness of the Au plating film 22 is the upper limit or less, segregation of the intermetallic compound on the bonding interface between the plating film 14 and the solder 26 may be readily inhibited, and reliability of solder mounting may be improved.

(33) When the plating film 14 is a multilayer film including a plurality of layers, there is no specific limitation on a method of forming each layer. In other words, in the plating film, all of the layers may be either an electrolytic plating film or an electroless plating film, or the layers may include an electrolytic plating film and an electroless plating film.

(34) When the solder 26 is bonded onto the plating film 14 of the pre-substrate 1a under a predetermined thermal condition, a wiring substrate 1 of the present exemplary embodiment is obtained.

(35) The solder 26 of the present exemplary embodiment has a melting point of lower than 140 C., and includes at least Sn and Bi. Examples of the solder may include Sn-58 wt % Bi, Sn-57 wt % Bi-1 wt % Ag, Sn-57 wt % Bi-0.5 wt % Sb, and the like.

(36) Thermal condition when the solder 26 is bonded will be described. First, a peak temperature in the reflow condition is maintained to be 139 C. or higher. The time of maintaining the temperature at 139 C. or higher is set to 90 seconds or longer in the case of the thickness of the Pd plating film 18 being 0.1 m or greater and no Pd concentrated layer is generated between the electrode 12 and the solder 26 in one reflow. In the case that a Pd concentrated layer is removed by heating treatment performed after thermal bonding in one reflow, the time of maintaining the temperature at 139 C. or higher in the reflow is set to shorter than 90 seconds.

(37) When the thickness of the Pd plating film 18 is less than 0.1 m, it is possible to prevent a Pd concentrated layer from being generated even in one reflow where the time of maintaining the temperature at 139 C. or higher is shorter than 90 seconds.

(38) For example, when the solder 26 is bonded onto a Ni/Pd/Au plating film or a Ni/Pd plating film by heating, an intermetallic compound layer such as (Cu, Ni).sub.3Sn.sub.4 and Ni.sub.3Sn.sub.4 is formed between the electrode and the solder. When the solder 26 is bonded onto a Pd/Au plating film or a Pd plating film by heating, an intermetallic compound layer consisting of Cu.sub.6Sn.sub.5 and Cu.sub.3Sn is formed on the electrode and the solder.

(39) Pd and Au are dissolved in the solder 26 when the solder 26 is bonded by heating. The Pd plating film 20 has a slower dissolving rate than the Au plating film 22 in the solder. Thus, for example, when the solder is bonded onto the Pd plating film 20 having the thickness of 0.1 m in one reflow performed under a reflow condition where a peak temperature is 139 C. or higher, and the time of maintaining the temperature at 139 C. or higher is shorter than 90 seconds, a Pd concentrated layer is formed on the bonding interface between the plating film 14 and the solder 26, and thus reliability of solder mounting deteriorates. However, when the solder is bonded in one reflow performed under a reflow condition where a peak temperature is 139 C. or higher, and the time of maintaining the temperature at 139 C. or higher is 90 seconds or longer, no Pd concentrated layer is formed between the electrode 12 and the solder 26, and thus reliability of solder mounting improves.

(40) However, when the solder is bonded in one reflow under a reflow condition where a peak temperature is 139 C. or higher, and the time of maintaining the temperature at 139 C. or higher is shorter than 90 seconds, a Pd concentrated layer may be formed between the electrode 12 and the solder 26. In such a case, Pd may be completely dissolved in the solder 26 to remove the Pd layer, by performing repeated reflow or performing heating treatment after bonding at a temperature at 139 C. or higher for 90 seconds or longer. Then, an intermetallic compound layer is uniformly formed on the bonding interface between the plating film 14 and the solder 26, which allows stable bonding, and this improves reliability of solder mounting.

(41) For the above reasons, the present exemplary embodiment can be applied to a substrate, for example, such as FC-BGA, requiring repeated reflow, and after repeated reflow, an intermetallic compound layer is uniformly formed between the electrode and the solder, thereby allowing stable bonding. As a result, the present exemplary embodiment can provide a wiring substrate having high reliability of solder mounting.

(42) Also, from a view point of preventing the solder from hardening in the finished wiring substrate, the total number of reflows is preferably 5 times or less (for example, the number of repetition is 4 times or less), and the total time of heating treatment including reflow is preferably 300 seconds or shorter.

(43) Method for Manufacturing Wiring Substrate

(44) Hereinafter, a method for manufacturing the wiring substrate 1 of the present exemplary embodiment will be described by referring to FIGS. 1 to 3.

(45) The present manufacturing method includes a plating film forming process of forming the plating film 14 on the electrode 12 and a solder bonding process of bonding the solder 26 under a predetermined thermal condition on the plating film.

(46) (Process of Forming Plating Film)

(47) The manufacturing method of the present exemplary embodiment includes the following three processes because the plating film 14 is a three-layered structure.

(48) Process of Ni plating: process of forming the Ni plating film 18 on the electrode 12 by electroless Ni plating or electrolytic Ni plating

(49) Process of Pd plating: process of forming the Pd plating film 20 on the Ni plating film 18 by electroless Pd plating or electrolytic Pd plating

(50) Process of Au plating: process of forming the Au plating film 22 on the Pd plating film 20 by electroless Au plating or electrolytic Au plating

(51) The plating film 14 is formed on the electrode 12 according to the above processes. Further, it is apparent that the details of the present process can be appropriately changed by the specific constitution of the plating film.

(52) (Process of Solder Bonding)

(53) In the process of solder bonding, a solder including at least Sn and Bi, with a melting point of lower than 140 C., described above, is bonded onto the plating film that is on the electrode 12.

(54) By performing the process of solder bonding under the above-described thermal condition, a Pb concentrated layer is not formed from the beginning or is removed after once the Pb concentrated layer has been formed, and thus the Pb concentrated layer is not recognized in the manufactured wiring substrate 1. The intermetallic compound layer 28 is formed on the bonding interface between the plating film 14 and the solder 26.

(55) Hereinafter, each plating process in the process of forming the plating film will be described.

(56) (Process of Ni Plating)

(57) The Ni plating film to be formed may be, but is not specifically limited to, an electroless Ni plating film including Pb in the plating film, a lead-free electroless Ni plating film including Bi and S, and a heavy metal free electroless Ni plating film including S. Here, in the electroless Ni plating film including Pb, the lead-free electroless Ni plating film, the heavy metal free electroless Ni plating film, each electroless Ni plating film 18 may be formed on the electrode 12 by adding a Pd catalyst to the surface of the electrode 12 on the insulating resin surface 10 and immersing each into an electroless Ni plating bath. In the case of electrolytic Ni plating, an electrolytic Ni plating film that is conductive to a substrate to be plated may be formed.

(58) (Process of Pd Plating)

(59) The Pd plating film to be formed may be, but is not specifically limited to, an electroless Pd phosphorus plating film, an electroless pure Pd plating film, an electrolytic Pd plating film, and the like. Here, in the electroless Pd phosphorus plating film and the electroless pure Pd plating film, the electroless Pd plating film 20 may be formed on the electroless Ni plating film 18 by forming the electroless Ni plating film 18 on the surface of the electrode 12 that is on the insulating resin substrate 10 and immersing it into an electroless Pd plating bath. In the case of electrolytic Pd plating film, an electrolytic Pd plating film that is conductive to a substrate to be plated may be formed. Further, either the electroless Pd plating or the electrolytic Pd plating may be formed directly on Cu or a Cu alloy.

(60) (Process of Au Plating)

(61) The Au plating film to be formed may be, but is not specifically limited to, a displacement Au plating film, a displacement reduction Au plating film, a reduction Au plating film, an electrolytic Au plating film, and the like. Here, in the displacement Au plating film, the displacement reduction Au plating film, and the reduction Au plating film, the electroless Au plating film 22 may be formed on the electroless Pd plating film 20 by layering the electroless Ni plating film 18 and the electroless Pd plating film 20 in order on the surface of the electrode 12 that is on the insulating resin substrate 10, and immersing it into an electroless Au plating bath. In the case of electrolytic Au plating, an electrolytic Au plating film that is conductive to a substrate to be plated may be formed.

(62) Hereinafter, Examples of various aspects of the process of solder bonding are provided.

(63) Example 1: A flux is applied on the plating film 14 that is formed on the electrode 12, a solder ball constituted with the solder 26 is mounted thereon, and the thermal bonding is performed under a reflow condition where a peak temperature is 139 C. or higher, and the time of maintaining the temperature at 139 C. or higher is shorter than 90 seconds.

(64) Example 2: A solder paste of the solder 26 is printed on the plating film 14, and the thermal bonding is performed under the above-described reflow condition.

(65) According to these processes, a wiring substrate where a Pd concentrated layer is formed on the bonding interface between the plating film 14 and the solder can be obtained.

(66) Thereafter, the Pd concentrated layer is removed by repeated reflow under the same condition, and thereby the wiring substrate 1 of the present exemplary embodiment is completed.

(67) In another aspect, only one reflow may be performed under a condition where a peak temperature is 139 C. or higher, and the time of maintaining the temperature at 139 C. or higher is 90 seconds or longer, instead of the above-described reflow condition. By doing this, Pd is completely dissolved in a solder bulk, and thus no Pd concentrated layer is generated.

(68) In yet another aspect, after the solder 26 is bonded, the Pd concentrated layer may be removed by performing heating treatment where the time of maintaining the temperature at 139 C. or higher is 90 seconds or longer.

(69) In the thus-formed wiring substrate 1, dissolved Pd is included in the solder 26, and thus no Pd concentrated layer is present between the solder 26 and the electrode 12.

(70) As described above, according to the wiring substrate and the method for manufacturing the wiring substrate of the present exemplary embodiment, the thickness of the Pd plating film in the plating film 14 is set to a predetermined range, and the thermal condition when the solder 26 is bonded is provided as described above. As a result, a structure where no Pd concentrated layer is present by dissolving Pd in a solder bulk, while using the solder having a low melting point, can be obtained, and a wiring substrate with high reliability of bonding can be provided.

(71) Also, as the thermal condition is relatively low temperature, the wiring substrate can be properly manufactured even with a material having not so high thermal resistance.

EXAMPLES

(72) Next, the wiring substrate of the present exemplary embodiment and its manufacturing method are further described with Examples and Comparative Examples. The following description is used to provide examples only, and the present invention is not limited by the following description.

(73) First, a basic substrate that is used for the manufacture of a pre-substrate is described.

(74) (Manufacture of Basic Substrate)

(75) Electrolytic Cu plating was performed on a copper coated laminate that is made of a glass epoxy resin, having the thickness of 0.8 mm, and the portion out of a pad (having a diameter of 300 m) is coated with a solder resist (product name: AUS308, manufactured by TAIYO INK MFG. CO., LTD.), to obtain a basic substrate having an electrode 12 consisting of Cu.

(76) (Pre-Substrate 1)

(77) The Ni plating film 18 having the thickness of 3 m was formed on the electrode 12 of the above-mentioned basic substrate, using an electroless Ni plating bath (bath temperature: 81 C.) in which sulfuric acid Ni (20 g/L), sodium hypophosphite (20 g/L) as a reducing agent, lactic acid (30 g/L) as a complexing agent, lead nitrate as a lead salt, and thiourea as a sulfur-based compound were dissolved in water.

(78) Then, the Pd plating film 20 having the thickness of 0.1 m was formed on the Ni plating film 18, using an electroless Pd plating bath (bath temperature: 43 C.) including Tetraammine Pd (0.8 g/L as Pd), sodium hypophosphite (10 g/L), bismuth nitrate (2 mg/L), and phosphoric acid (10 g/L).

(79) Thereafter, the Au plating film 22 having the thickness of 0.05 m was formed on the Pd plating film 20, using an electroless Au plating bath (bath temperature: 86 C.) including potassium Au cyanide (1.0 g/L as Au), thiosulfuric acid (1 mg/L), citric acid (25 g/L), and phosphoric acid (10 g/L). Thereby, the plating film 14 in which the electroless Ni plating film/electroless Pd plating film/electroless Au plating film were layered was formed on the electrode 12.

(80) (Pre-Substrate 2)

(81) The lead-free Ni plating film 18 having the thickness of 3 m was formed on the electrode 12 of the basic substrate, using an electroless Ni plating bath (bath temperature: 81 C.) in which sulfuric acid Ni (20 g/L), sodium hypophosphite (20 g/L) as a reducing agent, lactic acid (30 g/L) as a complexing agent, bismuth nitrate as a bismuth salt, and thiourea as a sulfur-based compound were dissolved in water.

(82) Then, the Pd plating film 20 having the thickness of 0.1 m was formed on the Ni plating film 18, using an electroless Pd plating bath (bath temperature: 43 C.) including Tetraammine Pd (0.8 g/L as Pd), sodium hypophosphite (10 g/L), bismuth nitrate (2 mg/L), and phosphoric acid (10 g/L).

(83) Thereafter, the Au plating film 22 having the thickness of 0.05 m was formed on the Pd plating film 20, using an electroless Au plating bath (bath temperature: 86 C.) including potassium Au cyanide (1.0 g/L as Au), thiosulfuric acid (I mg/L), citric acid (25 g/L), and phosphoric acid (10 g/L). Thereby, the plating film 14 in which the lead-free electroless Ni plating film/electroless Pd plating film/electroless Au plating film were layered was formed on the electrode 12.

(84) (Pre-Substrate 3)

(85) The lead-free Ni plating film having the thickness of 3 m was formed on the electrode 12 of the basic substrate, using an electroless Ni plating bath (bath temperature: 81 C.) in which sulfuric acid Ni (20 g/L), sodium hypophosphite (20 g/L) as a reducing agent, lactic acid (30 g/L) as a complexing agent, bismuth nitrate as a bismuth salt, and thiourea as a sulfur-based compound were dissolved in water.

(86) Thereafter, the Au plating film having the thickness of 0.05 m was formed on the Ni plating film, using an electroless Au plating bath (bath temperature: 86 C.) including potassium Au cyanide (1.0 g/L as Au), thiosulfuric acid (1 mg/L), citric acid (25 g/L), and phosphoric acid (10 g/L). Thereby, the plating film in which the lead-free electroless Ni plating film/electroless Au plating film were layered was formed on the electrode 12.

(87) (Pre-Substrate 4)

(88) The Pd plating film 20 having the thickness of 2.7 m was formed on the electrode 12 of the basic substrate, using an electroless Pd plating bath (bath temperature: 43 C.) including Tetraammine Pd (0.8 g/L as Pd), sodium hypophosphite (10 g/L), bismuth nitrate (2 mg/L), and phosphoric acid (10 g/L).

(89) Thereafter, the Au plating film 22 having the thickness of 0.06 m was formed on the Pd plating film 20, using an electroless Au plating bath (bath temperature: 86 C.) including potassium Au cyanide (1.0 g/L as Au), thiosulfuric acid (1 mg/L), citric acid (25 g/L), and phosphoric acid (10 g/L). Thereby, the plating film 14 in which the electroless Pd plating film/electroless Au plating film were layered was formed on the electrode 12.

(90) (Pre-Substrate 5)

(91) The Pd plating film having the thickness of 2.7 m was formed on the electrode 12 of the basic substrate, using an electroless Pd plating bath (bath temperature: 43 C.) including Tetraammine Pd (0.8 g/L as Pd), sodium hypophosphite (10 g/L), bismuth nitrate (2 mg/L), and phosphoric acid (10 g/L). Thereby, the plating film 14 with the single-layer electroless Pd plating film was formed on the electrode 12.

(92) (Pre-Substrate 6)

(93) The plating film 14 of a multilayer structure was formed on the electrode 12 of the basic substrate such that the thickness of the Ni plating film 18 is 4.4 m, the thickness of the Pd plating film 20 is 0.33 m, and the thickness of the Au plating film 22 is 0.07 m, using a Ni sulfamate plating bath (bath temperature: 50 C.) including Ni sulfamate (600 g/L), Ni chloride (5 g/L), and boric acid (40 g/L), a commercialized Pd plating bath (bath temperature: 25 C.), and a bright Au plating bath (bath temperature: 60 C.) including cyanide Au potassium (10 g/L), potassium monohydrogen phosphate (45 g/L), and a chelating agent (45 g/L).

Example 1

(94) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film 14 of the above-described pre-substrate 1, and reflow was preformed five times under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Example 1 was obtained. 10 specimens of Example 1 were manufactured.

Comparative Example 1

(95) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 1, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 1 was obtained. Ten specimens of Comparative Example 1 were manufactured.

Example 2

(96) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 1, and reflow was preformed five times under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Example 2 was obtained. Ten specimens of Example 2 were manufactured.

Comparative Example 2

(97) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 1, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 2 was obtained. 10 specimens of Comparative Example 2 were manufactured.

Example 3

(98) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 2, and reflow was preformed five times under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Example 3 was obtained. Ten specimens of Example 3 were manufactured.

Comparative Example 3

(99) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 2, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 3 was obtained. Ten specimens of Comparative Example 3 were manufactured.

Example 4

(100) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 2, and reflow was preformed five times under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Example 4 was obtained. Ten specimens of Example 4 were manufactured.

Comparative Example 4

(101) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 2, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 4 was obtained. Ten specimens of Comparative Example 4 were manufactured.

Comparative Example 4-1

(102) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film of the pre-substrate 3, and reflow was preformed five times under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 4-1 was obtained. Ten specimens of Comparative Example 4-1 were manufactured.

Comparative Example 4-2

(103) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film of the pre-substrate 3, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 4-2 was obtained. Ten specimens of Comparative Example 4-2 were manufactured.

Comparative Example 4-3

(104) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film of the pre-substrate 3, and reflow was preformed five times under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 4-3 was obtained. Ten specimens of Comparative Example 4-3 were manufactured.

Comparative Example 4-4

(105) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film of the pre-substrate 3, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 4-4 was obtained. Ten specimens of Comparative Example 4-4 were manufactured.

Example 5

(106) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 4, and reflow was preformed five times under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Example 5 was obtained. Ten specimens of Example 5 were manufactured.

Comparative Example 5

(107) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 4, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 5 was obtained. Ten specimens of Comparative Example 5 were manufactured.

Example 6

(108) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 4, and reflow was preformed five times under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Example 6 was obtained. Ten specimens of Example 6 were manufactured.

Comparative Example 6

(109) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 4, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 6 was obtained. Ten specimens of Comparative Example 6 were manufactured.

Example 7

(110) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 5, and reflow was preformed five times under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Example 7 was obtained. Ten specimens of Example 7 were manufactured.

Comparative Example 7

(111) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 5, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 7 was obtained. Ten specimens of Comparative Example 7 were manufactured.

Example 8

(112) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 5, and reflow was preformed five times under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Example 8 was obtained. Ten specimens of Example 8 were manufactured.

Comparative Example 8

(113) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 5, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 8 was obtained. Ten specimens of Comparative Example 8 were manufactured.

Example 9

(114) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 6, and reflow was preformed five times under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Example 9 was obtained. Ten specimens of Example 9 were manufactured.

Comparative Example 9

(115) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 6, and reflow was preformed once under a condition where the peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 9 was obtained. Ten specimens of Comparative Example 9 were manufactured.

Example 10

(116) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 6, and reflow was preformed five times under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Example 10 was obtained. 10 specimens of Example Ten were manufactured.

Comparative Example 10

(117) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 6, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 60 seconds. Thereby, a wiring substrate of Comparative Example 10 was obtained. Ten specimens of Comparative Example 10 were manufactured.

Example 11

(118) A solder ball made of Sn-58 wt % Bi, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 1, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 90 seconds. Thereby, a wiring substrate of Example 11 was obtained. Ten specimens of Example 11 were manufactured.

Example 12

(119) A solder ball made of Sn-57 wt % Bi-0.5 wt % Sb, with a diameter of 350 m, was mounted on the plating film 14 of the pre-substrate 1, and reflow was preformed once under a condition where a peak temperature was 169 C. and the time of maintaining the temperature at 139 C. or higher was 90 seconds. Thereby, a wiring substrate of Example 12 was obtained. Ten specimens of Example 12 were manufactured.

(120) (Evaluation Method)

(121) With respect to the specimens of Examples 1 to 4, Comparative Examples 1 to 4, and Comparative Examples 4-1 to 4-4, slow shear testing was performed using a bonding tester (Model: PTR-1102, manufactured by Rhesca Corporation), to evaluate the reliability of solder mounting with solder failure modes. Failure modes indicate that with respect to the area in the plane of the electrode 12, the remaining amount of solder that is 70% or larger is a solder failure mode, that 30 to 70% is a solder+IMC failure mode, and that 30% or smaller is an IMC failure mode. As the rate of solder failure mode is higher, the reliability of solder mounting is better.

(122) With respect to the specimens of Examples 5 to 12 and Comparative Examples 5 to 10, the reliability of solder mounting was evaluated with bonding strength during the slow shear test, because a difference in the rate of solder failure modes was not recognizable in the slow shear test performed according to the above-described manner.

(123) (Evaluation Results)

(124) The evaluation results on Examples 1 to 4, Comparative Examples 1 to 4, and Comparative Examples 4-1 to 4-4 is shown in Table 1. Also, the bonding strength during the slow shear test is shown.

(125) TABLE-US-00001 TABLE 1 Evaluation results of reliability Specimen of solder mounting Time of Rate of each failure mode (%) Type of Number maintaining Solder + Bonding plating of 139 C. or Solder IMC IMC strength film Type of solder reflow higher (s) failure failure failure (N) Example 1 Electroless Sn58wt%Bi 5 300 40 60 0 4.854 Ni/Pd/Au Comparative Electroless Sn58wt%Bi 1 60 0 70 30 4.627 Example 1 Ni/Pd/Au Example 2 Electroless Sn57wt%Bi0.5wt%Sb 5 300 80 20 0 4.826 Ni/Pd/Au Comparative Electroless Sn57wt%Bi0.5wt%Sb 1 60 10 80 10 4.464 Example 2 Ni/Pd/Au Example 3 Lead-free Sn58wt%Bi 5 300 70 30 0 5.117 electroless Ni/Pd/Au Comparative Lead-free Sn58wt%Bi 1 60 0 80 20 4.310 Example 3 electroless Ni/Pd/Au Example 4 Lead-free Sn57wt%Bi0.5wt%Sb 5 300 70 30 0 4.846 electroless Ni/Pd/Au Comparative Lead-free Sn57wt%Bi0.5wt%Sb 1 60 50 50 0 4.802 Example 4 electroless Ni/Pd/Au Comparative Lead-free Sn58wt%Bi 5 300 20 80 0 4.961 Example 4-1 electroless Ni/Au Comparative Lead-free Sn58wt%Bi 1 60 70 30 0 5.116 Example 4-2 electroless Ni/Au Comparative Lead-free Sn57wt%Bi0.5wt%Sb 5 300 30 70 0 4.888 Example 4-3 electroless Ni/Au Comparative Lead-free Sn57wt%Bi0.5wt%Sb 1 60 60 40 0 5.059 Example 4-4 electroless Ni/Au

(126) As shown in Table 1, when using the plating film of multilayer structure including the electroless Ni/Pd/Au plating, the specimens after 5 reflow treatments have higher rates of solder failure mode, and exhibit higher reliability of solder mounting compared with those of the Comparative Examples (where reflow was performed only once) corresponding to the each Example. The effect is also applied to the case where the Ni plating film 18 is a lead-free electroless Ni plating film, as shown in Examples 3 to 4 and Comparative Examples 3 to 4.

(127) According to Comparative Examples 4-1 to 4-4 using the plating film of multilayer structure consisting of the lead-free electroless Ni/Au, the rate of solder failure mode is lowered down to 30% or lower after 5 times reflow. Thus, low reliability of solder mounting is observed.

(128) From the above, it is demonstrated that in the wiring substrate of the present exemplary embodiment using the plating film including the Pd plating film, high reliability of solder mounting can be achieved after repeated reflow. The present exemplary embodiment is applicable to the use where reflow resistance is required.

(129) FIG. 4 shows images of element mapping of bonding sections in the wiring substrates of Example 1 and Comparative Example 1 where Sn-58 wt % Bi solder is mounted. As seen from the left images in FIG. 4, in the wiring substrate of Example 1, no Pd concentrated layer between the electrode and the solder is recognized, whereas in the wiring substrate of Comparative Example 1, in the right images in FIG. 4, Pd is distributed in the form of a layer, and a Pd concentrated layer is recognized. From the presence or absence of a Pd concentrated layer and the evaluation results of the reliability of solder mounting, it is demonstrated that the reliability of solder mounting is improved by having Pd dissolved uniformly in a solder bulk, in a solder bonding process.

(130) Next, evaluation results of Examples 5 to 12 and Comparative Examples 5 to 10 is shown in Table 2.

(131) TABLE-US-00002 TABLE 2 Evaluation results of Specimen reliability of solder Number Time of maintaining mounting Type of plating film Type of solder of reflow 139 C. or higher (s) Bonding strength (N) Example 5 Electroless Pd/Au Sn58 wt % Bi 5 300 5.410 Comparative Electroless Pd/Au Sn58 wt % Bi 1 60 3.570 Example 5 Example 6 Electroless Pd/Au Sn57 wt % Bi0.5 wt % Sb 5 300 4.902 Comparative Electroless Pd/Au Sn57 wt % Bi0.5 wt % Sb 1 60 3.374 Example 6 Example 7 Electroless Pd Sn58 wt % Bi 5 300 4.681 Comparative Electroless Pd Sn58 wt % Bi 1 60 4.272 Example 7 Example 8 Electroless Pd Sn57 wt % Bi0.5 wt % Sb 5 300 4.969 Comparative Electroless Pd Sn57 wt % Bi0.5 wt % Sb 1 60 4.275 Example 8 Example 9 Electrolytic Sn58 wt % Bi 5 300 5.270 Ni/Pd/Au Comparative Electrolytic Sn58 wt % Bi 1 60 4.712 Example 9 Ni/Pd/Au Example 10 Electrolytic Sn57 wt % Bi0.5 wt % Sb 5 300 4.983 Ni/Pd/Au Comparative Electrolytic Sn57 wt % Bi0.5 wt % Sb 1 60 4.414 Example 10 Ni/Pd/Au Example 11 Electroless Ni/Pd/Au Sn58 wt % Bi 1 90 5.599 Example 12 Electroless Ni/Pd/Au Sn57 wt % Bi0.5 wt % Sb 1 90 5.522

(132) As seen from Table 2, when using the plating film of multilayer structure consisting of electroless Pd/Au plating, the plating film of single layer consisting of electroless Pd plating, and the plating film of multilayer structure consisting of electrolytic Ni/Pd/Au, the specimens after 5 times reflow have higher solder bonding, and exhibit higher reliability of solder mounting compared with Comparative Examples corresponding to the each Example. Also, as shown in Examples 11 to 12, in the case where the time of maintaining the temperature at 139 C. or higher is set to 90 seconds, even though reflow is performed only once, the increase in bonding strength is recognized compared with Comparative Examples 1 and 2.

(133) Also, from the results of Examples 3 to 4, Comparative Examples 3 to 4, Examples 9 to 10, and Comparative Examples 9 to 10, the increase in bonding strength after 5 times reflow is recognized, irrespective of whether the type of Ni plating film is a lead-free Ni plating film or an electrolytic Ni plating film.

(134) The foregoing exemplary embodiments and Examples of the present invention are described but the technical scope of present invention is not limited to the exemplary embodiments. Various changes of combinations of elements can be made or modifications to each element can be added or deleted, without departing from the idea of the invention.