Method for manufacturing a metal structure for an opto-semiconductor device, package, and solution containing a polyallylamine polymer

Abstract

A metal structure for an optical semiconductor device with improved adhesion to a resin material (3) is manufactured by impregnating and / or coating a substrate (10) having a topmost layer containing at least one selected from gold, silver, gold alloys, and silver alloys on a part or the whole surface with a solution containing a polyallylamine polymer.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a metal structure for an opto-semiconductor device, a package, and a solution containing a polyallylamine polymer. Background Art

[0002] An opto-semiconductor device including a semiconductor light-emitting element such as a light-emitting diode (hereinafter also referred to as "LED") is used, for example, as a light source for vehicles, a light source for general lighting, a backlight for a liquid crystal display device, a light source for a projector, or the like.

[0003] In an opto-semiconductor device, a lead frame or a substrate having a coating film of silver or a silver alloy having a high reflectivity to light from a light-emitting element is usually used on the surface. On the other hand, since silver or a silver alloy is easily sulfided by a sulfide, an opto-semiconductor device having a substrate having a gold coating film excellent in sulfidation resistance provided on the surface is sometimes used (for example, see Patent Documents 1 and 2). An opto-semiconductor device having a lead frame or a substrate having gold or a gold alloy provided on the surface can be used, for example, as an opto-semiconductor device for vehicles that requires high reliability.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-347596

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2006-093365 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] An object of the present application is to provide a method for manufacturing a metal structure for an opto-semiconductor device with improved adhesion to a resin material.

[0010] Means for Solving the Problems

[0011] A method for manufacturing a metal structure for an opto-semiconductor device according to an embodiment of the present invention includes:

[0012] (1) A treatment step of impregnating and / or coating a substrate having a top layer having a plating material containing at least one selected from gold, silver, a gold alloy, and a silver alloy on a part or the whole surface with a solution containing a polyallylamine polymer.

[0013] The package according to an embodiment of the present invention includes a substrate and a resin molded body formed on the substrate. The substrate has a topmost layer having at least one plating material selected from gold, silver, gold alloy, and silver alloy on a part or the whole of its surface, and a polyallylamine polymer is attached to the topmost layer of the substrate.

[0014] A solution containing a polyallylamine polymer according to an embodiment of the present invention is used to improve the adhesion between the lead frame and the adjacent resin molded body in an optical semiconductor device.

[0015] A method for manufacturing a metal structure for an optical semiconductor device according to an embodiment of the present invention includes: (1) a processing step of impregnating and / or coating a solution containing a polyallylamine polymer on a substrate having a topmost layer with at least one selected from gold, silver, gold alloy, and silver alloy on a part or the whole of its surface.

[0016] Effects of the Invention

[0017] According to the present application, a method for manufacturing a metal structure for an optical semiconductor device with improved adhesion to a resin material can be provided. Description of the Drawings

[0018] Figure 1 (A) is a top view schematic diagram showing an optical semiconductor device according to an embodiment. (B) is a cross-sectional schematic diagram of the cross-section along the Figure 1 (A)'s X-X line of the optical semiconductor device.

[0019] Figure 2 (A) is a cross-sectional schematic diagram of a part of a metal structure for an optical semiconductor device according to an embodiment. (B) is a cross-sectional schematic diagram of a part of a metal structure for an optical semiconductor device according to another embodiment.

[0020] Figure 3 (A) is a three-dimensional schematic diagram showing an optical semiconductor device according to another embodiment. (B) is a cross-sectional schematic diagram of the cross-section along the Figure 3 (A)'s Y-Y line of the optical semiconductor device.

[0021] Figure 4 It is a cross-sectional schematic diagram of a manufacturing process for explaining the manufacturing method of the (A) optical semiconductor device. (B) is a cross-sectional schematic diagram of a manufacturing process for explaining the manufacturing method of the optical semiconductor device. (C) is a cross-sectional schematic diagram of a manufacturing process for explaining the manufacturing method of the optical semiconductor device. (D) is a cross-sectional schematic diagram of a manufacturing process for explaining the manufacturing method of the optical semiconductor device.

[0022] Symbol Explanation

[0023] 1 Metal structure for optical semiconductor device

[0024] 1a Base material

[0025] 1b Nickel or nickel alloy coating

[0026] 1c Base layer

[0027] 1c1 Precious metal coating

[0028] 1c2 Gold or gold alloy coating

[0029] 1d Outermost layer of gold, silver, gold alloy or silver alloy

[0030] 12 First embedding part

[0031] 13 Second embedding part

[0032] 2 Light-emitting element

[0033] 3 Resin molded body

[0034] 31 Side wall part

[0035] 32 Part of the bottom surface

[0036] 4 Joining member

[0037] 5 Sealing member

[0038] 6 Lead wire

[0039] 10 Lead frame

[0040] 100 Opto-semiconductor device

[0041] 200 Opto-semiconductor device Detailed implementation mode

[0042] Hereinafter, the embodiments of the invention will be described with appropriate reference to the drawings. However, the manufacturing method of the metal structure for the opto-semiconductor device, the package, and the solution containing the polyallylamine polymer described below are examples for embodying the technical idea of the present invention. The present invention is not limited to the following embodiments unless otherwise specified. In addition, the composition of the plating solution and the plating operation conditions described in the embodiments are examples. In addition, the content described in the embodiments can also be applied to other embodiments. Sometimes, the sizes and positional relationships of the components shown in the drawings are exaggerated for clarity. In the following description, the same names or symbols generally represent the same or homogeneous components, and the detailed description is appropriately omitted.

[0043] It should be noted that in this specification, "containing" is a concept that encompasses any of the meanings of "comprise", "consist essentially of", and "consist of". Additionally, in this specification, when expressing a numerical range as A to B, it means greater than or equal to A and less than or equal to B.

[0044] Embodiment 1: Optical semiconductor device (1)

[0045] In Figure 1 A and Figure 1 B shows the structure of the optoelectronic semiconductor device 100 of Embodiment 1. The optoelectronic semiconductor device 100 of this embodiment includes: a light-emitting element 2 that is rectangular in plan view, a lead frame 10 formed of a pair of plate-like metal structures 1 for optoelectronic semiconductor devices (hereinafter also simply referred to as "lead frame 10"), and a resin molded body 3 in which part of the lead frame 10 is embedded.

[0046] The resin molded body 3 can be composed of a resin composition containing a thermoplastic resin or a thermosetting resin. Additionally, the resin molded body 3 can contain, in the resin composition, TiO as described later 2Filling materials (fillers) such as these. The filling material can serve as a reflective material that reflects light from the light-emitting element 2. The resin molded body 3 forms a recess having a bottom surface and side surfaces, and the bottom surface of the recess is constituted by a part of a pair of lead frames 10. A side wall portion 31 is formed on the side surface as a reflective surface having a given inclination angle. The space between the pair of lead frames 10 is filled with a resin composition that constitutes the resin molded body 3, forming a part 32 of the bottom surface of the resin molded body 3. The resin molded body 3 of the present embodiment has a horizontally long shape when viewed from above. On the outer surface of the resin molded body 3, a part of a pair of plate-like lead frames 10 is exposed as an external terminal portion, and the external terminal portion is bent along the lower surface of the resin molded body 3. The light-emitting element 2 is mounted on one of the lead frames 10 that constitutes the bottom surface of the recess. The light-emitting element 2 is covered with a sealing member 5. The sealing member 5 contains, for example, a phosphor that performs wavelength conversion on the light from the light-emitting element 2 and a sealing material. The material of the sealing member 5 preferably contains a light-transmissive resin. The phosphor is excited by the light from the light-emitting element 2, performs wavelength conversion on the light from the light-emitting element 2, and emits light having at least one emission peak wavelength in a specific wavelength range. In addition, the light-emitting element 2 has a pair of positive and negative electrodes, and the pair of positive and negative electrodes are electrically connected to the pair of lead frames 10 via wires 6 respectively. Electric power can be supplied from the outside via the pair of lead frames 10 to cause the optoelectronic device 100 to emit light. The lead frame 10 or the substrate constituted by the metal structure for optoelectronic devices described in the embodiments to be described later has a portion that contacts members formed of resin materials such as the resin molded body 3 and the sealing member 5. At this time, the package including the metal structure 1 for optoelectronic devices that constitutes the lead frame 10 or the substrate and the resin molded body 3 constitutes the present embodiment, and the adhesion between the metal structure 1 for optoelectronic devices that constitutes the lead frame 10 or the substrate and the resin molded body 3 is improved. It should be noted that the metal structure 1 for optoelectronic devices that constitutes the lead frame 10 or the substrate will be described in detail later. In this specification, the resin material refers to a material that contains at least resin. Examples of the resin material include resin compositions containing resin and the like.

[0047] The lead frame 10 constituted by the metal structure 1 for optoelectronic devices has functions as a mounting member for mounting the light-emitting element 2, a reflective member for reflecting the light emitted from the light-emitting element 2, and a conductive member for electrically connecting to the light-emitting element 2. In addition, the lead frame 10 can also have a function as a heat dissipation member for diffusing the heat generated from the light-emitting element 2. The lead frame 10 constituted by the metal structure 1 for optoelectronic devices can be disposed below the light-emitting element 2 as in Embodiment 1, or can be formed in a reflector shape surrounding the light-emitting element 2. In addition, the lead frame 10 can also be a plate-like lead frame.

[0048] In addition, the metal structure 1 for an opto-semiconductor device has a outermost layer 1d made of gold, silver, a gold alloy or a silver alloy formed by a process of impregnating and / or coating a solution containing a polyallylamine polymer. Therefore, the adhesion to the resin is good, and in the opto-semiconductor device 100, for example, the adhesion to the sealing member 5 and the resin molded body 3 can be improved. It should be noted that the method for forming the outermost layer 1d is not particularly limited as long as it is a known surface treatment. For example, plating (electroplating, electroless plating, hot dip plating, sputtering, vapor deposition including physical vapor deposition and chemical vapor deposition), thermal spraying, etc. can be used. Generally, in an opto-semiconductor device, in order to increase the reflectance of the resin molded body and increase the total luminous flux, the content of filling materials such as TiO 2 etc. in the resin molded body may be increased, or in order to improve the color rendering property, the content of the phosphor in the sealing member may be increased. If a large amount of such impurities are added to the resin material, there is a tendency for the adhesion between the lead frame of the opto-semiconductor device and the resin material to decrease. On the other hand, the lead frame 1 of the opto-semiconductor device 100 according to the present embodiment, which is composed of the metal structure 1 for an opto-semiconductor device, has high adhesion to the resin material. Therefore, even when the content of impurities (such as titanium oxide and phosphor) in the resin material is increased, in the process of mounting the opto-semiconductor device 100 using the lead frame 1 on the printed circuit board by reflow soldering, it is possible to prevent solder from entering the opto-semiconductor device 100 and the sealing material from leaking outside the resin molded body 3. It should be noted that the solution containing the polyallylamine polymer will be described in detail later.

[0049] Furthermore, the metal structure 1 for an opto-semiconductor device has a outermost layer 1d made of gold, silver, a gold alloy or a silver alloy formed by a process of impregnating and / or coating a solution containing a polyallylamine polymer. Therefore, even when there is a silver or silver alloy plating as the outermost layer, discoloration caused by sulfidation or oxidation can be suppressed, and a decrease in luminous flux caused by sulfidation discoloration or oxidation discoloration can be suppressed, maintaining a high luminous flux.

[0050] Embodiment 2: Metal structure for optical semiconductor device (1)

[0051] The metal structure 1 for an opto-semiconductor device can be used for a lead frame, a substrate. In addition, by forming the metal structure 1 for an opto-semiconductor device as a wiring on an insulating substrate, it can be used for a printed circuit board, a ceramic substrate, etc. In the present application, a substrate refers to a member that can have the metal structure 1 for an opto-semiconductor device. For example, it can be a lead frame, a metal plate, a wire, a ceramic component with a metal terminal such as a ceramic substrate, a printed circuit board, a flexible substrate, a silicon wafer, a GaAs wafer, a GaN wafer, a capacitor, an organic component with a metal terminal such as a resistor, a pin connector, a circular connector, a socket, a connector with resin, an airtight component such as a laser bar.

[0052] Figure 2 FIG. A is a cross-sectional schematic view showing one embodiment of the metal structure 1 for an opto-semiconductor device.

[0053] The metal structure 1 for an opto-semiconductor device may include at least one selected from a nickel or nickel alloy plating layer, a palladium or palladium alloy plating layer, a rhodium or rhodium alloy plating layer, and a platinum or platinum alloy plating layer between the outermost layer and the base material 1a.

[0054] As Figure 2 As shown in FIG. A, the metal structure 1 for an opto-semiconductor device may successively have, in a pair of two surfaces facing each other with the base material 1a as the center: for example, a conductive base material 1a containing copper or a copper alloy, a nickel or nickel alloy plating layer 1b formed on the base material 1a, and an outermost layer 1d of gold, silver, a gold alloy, or a silver alloy formed by treating with an impregnation and / or coating of a solution containing a polyallylamine polymer.

[0055] From the viewpoint of improving the reliability by improving the chip bonding property, wire bonding property, and solder mounting property with the light-emitting element 2, the metal structure 1 for an opto-semiconductor device has gold, silver, a gold alloy, or a silver alloy as the outermost layer. The Vickers hardness of gold and silver is less than that of nickel, palladium, rhodium, and platinum, and they are soft metals. Therefore, chip bonding and wire bonding of the light-emitting element 2 are easy. In addition, gold and silver are noble metals and are less likely to be oxidized compared with nickel, palladium, rhodium, and platinum. Therefore, they are less likely to affect solder mounting.

[0056] When the outermost layer of the metal structure 1 for an opto-semiconductor device is a gold or gold alloy layer, it is preferable to form a gold or gold alloy plating layer as the outermost layer 1d. In addition, when the outermost layer 1d is a silver or silver alloy layer, it is preferable to form a silver or silver alloy plating layer as the outermost layer 1d and form a gold or gold alloy plating layer 1c2 as the base layer of the silver or silver alloy plating layer. This is because gold is a more stable metal than silver. That is, when the outermost layer 1d is a silver or silver alloy layer, a gold or gold alloy plating layer 1c2 may be provided between the nickel or nickel alloy plating layer 1b and the outermost layer 1d.

[0057] It should be noted that the details of the outermost layer 1d of gold, silver, a gold alloy, or a silver alloy will be described later.

[0058] A pair of two opposing surfaces of the plate-shaped base material 1a are sometimes referred to as the upper surface or the bottom surface, and the other pair of two opposing surfaces of the plate-shaped base material 1a are sometimes referred to as the side surfaces.

[0059] The outermost layer 1d of gold, silver, a gold alloy, or a silver alloy does not have to be provided on the entire surface of the metal structure 1 for an opto-semiconductor device. That is, at least a part of the surface of the metal structure 1 for an opto-semiconductor device may be the outermost layer 1d of gold, silver, a gold alloy, or a silver alloy. For example, for those not in Figure 1In the lead frame 10 where the bottom surface of the concave portion of the resin molded body 3 shown is exposed, for the first buried portion 12 buried inside the side wall portion 31 of the resin molded body 3 and the second buried portion 13 that is bonded to the sealing member 5, from the viewpoint of adhesion to the resin, it is preferably provided with a topmost layer 1d of gold, silver, gold alloy or silver alloy formed by treating with a solution containing a polyallylamine polymer by impregnation and / or coating on its surface. However, for the external terminal portion exposed outside the resin molded body 3 and the mounting portion exposed on the bottom surface side of the optoelectronic device, the topmost layer 1d of gold, silver, gold alloy or silver alloy may not be provided on its surface. In order to provide the topmost layer 1d of gold, silver, gold alloy or silver alloy on a part of the metal structure 1 for optoelectronic devices as described above, when forming the topmost layer 1d of gold, silver, gold alloy or silver alloy, parts that do not require the topmost layer 1d of gold, silver, gold alloy or silver alloy can be masked with a protective tape or the like, and the topmost layer 1d of gold, silver, gold alloy or silver alloy is formed on a part of the surface.

[0060] For the topmost layer 1d of gold, silver, gold alloy or silver alloy formed by treating with a solution containing a polyallylamine polymer by impregnation and / or coating, if it is a portion that is not directly bonded to the resin molded body 3 or the sealing member 5, it can be provided on both of a pair of opposed surfaces of the plate-shaped metal structure 1 for optoelectronic devices like in the present embodiment, such as the upper surface and the bottom surface, or it can be provided only on a certain surface and not on the other surface. Additionally, it can also be provided only on a part of one surface. Moreover, the topmost layer 1d of gold, silver, gold alloy or silver alloy formed by treating with a solution containing a polyallylamine polymer by impregnation and / or coating has the same thickness throughout the region where the topmost layer 1d is provided, or the thickness can also be different. By making the thickness different, the cost can be reduced more effectively. For example, the topmost layer 1d of gold, silver, gold alloy or silver alloy formed by treating with a solution containing a polyallylamine polymer by impregnation and / or coating can be provided on the upper surface and the bottom surface of the metal structure 1 for optoelectronic devices, and the thickness on one surface is thicker than that on the other surface. By providing the topmost layer 1d of gold, silver, gold alloy or silver alloy formed by treating with a solution containing a polyallylamine polymer by impregnation and / or coating on the portion directly bonded to the resin molded body 3 or the sealing member 5, for example, when mounting the optoelectronic device 100 on a printed circuit board by reflow soldering, the intrusion of solder into the optoelectronic device 100 can be more effectively suppressed.

[0061] [Base material 1a]

[0062] The optical semiconductor device metal structure 1 has a base material 1a having an outermost layer 1d of gold, silver, gold alloy or silver alloy formed by immersion and / or coating with a solution containing a polyallylamine polymer. In the present embodiment, the base material 1a is used as a material for determining the approximate shape of the optical semiconductor device metal structure 1.

[0063] There is no particular limitation on the material of the base material 1a, and copper, iron, their alloys, covering materials (e.g., a stack of copper / iron-nickel alloy / copper), etc. can be appropriately used. In the case of using a copper alloy, an alloy of copper with iron, tin, nickel, etc. can be used, and the copper content in this case is preferably set to be greater than 77.5% by mass and less than 99.5% by mass. In the case of using an iron alloy, an alloy of iron with nickel, cobalt, etc. can be used, and the iron content in this case is preferably set to be greater than 55.0% by mass and less than 99.9% by mass. Copper and copper alloys can be preferably used due to their excellent heat release properties. In particular, plate-shaped copper and copper alloys are also excellent in mechanical properties, electrical properties, processability, etc., and are therefore preferred. The covering material can suppress the linear expansion coefficient to a lower level, thereby improving the reliability of the optical semiconductor device 100.

[0064] The thickness and shape of the base material 1a can be selected from various thicknesses and shapes according to the shape of the optical semiconductor device 100. For example, it can be formed into a plate, a block, a film, etc. In addition, it can also be a wiring pattern provided on ceramics by printing, etc., and the formed wiring pattern can be plated with copper or a copper alloy.

[0065] In order to improve the reflectivity of light of the metal structure 1 for optical semiconductor devices, it is preferred that the flatness of the base material 1a is as high as possible. For example, the surface roughness Ra of the base material 1a is preferably 0.5 μm or less. As a result, the flatness of the nickel or nickel alloy plating 1b, the noble metal plating 1c1 including palladium or palladium alloy plating, rhodium or rhodium alloy plating, platinum or platinum alloy plating, etc., which are provided as required on the base material 1a, and the outermost layer 1d of gold, silver, gold alloy or silver alloy can be further improved. In addition, when the flatness of the base material 1a is high, the flatness of the outermost layer 1d of gold, silver, gold alloy or silver alloy with a thickness of 0.01 μm or more and 0.5 μm or less can also be improved, which can well improve the reflectivity of the metal structure 1 for optical semiconductor devices. In addition to being improved by rolling treatment, physical grinding, chemical grinding and other treatments, the flatness of the base material 1a can also be improved by plating the same type of material as the material constituting the base material 1a. For example, in the case of a base material 1 a made of a copper alloy, copper alloy plating may be performed to improve the flatness of the base material 1 a.

[0066] [Nickel or nickel alloy plating 1b]

[0067] The metal structure 1 for an opto-semiconductor device according to the present embodiment preferably has a nickel or nickel alloy plating layer 1b on the base material 1a.

[0068] The thickness of the nickel or nickel alloy plating layer 1b is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 10 μm or less. When the thickness of the nickel or nickel alloy plating layer 1b is 0.5 μm or more, it is possible to more effectively reduce the diffusion of the metal contained in the base material 1a from the base material 1a to the outermost layer 1d of the noble metal plating layer 1c1, gold, silver, gold alloy or silver alloy, which is the base layer. When the thickness of the nickel or nickel alloy plating layer 1b is 10 μm or less, the raw material and manufacturing costs can be reduced. As the material of the nickel or nickel alloy plating layer 1b, for example, in addition to nickel, alloys such as nickel-phosphorus, nickel-tin, and nickel-cobalt can also be used. In the case of using a nickel alloy, the content of nickel is preferably set to 90.0 mass% or more and 99.0 mass% or less.

[0069] Embodiment 3: Metal structure for optical semiconductor device (2)

[0070] Figure 2 B is a cross-sectional schematic view showing another embodiment of the metal structure 1 for an opto-semiconductor device. The metal structure 1 for an opto-semiconductor device may have a base layer 1c between the nickel or nickel alloy plating layer 1b and the outermost layer 1d of gold, silver, gold alloy or silver alloy. The base layer 1c preferably has a noble metal plating layer 1c1 including a palladium or palladium alloy plating layer, a rhodium or rhodium alloy plating layer, a platinum or platinum alloy plating layer, etc.

[0071] As Figure 2 shown in B, the metal structure 1 for an opto-semiconductor device may successively have, on the base material 1a, in a pair of two surfaces facing each other with the base material 1a as the center: for example, a nickel or nickel alloy plating layer 1b and an outermost layer 1d of gold, silver, gold alloy or silver alloy formed by treating with a solution containing a polyallylamine polymer by impregnation and / or coating. In Figure 2In B, the metal structure 1 for an opto-semiconductor device further includes a noble metal coating 1c1 containing a palladium or palladium alloy coating, a rhodium or rhodium alloy coating, a platinum or platinum alloy coating, etc. between the nickel or nickel alloy coating 1b and the outermost layer 1d of gold, silver, a gold alloy or a silver alloy. That is, the metal structure 1 for an opto-semiconductor device is laminated in sequence with: a base material 1a, a nickel or nickel alloy coating 1b, a noble metal coating 1c1 containing a palladium or palladium alloy coating, a rhodium or rhodium alloy coating, a platinum or platinum alloy coating, etc., and an outermost layer 1d of gold, silver, a gold alloy or a silver alloy formed by treating with impregnation and / or coating a solution containing a polyallylamine polymer. The metal structure 1 for an opto-semiconductor device can have, for example, a nickel or nickel alloy coating 1b, a noble metal coating 1c1 containing a palladium or palladium alloy coating, a rhodium or rhodium alloy coating, a platinum or platinum alloy coating, etc. provided as needed, and an outermost layer 1d of gold, silver, a gold alloy or a silver alloy formed by treating with impregnation and / or coating a solution containing a polyallylamine polymer in a manner that surrounds the base material 1a among four surfaces in two pairs that are opposed to each other with the plate-shaped base material 1a as the center.

[0072] As described above, from the viewpoint of improving reliability by enhancing the chip bonding property, wire bonding property, and solder mounting property with the light-emitting element 2, the metal structure 1 for an opto-semiconductor device has gold, silver, a gold alloy or a silver alloy as the outermost layer. When the outermost layer of the metal structure 1 for an opto-semiconductor device is a gold or gold alloy layer, it is preferable to form a gold or gold alloy coating as the outermost layer 1d. In addition, when the outermost layer 1d is a silver or silver alloy layer, it is preferable to form a silver or silver alloy coating as the outermost layer 1d and form a gold or gold alloy coating 1c2 as the base layer of the silver or silver alloy coating.

[0073] The base layer 1c can be set only as the above-mentioned noble metal coating 1c1, or can be set only as a gold or gold alloy coating 1c2. In addition, a gold or gold alloy coating 1c2 can be laminated on the noble metal coating 1c1, and the noble metal coating 1c1 and the gold or gold alloy coating 1c2 can be combined as the base layer 1c.

[0074] [Noble metal coating 1c1 containing a palladium or palladium alloy coating, a rhodium or rhodium alloy coating, a platinum or platinum alloy coating, etc.]

[0075] The metal structure 1 for an opto-semiconductor device according to this embodiment preferably has a noble metal coating 1c1 including a palladium or palladium alloy coating, a rhodium or rhodium alloy coating, a platinum or platinum alloy coating, etc. as a base layer in contact with the nickel or nickel alloy coating 1b. When using a base material 1a containing a copper-containing material, it is preferable to sequentially stack a nickel or nickel alloy coating 1b, a noble metal coating 1c1 including a palladium or palladium alloy coating, a rhodium or rhodium alloy coating, a platinum or platinum alloy coating, etc. provided on the nickel or nickel alloy coating 1b as a second base layer, and a topmost layer 1d of gold, silver, a gold alloy or a silver alloy on the base material 1a. By adopting such a configuration, for example, when the base material 1a contains copper, it is possible to further suppress the copper contained in the base material 1a from diffusing to the topmost layer 1d of gold, silver, a gold alloy or a silver alloy, and improve the adhesion of the stacked layers. In addition, by further suppressing the diffusion of the copper contained in the base material 1a, when using the metal structure 1 for an opto-semiconductor device as the lead frame 10, the wire bonding property can be further improved.

[0076] The thickness of the noble metal coating 1c1 is preferably 0.01 μm or more and 0.3 μm or less, more preferably 0.02 μm or more and 0.2 μm or less, and still more preferably 0.03 μm or more and 0.1 μm or less. When the thickness of the noble metal coating 1c1 is 0.01 μm or more and 0.3 μm or less, it is possible to further suppress the diffusion of the metal contained in the base material 1a to the topmost layer 1d of gold, silver, a gold alloy or a silver alloy, and when using the metal structure 1 for an opto-semiconductor device as the lead frame 10, the wire bonding property can be further improved. As the material for the palladium or palladium alloy coating, for example, in addition to palladium, alloys such as nickel, phosphorus, cobalt, and copper can also be used. When using a palladium alloy, the content of palladium is preferably set to 75.0 mass% or more and 97.0 mass% or less. As the material for the rhodium or rhodium alloy coating, for example, in addition to rhodium, alloys such as nickel, cobalt, and platinum can also be used. When using a rhodium alloy, the content of rhodium is preferably set to 75.0 mass% or more and 99.0 mass% or less. As the material for the platinum or platinum alloy coating, for example, in addition to platinum, alloys such as nickel, cobalt, and copper can also be used. When using a platinum alloy, the content of platinum is preferably set to 75.0 mass% or more and 99.0 mass% or less.

[0077] The noble metal coating 1c1 as the base layer of the topmost layer 1d of gold, silver, a gold alloy or a silver alloy can serve as a layer that takes into account both the functions of preventing sulfidation and preventing the diffusion of the metal contained in the base material 1a to other layers. Thereby, the cost can be further reduced. For example, gold is not easily reactive with sulfur components and has a high effect of preventing the diffusion of the metal contained in the base material 1a, so it can be preferably used.

[0078] For example, as described later Figure 3As shown in FIGS. A and 3B, the metal structure 1 for an optical semiconductor device is preferably a lead frame 10 having a substantially flat plate shape. Thereby, the reliability of the reflection member as the metal structure 1 for an optical semiconductor device can be improved. The nickel or nickel alloy plating 1b is somewhat brittle compared to copper, iron, their alloys, covering materials (such as a laminate of copper / iron-nickel alloy / copper), etc. used as the base material 1. Therefore, the metal structure 1 for an optical semiconductor device having the nickel or nickel alloy plating 1b can be used directly in a flat plate shape without being bent.

[0079] Embodiment 4: Optical semiconductor device (2)

[0080] Figure 3 A and Figure 3 FIGS. B show the structure of the optical semiconductor device 200 according to Embodiment 4. The optical semiconductor device 200 of this embodiment has a lead frame 10 that does not have a bent portion. In the optical semiconductor device 200 of Embodiment 4, the same reference numerals are given to the components common to the optical semiconductor device 100 of Embodiment 1.

[0081] Next, each component constituting the optical semiconductor device 100 of Embodiment 1 and the optical semiconductor device 200 of Embodiment 4 will be described.

[0082] [Light-emitting element 2]

[0083] The light-emitting element 2 can be a semiconductor light-emitting element having any wavelength. For example, as the light-emitting element 2 that emits blue or green light, nitride semiconductors such as InGaN, GaN, and AlGaN, and light-emitting elements using GaP can be used. In addition, as the red light-emitting element, GaAlAs, AlInGaP, etc. can be used. Furthermore, a light-emitting element 2 containing materials other than these can also be used. The composition, emission color, size, number, etc. of the light-emitting element 2 used can be appropriately selected according to the purpose.

[0084] When the optical semiconductor device 100 or the optical semiconductor device 200 includes a component capable of wavelength conversion, a nitride semiconductor that can efficiently excite the component capable of wavelength conversion and emit short-wavelength light can be appropriately cited. Various emission wavelengths can be selected according to the material of the semiconductor layer and its alloy ratio. In addition, the light-emitting element 2 can be set to output not only light in the visible light region but also ultraviolet light and infrared light.

[0085] The light-emitting element 2 is preferably mounted on the lead frame 10 constituted by the metal structure 1 for an optical semiconductor device. Thereby, the light extraction efficiency of the optical semiconductor device 100 or the optical semiconductor device 200 can be further improved.

[0086] The light-emitting element 2 preferably has positive and negative electrodes electrically connected to the conductive member. These positive and negative electrodes may be provided on one side, or may be provided on the upper and lower surfaces of the light-emitting element 2. The connection to the conductive member can be achieved by the bonding member 4 and the wire 6 described later, or can be achieved by flip-chip mounting.

[0087] [Resin molded body 3]

[0088] The resin molded body 3s is a member formed of a resin composition that integrally holds a pair of lead frames 10. The top view shape of the resin molded body 3 can be a shape in which a pair of opposing sides are longer than the other opposing sides as shown in Figure 1 A, and its plane is substantially rectangular, or can be a quadrilateral as shown in Figure 3 A. In addition, the resin molded body 3 can be set to a polygon or a shape that combines them. When the resin molded body 3 has a recess, the inner surface of the side wall portion 31 of the recess can have an inclined surface provided at an angle inclined with respect to the bottom surface as shown in Figure 3 B, can be at a substantially vertical angle, or can have a stepped surface. In addition, regarding its height, the shape of the opening portion, etc., it can also be appropriately selected according to the purpose and use. It is preferable to provide a lead frame 10 inside the recess. It is preferable that the space between the pair of lead frames 10, 10 is filled with the resin composition constituting the resin molded body 3, which forms a part 32 of the bottom surface of the resin molded body 3.

[0089] The resin molded body 3 can be formed using a resin composition containing a thermosetting resin or a thermoplastic resin. It is particularly preferable to use a resin composition containing a thermosetting resin. As a composition containing a thermosetting resin, compared with the resin used for the sealing member 5, a resin with low gas permeability is preferred. Specifically, examples include: epoxy resin compositions, silicone resin compositions, modified epoxy resin compositions such as silicone-modified epoxy resins, modified silicone resin compositions such as epoxy-modified silicone resins, polyimide resin compositions, modified polyimide resin compositions, urethane resins, modified urethane resin compositions, etc. In addition, as a composition containing a thermoplastic resin, a resin with low viscosity and easy flow is preferred. Specifically, examples include: polyamide, polyphthalamide (PPA), polycarbonate resin, polyphenylene sulfide (PPS), liquid crystal polymer (LCP), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), phenolic resin, acrylic resin, polybutylene terephthalate resin (PBT resin), etc. The resin composition constituting the resin molded body 3 may contain TiO 2 , SiO 2 , Al 2 O 3 , MgO, MgCO 3 , CaCO 3 , Mg(OH) 2, Ca(OH) 2 At least one inorganic particle such as those mentioned above is used as a filler. By including the above inorganic particles as a filler in the resin composition constituting the resin molded body 3, the light transmittance of the resin molded body 3 can be adjusted. It should be noted that, for the purpose of increasing the total luminous flux of the light-emitting device, the reflectivity of the resin material is increased, and when increasing TiO 2 (for example, when the total amount of the resin composition is set to 100% by mass and the content of TiO 2 is set to 20% by mass or more and 60% by mass or less), there is a concern that the adhesion may decrease between the metal structure 1 for the opto-semiconductor device and the resin material. However, in this embodiment, even in such a case, the adhesion between the substrate (lead frame 10, substrate, etc.) having gold, silver, a gold alloy, or a silver alloy on the outermost layer and the resin material can be improved.

[0090] It should be noted that the member for holding the lead frame 10 other than the resin molded body 3 can be formed of an inorganic substance such as ceramics, glass, or metal. Thereby, an opto-semiconductor device 100 or an opto-semiconductor device 200 with less deterioration and high reliability can be manufactured.

[0091] [Bonding member 4]

[0092] The bonding member 4 is a member for fixing and mounting the light-emitting element 2 to the lead frame 10. As the material of the conductive bonding member 4, a conductive paste containing at least one of silver, gold, palladium, etc., a eutectic solder material such as Au—Sn, Sn—Ag—Cu, a solder such as a low-melting metal, copper, silver, gold particles, and the same material as the outermost layer 1d of gold, silver, a gold alloy, or a silver alloy can be used. As the insulating bonding member 4, an epoxy resin composition, a silicone resin composition, a polyimide resin composition, a modified resin thereof, a mixed resin, etc. can be used. In the case of using these resins, considering the deterioration caused by the light and heat from the light-emitting element 2, a metal layer with high reflectivity such as an aluminum film or a silver film, a dielectric reflective film can be provided on the mounting surface of the light-emitting element 2.

[0093] [Sealing member 5]

[0094] The sealing member 5 is provided so as to cover each member of the light-emitting element 2, the lead frame 10, the wire 6, and the protective film described later. By including the sealing member 5, the opto-semiconductor device 100 or the opto-semiconductor device 200 can protect the covered members from damage by dust, moisture, external force, etc., and can improve the reliability of the opto-semiconductor device. In particular, by providing the sealing member 5 on the protective film after forming the protective film, the protective film can be protected, and thus the reliability of the opto-semiconductor device is improved.

[0095] Preferably, the sealing member 5 has light transmissibility that allows the light from the light-emitting element 2 to pass through, and thus has light resistance that is not easily deteriorated. As specific materials for the sealing member 5, insulating resin compositions having light transmissibility that allows the light from the light-emitting element to pass through, such as silicone resin compositions, modified silicone resin compositions, modified epoxy resin compositions, and fluororesin compositions, can be cited. In particular, a mixed resin containing at least one or more of resins having a siloxane skeleton as a base, such as dimethyl silicone, phenyl silicone with a small phenyl content, and fluorine-based silicone resin, can also be used.

[0096] When the material constituting the sealing member 5 contains a resin, the forming method of the sealing member 5 can utilize a casting (dropping) method, a compression molding method, a printing method, a transfer molding method, a jet dispensing method, a spray coating, etc. When the optoelectronic device includes a resin molded body 3 having a recess, the casting method is preferred. When the optoelectronic device uses a flat substrate, the compression molding method and the transfer molding method are preferred.

[0097] As Figure 1 shown in Figure 3 B or

[0098] As shown in

[0099] The sealing member 5 may also contain a colorant, a light diffusing material, a light reflecting material, various fillers, a wavelength conversion member, etc.

[0100] The wavelength conversion member is a material that converts the wavelength of the light from the light-emitting element 2. When the light emitted from the light-emitting element 2 is blue light, as the wavelength conversion member, a yttrium-aluminum-garnet-based phosphor (hereinafter referred to as "YAG:Ce"), which is a kind of aluminum oxide-based phosphor, can be appropriately used. The YAG:Ce phosphor absorbs a part of the blue light from the light-emitting element and emits yellow light that is a complementary color. Therefore, an optoelectronic device that emits high-output mixed white light can be formed relatively simply.

[0101] [Lead wire 6]

[0102] The wire 6 connects conductive components such as the light-emitting element 2 and the lead frame 10 together. As the material of the wire 6, gold, silver, aluminum, copper, their alloys, etc. can be appropriately used. Additionally, as the wire 6, a wire having a coating layer formed of a material different from that of the core on the surface of the core can be used, for example, a wire having palladium, a palladium-gold alloy, etc. provided as the coating layer on the surface of a copper core. Among them, the material of the wire 6 is preferably selected from any one of gold, silver, and silver alloys with high reliability. Additionally, silver or a silver alloy with a high light reflectivity is particularly preferred. In this case, it is particularly preferred that the wire 6 is coated with a protective film. Thereby, sulfidation and disconnection of the silver-containing wire can be further prevented, and the reliability of the optoelectronic device 100 can be further improved. Further, when the base material 1a of the metal structure for optoelectronic devices constituting the lead frame 10 contains copper and the wire 6 contains silver or a silver alloy, by providing the metal structure 1 for optoelectronic devices with a nickel or nickel alloy plating layer 1b, the formation of a local battery between copper and silver can be suppressed. Thereby, deterioration of the lead frame 10 and the wire 6 can be further suppressed, and an optoelectronic device with higher reliability can be manufactured. In addition, similar to the lead frame 10 having the above-described metal structure 1 for optoelectronic devices, the wire 6 can have the metal structure 1 for optoelectronic devices. Thus, since it has the outermost layer 1d formed by treating with a solution containing a polyallylamine polymer by impregnation and / or coating, the adhesion to the resin is good, and in the optoelectronic device 100 or the optoelectronic device 200, for example, the adhesion to the sealing member 5 can be improved.

[0103] [Protective film]

[0104] The optoelectronic device 100 or the optoelectronic device 200 can further include a protective film. The protective film can at least coat the outermost layer 1d of gold, silver, a gold alloy, or a silver alloy provided on the surface of the metal structure 1 for optoelectronic devices constituting the lead frame 10. The protective film is a member that mainly inhibits discoloration or corrosion of the outermost layer 1d of gold, silver, a gold alloy, or a silver alloy on the surface of the metal structure 1 for optoelectronic devices constituting the lead frame 10. The protective film can further optionally coat the surfaces of components other than the lead frame 10 or the substrate, such as the light-emitting element 2, the bonding member 4, and the resin molded body 3, and the surface of the metal structure 1 for optoelectronic devices where the outermost layer 1d of gold, silver, a gold alloy, or a silver alloy is not provided. When the wire 6 is silver or a silver alloy, and the outermost layer 1d of gold, silver, a gold alloy, or a silver alloy is a silver or silver alloy layer, the protective film is preferably provided so as to coat the wire 6 and the outermost layer 1d. Thereby, sulfidation and disconnection of the silver-containing wire can be further prevented, and the reliability of the optoelectronic device 100 or the optoelectronic device 200 can be further improved.

[0105] The protective film is preferably formed by sputtering, chemical vapor deposition, or atomic layer deposition (hereinafter also referred to as ALD (Atomic Layer Deposision)). In particular, according to the ALD method, a very uniform protective film can be manufactured, and the formed protective film is denser than the protective films obtained by other film-forming methods. Therefore, for example, it is possible to very effectively prevent the outermost surface 1d of the metal structure 1 for the opto-semiconductor device that constitutes the lead frame 10 from being sulfided and discolored.

[0106] Examples of the material for the protective film include Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , ZnO, Nb 2 O 5 , MgO, In 2 O 3 , Ta 2 O 5 , HfO 2 , SeO, Y 2 O 3 , SnO 2 and other oxides, nitrides such as AlN, TiN, ZrN, fluorides such as ZnF 2 , SrF 2 and the like. They can be used alone, mixed, or laminated.

[0107] In addition to the above components, the opto-semiconductor device 100 or the opto-semiconductor device 200 may further include various components. For example, a Zener diode can be mounted as a protection element.

[0108] [Manufacturing Method of Opto-Semiconductor Device]

[0109] Next, as an example of the manufacturing method of the opto-semiconductor device, based on Figure 4 A, Figure 4 B, Figure 4 C and Figure 4 D, the manufacturing method of the opto-semiconductor device 200 of Embodiment 4 will be described.

[0110] As Figure 4As shown in A, a lead frame 10 made of the metal structure 1 for an opto-semiconductor device according to Embodiment 2 or 3 is prepared. Specifically, a metal plate such as copper as the base material 1a constituting the metal structure 1 for an opto-semiconductor device is punched, and as described in the manufacturing method of the metal structure 1 for an opto-semiconductor device described later, a nickel or nickel alloy plating 1b provided as needed, a noble metal plating 1c1 including a palladium or palladium alloy plating, a rhodium or rhodium alloy plating, a platinum or platinum alloy plating, etc. provided as needed, and a topmost layer 1d of gold, silver, a gold alloy or a silver alloy are formed. After performing a treatment of impregnating and / or coating a solution containing a polyallylamine polymer, washing with water or hot water (cleaning) is performed as needed, and drying is performed, thereby forming the lead frame 10 as the lead frame.

[0111] As Figure 4 As shown in B, the resin molded body 3 can be molded by a transfer molding method in such a manner as to be connected to the lead frame 10 using the metal structure 1 for an opto-semiconductor device. The resin molded body 3 can be formed in such a manner that a pair of lead frames 10 are respectively exposed on the bottom surface of the recess of the resin molded body 3. That is, the lead frame 10 can be exposed on the bottom surface of the recess of each resin molded body 3.

[0112] Next, as Figure 4 As shown in C, in the region where the light-emitting element 2 is mounted on the lead frame 10 on which the resin molded body 3 is formed, the light-emitting element 2 can be mounted via the bonding member 4. Moreover, the light-emitting element 2 and the lead frame 10 can be connected together by a wire. Then, a sealing member 5 can be provided in each recess of the resin molded body 3.

[0113] Then, a dicing saw or the like can be used to cut the lead frame 10 and the resin molded body 3 as shown in Figure 4 D, and singulated into each opto-semiconductor device as shown in Figure 3 A and Figure 3 B. By this cutting, the cross-section of the lead frame 10 is exposed on the outer side surface of the opto-semiconductor device 200. In this cross-section, the base material 1a such as copper of the metal structure 1 for an opto-semiconductor device constituting the lead frame 10, the nickel or nickel alloy plating 1b provided as needed, the noble metal plating 1c1 including a palladium or palladium alloy plating, a rhodium or rhodium alloy plating, a platinum or platinum alloy plating, etc. provided as needed, and the topmost layer 1d of gold, silver, a gold alloy or a silver alloy that has been subjected to the treatment of impregnating and / or coating a solution containing a polyallylamine polymer are exposed.

[0114] Embodiment 5: Manufacturing method of metal structure for optical semiconductor device

[0115] Next, a manufacturing method of the metal structure for an opto-semiconductor device will be described.

[0116] The manufacturing method of the metal structure for the opto-semiconductor device of Embodiment 1 includes:

[0117] (1) A treatment step of impregnating and / or coating a solution containing a polyallylamine polymer on a substrate having a topmost layer (the topmost layer 1d of gold, silver, a gold alloy, or a silver alloy) containing at least one selected from gold, silver, a gold alloy, and a silver alloy (preferably a plating material selected from at least one of gold, silver, a gold alloy, and a silver alloy) on a part or the whole surface.

[0118] In the present application, the coating film means a metal film formed by, for example, wet plating such as electroplating and electroless plating, hot dip plating, sputtering, dry plating such as evaporation plating including physical vapor deposition and chemical vapor deposition, etc.

[0119] In addition, the substrate only needs to have a topmost layer containing at least one selected from gold, silver, a gold alloy, and a silver alloy, and the topmost layer may not be a metal film formed by surface treatment. In other words, the substrate itself may be at least one selected from gold, silver, a gold alloy, and a silver alloy.

[0120] A height difference may also be formed at a given position of the substrate by wet etching, and after the height difference is formed, the above-mentioned step is performed.

[0121] In addition, as described above, it is preferable to form a nickel or nickel alloy plating layer 1b provided as needed and a noble metal plating layer 1c1 including a palladium or palladium alloy plating layer, a rhodium or rhodium alloy plating layer, a platinum or platinum alloy plating layer, etc. provided as needed on the base material 1a. Therefore, before performing the above-mentioned step (1), it is preferable to include: a step of forming a nickel or nickel alloy plating layer 1b on the base material 1a as needed; a step of forming a noble metal plating layer 1c1 including a palladium or palladium alloy plating layer, a rhodium or rhodium alloy plating layer, a platinum or platinum alloy plating layer, etc. on the nickel or nickel alloy plating layer 1b as needed; and a step of forming the topmost layer 1d of gold, silver, a gold alloy, or a silver alloy. In addition, as described above, when the topmost layer is a silver or silver alloy layer, it is preferable to form a gold or gold alloy plating layer 1c2 on the above-mentioned noble metal plating layer 1c1 and form a silver or silver alloy layer thereon. Therefore, when the topmost layer is a silver or silver alloy layer, the step of forming the topmost layer 1d of gold, silver, a gold alloy, or a silver alloy preferably includes: a step of forming a gold or gold alloy plating layer; and a step of forming the topmost layer of silver or silver alloy. The thickness of the gold or gold alloy plating layer 1c2 can be set to 0.003 μm or more and 0.5 μm or less. It should be noted that the topmost layer 1d is not necessarily limited to the coating film and may be a metal film formed by thermal spraying. In order to easily form the above-mentioned respective layers, the steps of forming the above-mentioned respective layers are preferably performed by a method of forming a metal film by using the above-mentioned plating, and more preferably by electroplating or electroless plating. Among them, electroplating is preferable because of the fast layer formation speed and the ability to improve mass productivity.

[0122] Prior to forming each of the above-described layers, pretreatment of the base material 1a can also be performed. Examples of the pretreatment include acid treatment such as dilute sulfuric acid, dilute nitric acid, and dilute hydrochloric acid, and alkali treatment such as sodium hydroxide. These treatments can be performed once or multiple times, and the same treatment or different treatments can be combined. When performing multiple pretreatments, it is preferable to perform running water rinsing with pure water after each treatment. When the base material 1a is a metal plate containing copper or a copper alloy, it is preferable to use dilute sulfuric acid in the pretreatment. When the base material 1a is a metal plate containing iron or an iron alloy, it is preferable to use dilute hydrochloric acid in the pretreatment.

[0123] In the process of forming the nickel or nickel alloy plating layer 1b, when the material constituting the above plating layer is pure nickel, for example, electroplating can be performed using a plating solution containing nickel sulfamate to form the layer. In addition, when using a nickel-phosphorus alloy, electroless plating can be performed using a nickel hypophosphite plating solution to form the layer.

[0124] In the process of forming a noble metal plating layer 1c1 such as a plating layer containing palladium or a palladium alloy, a plating layer containing rhodium or a rhodium alloy, or a plating layer containing platinum or a platinum alloy, when the material constituting the above plating layer is palladium or a palladium alloy, for example, electroplating can be performed using a plating solution containing tetramminepalladium chloride to form the layer. When the material constituting the above plating layer is rhodium or a rhodium alloy, for example, electroplating can be performed using a plating solution containing rhodium sulfate to form the layer. When the material constituting the above plating layer is platinum or a platinum alloy, for example, electroplating can be performed using a plating solution containing dinitrodiammineplatinum salt to form the layer.

[0125] [The outermost layer 1d of gold, silver, a gold alloy, or a silver alloy]

[0126] The outermost layer 1d of gold, silver, a gold alloy, or a silver alloy is provided on the surface of the metal structure 1 for an opto-semiconductor device. The thickness of the outermost layer 1d of gold, silver, a gold alloy, or a silver alloy is 0.003 μm or more and 0.5 μm or less, preferably 0.01 μm or more and 0.3 μm or less. When the thickness of the outermost layer 1d of gold, silver, a gold alloy, or a silver alloy is 0.003 μm or more, the chip bonding property with the light-emitting element 2 and the wire bonding property with the wire 6 can be further improved. In addition, when the thickness of the outermost layer 1d of gold, silver, a gold alloy, or a silver alloy is 0.5 μm or less, the amount of expensive noble metal used can be further reduced, and the cost can be further lowered. It should be noted that when using a gold alloy, the gold content is preferably 75.0 mass% or more and 99.9 mass% or less, and when using a silver alloy, the silver content is preferably 75.0 mass% or more and 99.9 mass% or less.

[0127] In the case where the outermost layer 1d is a gold or gold alloy layer and the gold or gold alloy layer is formed by electroplating, it is preferable to use a plating solution containing 0.5 g / L or more and 10 g / L or less of potassium chloroaurate or chloroauric acid in terms of metallic gold concentration and containing 30 g / L or more and 150 g / L or less of a conductivity salt. In the case of gold alloy plating, by adding 1 g / L or more and 5 g / L or less of potassium argentocyanide, potassium cuprocyanide, etc. as alloy metals, a gold-silver alloy coating film or a gold-copper alloy coating layer can be obtained respectively.

[0128] In the case where the outermost layer 1d is a silver or silver alloy layer and the silver or silver alloy layer is formed by electroplating, it is preferable to use a plating solution containing 20 g / L or more and 80 g / L or less of potassium argentocyanide or argentocyanic acid in terms of metallic silver and containing 50 g / L or more and 150 g / L or less of free potassium cyanide or a conductivity salt. In addition, a selenium compound and an organic sulfur compound can be further added as brighteners to the plating solution. In the case of silver alloy plating, by adding 5 g / L or more and 20 g / L or less of potassium chloroaurate, potassium cuprocyanide, etc. as alloy metals, a silver-gold alloy coating film or a silver-copper alloy coating layer can be obtained respectively.

[0129] The above plating solution preferably contains 5 g / L or more and 150 g / L or less of one or more conductivity salts such as cyanide salts, carbonate salts, phosphate salts, nitrate salts, citrate salts, sulfate salts, etc. If the conductivity salt contained in the plating solution is 5 g / L or more and 150 g / L or less, the resistance of the plating solution will not become too high, and in addition, the viscosity of the plating solution will not become too viscous, the ion mobility is not easily reduced, and the plating solution can be used more stably industrially. In addition, if the conductivity salt contained in the plating solution is 5 g / L or more and 150 g / L or less, the viscosity of the plating solution will not be too viscous, and the so-called carry-out of the plating solution caused by the object to be plated will also be less. Therefore, plating of gold, silver, gold alloy or silver alloy can be carried out more economically. Examples of the cyanide salt include potassium cyanide and sodium cyanide. Examples of the carbonate salt include potassium carbonate, sodium carbonate, ammonium carbonate, etc. Examples of the phosphate salt include potassium phosphate, sodium phosphate, ammonium phosphate, potassium pyrophosphate, etc. Examples of the nitrate salt include potassium nitrate, sodium nitrate, ammonium nitrate, etc. Examples of the citrate salt include potassium citrate, sodium citrate, ammonium citrate, etc. Examples of the sulfate salt include potassium sulfate, sodium sulfate, etc.

[0130] In the process of forming the outermost layer 1d of the above gold, silver, gold alloy or silver alloy, it is preferable to carry out electroplating using the above plating solution under the following conditions: the liquid temperature of the plating solution is 20 °C or more and 70 °C or less, the anode uses a soluble electrode containing gold, silver or a gold-silver alloy, or a stainless steel or platinum or platinum-coated titanium electrode, and the cathode current density of the conductive substrate is set to 0.1 A / dm 2 above and 10 A / dm 2 below, and the plating time is 5 seconds or more and 10 minutes or less.

[0131] It should be noted that in the case where the gold, silver, gold alloy or silver alloy layer as the outermost 1d layer is, for example, a metal plate or a wire rather than a metal film formed by plating, thermal spraying, etc., it can be formed or prepared by a conventional method.

[0132] The outermost 1d layer of gold, silver, gold alloy or silver alloy is formed by a process of impregnating and / or coating a solution containing a polyallylamine polymer. Thereby, a film containing a polyallylamine polymer adheres to the substrate having the outermost 1d layer of gold, silver, gold alloy or silver alloy. The thickness of the film containing a polyallylamine polymer is preferably 10 nm or more and 500 nm or less. By setting the thickness of the film containing a polyallylamine polymer to 500 nm or less, chip bonding, wire bonding or solder mounting of the light-emitting element can be performed more favorably. In addition, by setting the thickness of the film containing a polyallylamine polymer to 10 nm or more, the adhesion between the metal structure 1 for an optical semiconductor device and the resin material can be further improved.

[0133] The polyallylamine polymer is not particularly limited and is generally assumed to be a homopolymer of allylamine as a primary amine. Specifically, examples include polyallylamine polymers represented by the general formula (1):

[0134] [Chemical formula 1]

[0135]

[0136] [In the formula, n represents 25 to 440.]

[0137] These polyallylamine polymers can be used alone or in combination of two or more.

[0138] From the viewpoint of adhesion to the resin material, the weight-average molecular weight of the above polyallylamine polymer is preferably 1600 or more and 25000 or less, more preferably 3000 or more and 18000 or less.

[0139] The polyallylamine polymer as described above can be a known product or a commercially available product, or can be used after polymerization. In the case of using a commercially available product, it is sold under the trade name of PAA (registered trademark) by Nittobo Medical Co., Ltd., and thus can be easily obtained.

[0140] The polyallylamine polymer is a water-soluble polymer, and thus, aqueous solutions of various concentrations can be prepared. Among them, considering economy and ease of operation, the total amount of the solution containing the polyallylamine polymer is set to 100% by mass, and it is preferably prepared into an aqueous solution of 0.01% by mass or more and 1.0% by mass or less. More preferably, it is prepared into an aqueous solution of 0.05% by mass or more and 0.5% by mass or less. By setting the concentration of the solution containing the polyallylamine polymer to 0.01% by mass or more, it can be sufficiently adhered to the outermost layer 1d of gold, silver, gold alloy or silver alloy, and it is easy to further improve the adhesion to the resin material. By setting the concentration of the solution containing the polyallylamine polymer to 1.0% by mass or less, not only can the adhesion to the resin material be improved, but also the viscosity of the aqueous solution is not excessively increased, the treatment liquid is not easily carried out together with the metal structure 1 for the opto-semiconductor device, and it is more economical.

[0141] In the present embodiment, the solution containing the polyallylamine polymer may contain a triazine compound. That is, the film containing the polyallylamine polymer adhered to the substrate may contain a triazine compound. In this way, by containing both the polyallylamine polymer and the triazine compound, the adhesion to the resin material can be further improved. Since the triazine compound has excellent adhesion to gold, in the case of using a gold or gold alloy layer as the outermost layer 1d, the adhesion to the resin material can be particularly improved.

[0142] As the triazine compound, from the viewpoint of easily further improving the adhesion to the resin material, a triazine thiol compound is preferred. In particular, the triazine compound represented by the general formula (2) can be cited:

[0143] [Chemical formula 2]

[0144]

[0145] [In the formula, Y represents a nitrogen atom or a sulfur atom. R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, an alkali metal atom or a substituted or unsubstituted alkyl group. m represents 1 or 2. When Y is a nitrogen atom, m represents 2, and when Y is a sulfur atom, m represents 1.]

[0146] In the general formula (2), as the alkali metal atom represented by R 1 , R 2 and R 3 , lithium atom, sodium atom, potassium atom, cesium atom, etc. can be cited.

[0147] In the general formula (2), as the group represented by R 1 , R 2 and R 3Examples of the alkyl group represented include alkyl groups having 1 to 10 (especially 1 to 6) carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. These alkyl groups may have substituents such as 1 to 3 halogen atoms (chlorine atom, bromine atom, iodine atom, etc.).

[0148] Specific examples of such triazine compounds include:

[0149] [Chemical formula 3]

[0150] etc.

[0151] These triazine compounds can be used alone or in combination of two or more.

[0152] These triazine compounds can be public-known products or commercially available products. For example, the sodium salt of 1,3,5-triazine-2,4,6-thiol is sold by Sankyo Chemical Co., Ltd. under the trade name Santhiol, can be easily obtained, and since it is water-soluble, a treatment solution with an appropriate concentration can be prepared, so it is preferred.

[0153] Regarding the above triazine compounds, considering economy and ease of operation, when the solution containing the polyallylamine polymer further contains a triazine compound, the total amount of the solution containing the polyallylamine polymer is set to 100% by mass, and an aqueous solution with the content of the triazine compound preferably being 0.01% by mass or more and 1.0% by mass or less, more preferably 0.05% by mass or more and 0.5% by mass or less is prepared. By setting the concentration of the solution containing the triazine compound to 0.01% by mass or more, it can be more fully attached to the outermost layer 1d of gold, silver, gold alloy or silver alloy, and it is easy to further improve the adhesion to the resin material. By setting the concentration of the solution containing the triazine compound to 1.0% by mass or less, not only can the adhesion to the resin material be improved, but also the viscosity of the aqueous solution will not be excessively increased, the treatment solution is not easily carried out together with the metal structure 1 for the opto-semiconductor device, and it is more economical.

[0154] The triazine compound has excellent adhesion to gold and silver (especially gold). In particular, the triazine thiol compound has good adhesion to gold due to the intermolecular force between gold and S (sulfur). However, if it is washed with water, there is a concern that its effect may weaken. On the other hand, the polyallylamine polymer has a large molecular weight, and the solution containing the polyallylamine polymer is viscous. Therefore, through the treatment of this embodiment, it is easily attached to the surface of the outermost layer 1d of gold, silver, gold alloy or silver alloy to form a film containing the polyallylamine polymer. Through this film containing the polyallylamine polymer, the adhesion between the outermost layer 1d of gold, silver, gold alloy or silver alloy and the resin material is improved. In addition, when the film containing the polyallylamine polymer contains a triazine compound, the film containing the polyallylamine polymer retains the triazine compound. Therefore, it is speculated that a better effect can be obtained in terms of improving adhesion.

[0155] In order to easily further improve the wettability and dissolution stability of the outermost layer 1d of gold, silver, gold alloy or silver alloy, an appropriate anionic surfactant, cationic surfactant, nonionic surfactant, etc. can also be added to the above solution containing the polyallylamine polymer.

[0156] In order to easily maintain the dissolution stability, an appropriate organic solvent and an appropriate pH buffer can also be added to the above solution containing the polyallylamine polymer. As the pH buffer, for example, boric acid or its salt, diphosphoric acid or its salt, phosphoric acid or its salt, or citric acid or its salt can be cited.

[0157] It should be noted that for the above solution containing the polyallylamine polymer, when a concentrated solution is prepared in advance and used in a processing device, the concentrated solution can be appropriately diluted with water and used.

[0158] The above solution containing the polyallylamine polymer is particularly useful when it is used to improve the adhesion between the lead frame 10 and the adjacent resin molding 3 in the optical semiconductor device 100 or the optical semiconductor device 200.

[0159] As a method for treating a gold, silver, gold alloy or silver alloy layer with a solution containing a polyallylamine polymer, an impregnation and / or coating treatment is preferably performed. In the case of performing an impregnation treatment, the entire gold, silver, gold alloy or silver alloy layer can be impregnated in the solution containing the polyallylamine polymer, or only the portion in contact with the resin material can be impregnated. In the case of performing an impregnation treatment, an appropriate stirring treatment and a jet flow treatment are preferably performed. On the other hand, in the case of performing a coating treatment (especially a blowing treatment), the solution containing the polyallylamine polymer can be coated by a known method, or the blowing treatment (spray treatment, etc.) can be performed by a known method. Specifically, the gold, silver, gold alloy or silver alloy layer can be vertically blown by spraying, or can be blown horizontally or at an angle. In addition, it can be a blowing jet flow, or can be like a shower. In addition, both the above-mentioned impregnation and coating can be performed, and their order is not particularly limited.

[0160] When impregnating and / or coating a gold, silver, gold alloy or silver alloy layer, the temperature of the solution containing the polyallylamine polymer is preferably 15°C or higher and 50°C or lower. By setting the temperature of the solution to 15°C or higher, the films of the polyallylamine polymer and the triazine compound used as needed can adhere to the surface of the gold, silver, gold alloy or silver alloy layer in an appropriate time. In addition, by setting the temperature of the solution to 50°C or lower, it is easy to further suppress the formation of spots during drying.

[0161] The treatment time for impregnating and / or coating a gold, silver, gold alloy or silver alloy layer with a solution containing a polyallylamine polymer can be appropriately adjusted according to the impregnation and / or coating method and the temperature of the treatment solution, but is usually preferably 3 seconds or more and 60 seconds or less. By setting the treatment time to 3 seconds or more, it is easy for the films of the polyallylamine polymer and the triazine compound used as needed to adhere more uniformly to the surface of the gold, silver, gold alloy or silver alloy layer. In addition, by setting the treatment time to 60 seconds or less, it is easy to further improve productivity.

[0162] In the manufacturing method of the present embodiment, after the above-mentioned step (1) is passed, the following steps can be sequentially included:

[0163] (2) A step of cleaning the substrate after the above-mentioned step (1); and;

[0164] (3) A step of drying the substrate after the above-mentioned step (2).

[0165] Cleaning (especially water washing or hot water washing) and drying can be performed according to conventional methods.

[0166] For the metal structure 1 for an opto-semiconductor device, after forming each layer, a heat treatment process may be further included as process (4). Specifically, after process (3) described above, a process (4) of heat-treating the substrate after process (2) may be provided. The heat treatment may be carried out in the atmosphere, or in an inert atmosphere such as nitrogen, or a reducing atmosphere such as hydrogen. In addition, as the heat treatment method, it may be a batch treatment in a hot air thermostat, or a hot air furnace or an infrared furnace may be provided in the final process of a continuous plating apparatus to continuously carry out the heat treatment. Through these heat treatments, the base material 1a and the metals of each layer appropriately diffuse into each other, and the adhesion between the base material 1a and the nickel or nickel alloy plating 1b, and between each of the layers 1b, 1c, and 1d is easily improved. It should be noted that the heat treatment temperature and treatment time may be determined in consideration of the combination of the thicknesses of each layer, and the heat treatment temperature is generally preferably 100 °C or higher and 500 °C or lower.

[0167] Examples

[0168] Hereinafter, the present invention will be described more specifically by way of examples, but is not limited to these examples.

[0169] Examples 1, 4, 5, 7 and 11

[0170] As Figure 2 shown in A, using each plating solution having the bath composition shown below, under each condition, a nickel plating, a nickel-tin alloy plating or a nickel-cobalt alloy plating as the nickel or nickel alloy plating 1b, and a gold plating as the outermost layer 1d provided on the nickel or nickel alloy plating 1b were sequentially formed on the surface of the following base material 1a by electroplating, thereby forming the metal structure 1 for an opto-semiconductor device. Then, a process of treating by impregnating or blowing a solution containing a polyallylamine polymer, a process of cleaning, and a process of drying were carried out, and using the metal structure 1 for an opto-semiconductor device, a lead frame 10 as a pair of lead frames was prepared. The thickness (μm) of each layer, the composition of the solution containing the polyallylamine polymer, and the treatment conditions in the examples are shown in Table 1.

[0171] [Base materials 1a of Examples 1, 4, 5, 7, and 11]

[0172] In Examples 1, 4, 5, and 7, copper was used as the base material, and in Example 11, iron was used as the base material.

[0173] Base material of copper: A material obtained by forming a lead frame shape from TAMAC194 material manufactured by Mitsubishi Shindoh Co., Ltd. using a pressing die was used.

[0174] Base material of iron: A material obtained by forming a lead frame shape from SPCE-SB manufactured by Nippon Steel Corporation using a pressing die was used.

[0175] [Nickel or nickel alloy coatings 1b of Examples 1, 4, 5, 7, and 11]

[0176] As the nickel or nickel alloy coating 1b, a nickel coating was formed in Examples 1, 4, and 11, a nickel - tin alloy coating was formed in Example 5, and a nickel - cobalt alloy coating was formed in Example 7.

[0177] For the nickel coating, a plating solution with the following bath composition was used as a standard sulfamic acid electroplating bath.

[0178] Nickel plating solution

[0179] Nickel sulfamate = 450 g / L

[0180] Nickel chloride = 10 g / L

[0181] Boric acid = 30 g / L

[0182] pH 4.0.

[0183] For the nickel - tin alloy coating, a plating solution obtained by adding an appropriate amount of tin sulfamate (5 g / L) to the above - mentioned nickel coating was used.

[0184] For the nickel - cobalt alloy coating, a plating solution obtained by adding an appropriate amount of cobalt sulfamate (15 g / L) to the above - mentioned nickel coating was used.

[0185] Using the above - mentioned plating solutions, the plating time was adjusted, and electroplating was carried out under the conditions of a liquid temperature of 55 °C and a cathode current density of 5 A / dm 2 to form a nickel coating, a nickel - tin alloy coating, or a nickel - cobalt alloy coating. A nickel plate added with sulfur was used as the anode.

[0186] [The outermost layer 1d of Examples 1, 4, 5, 7, and 11]

[0187] Gold plating solution

[0188] Potassium gold cyanide calculated as gold is 9 g / L

[0189] Potassium citrate = 120 g / L

[0190] Dipotassium hydrogen phosphate = 30 g / L

[0191] Thallium sulfate calculated as thallium is 10 mg / L

[0192] pH 6.3.

[0193] Using the above - mentioned plating solution, the plating time was adjusted, and electroplating was carried out under the conditions of a liquid temperature of 68 °C and a cathode current density of 0.5 A / dm 2 to form a gold coating. A platinum - coated titanium insoluble electrode was used as the anode.

[0194] Then, in Examples 1, 4, and 7, a treatment of impregnating or blowing a 0.5 mass% aqueous solution of polyallylamine polymer PAA-03 (registered trademark; weight-average molecular weight: 3000) manufactured by Nittobo Medical Co., Ltd. was carried out, followed by washing with water and drying. Note that the conditions for the impregnation or blowing treatment are shown in Table 1.

[0195] In addition, in Example 5, a treatment of blowing a 35-second aqueous solution containing 0.02 mass% of polyallylamine polymer PAA-08 (registered trademark; weight-average molecular weight: 8000) manufactured by Nittobo Medical Co., Ltd. and 0.2 mass% of trisodium 1,3,5-triazine-2,4,6-trithiolate (Santhiol N-W manufactured by Sankyo Chemical Co., Ltd.) at 50°C was carried out, followed by washing with water and drying.

[0196] In addition, in Example 11, it was immersed in an aqueous solution containing 0.01 mass% of polyallylamine polymer PAA-15 (registered trademark; weight-average molecular weight: 15000) manufactured by Nittobo Medical Co., Ltd. and 0.1 mass% of trisodium 1,3,5-triazine-2,4,6-trithiolate (Santhiol N-W manufactured by Sankyo Chemical Co., Ltd.) at 15°C for 3 seconds, followed by washing with water and drying.

[0197] Examples 2, 3, 6, 8, 9 and 10

[0198] As Figure 2 shown in B, using each plating solution having the bath composition shown below, under each condition, a nickel plating layer or a nickel-phosphorus alloy plating layer as a nickel or nickel alloy plating layer 1b, a palladium plating layer, a palladium-nickel alloy plating layer, a rhodium plating layer, or a rhodium-cobalt alloy plating layer as a base layer 1c provided on the nickel or nickel alloy plating layer 1b, and a gold plating layer, a gold-silver alloy plating layer, or a gold-cobalt plating layer as the outermost layer 1d provided on the base layer 1c were sequentially formed on the surface of the following base material 1a by electroplating, thereby forming a metal structure 1 for an optical semiconductor device. Then, a treatment step of immersing in a solution containing a polyallylamine polymer, a cleaning step, a drying step, and a heat treatment step carried out as needed were implemented, and using the metal structure 1 for an optical semiconductor device, a lead frame 10 as a pair of lead frames was prepared. The thicknesses of the respective layers, the composition of the solution containing the polyallylamine polymer, and the treatment conditions in the examples are described in Table 1.

[0199] [Base material 1a of Examples 2, 3, 6, 8, 9, and 10]

[0200] In Examples 2, 3, 6, 8, and 10, a copper substrate was used, and in Example 9, a 42alloy alloy substrate was used.

[0201] The copper substrate used was the same copper substrate as in Example 1.

[0202] Substrate of 42alloy alloy: A material obtained by forming a lead frame shape from a 42% Ni-Fe iron-nickel alloy (Fe-42% Ni) manufactured by Dowa Metanix Co., Ltd. using a pressing die was used.

[0203] [Nickel or nickel alloy plating layer 1b of Examples 2, 3, 6, 8, 9, and 10]

[0204] As the nickel or nickel alloy plating layer 1b, a nickel plating layer was formed in Examples 2, 3, 6, 8, and 10, and a nickel-phosphorus alloy plating layer was formed in Example 9.

[0205] The nickel plating layers of Examples 2, 3, 6, 8, and 10 used the same plating solution as in Example 1, except for the plating thickness shown in Table 1.

[0206] The nickel-phosphorus alloy plating layer used a plating solution obtained by adding an appropriate amount of phosphorous acid (20 g / L) to the above nickel plating layer.

[0207] Using the above plating solution, adjusting the plating time, electroplating was carried out under the conditions of a liquid temperature of 55 °C and a cathode current density of 5 A / dm 2 , and a nickel plating layer or a nickel-phosphorus alloy plating layer was formed. A nickel plate added with sulfur was used as the anode.

[0208] [Base layer 1c of Examples 2, 3, 6, 8, 9, and 10]

[0209] As the base layer 1c, a palladium plating layer was formed in Examples 2, 9, and 10, a rhodium plating layer was formed in Example 3, a palladium-nickel alloy plating layer was formed in Example 6, and a rhodium-cobalt alloy plating layer was formed in Example 8.

[0210] The palladium plating layer as the base layer 1c in Examples 2, 9, and 10 used a plating solution with the following bath composition.

[0211] Palladium plating solution

[0212] Tetraamminepalladium chloride 5 g / L in terms of palladium

[0213] Ammonium nitrate = 150 g / L

[0214] 3-Pyridinesulfonic acid sodium salt = 5 g / L

[0215] pH 8.5.

[0216] The palladium-nickel alloy plating layer of Example 6 used a plating solution obtained by adding an appropriate amount of nickel sulfate (1.0 g / L) to the above palladium plating solution.

[0217] Using the above plating solution, adjusting the plating time, electroplating was carried out under the conditions of a bath temperature of 50 °C and a cathode current density of 1 A / dm 2 , and a palladium coating or a palladium-nickel alloy coating was formed. A platinum-coated titanium electrode was used as the anode.

[0218] As the rhodium coating of the base layer 1c in Example 3, a plating solution having the following bath composition was used.

[0219] Rhodium plating solution

[0220] Rhodium sulfate was 2 g / L in terms of rhodium

[0221] Sulfuric acid = 50 g / L

[0222] Lead sulfate was 10 mg / L in terms of lead.

[0223] For the rhodium-cobalt alloy coating in Example 8, a plating solution obtained by adding an appropriate amount of cobalt sulfate (0.3 g / L) to the above rhodium plating solution was used.

[0224] Using the above plating solution, adjusting the plating time, electroplating was carried out under the conditions of a bath temperature of 45 °C and a cathode current density of 1 A / dm 2 , and a rhodium coating was formed. A platinum-coated titanium electrode was used as the anode.

[0225] [The outermost layer 1d of Examples 2, 3, 6, 8, 9 and 10]

[0226] As the outermost layer 1d, a gold-silver alloy coating was formed in Example 2, a gold coating was formed in Examples 3, 6, 8 and 10, and a gold-cobalt alloy coating was formed in Example 9.

[0227] For the gold-silver alloy coating 1d in Example 2, a plating solution having the following bath composition was used.

[0228] Gold-silver alloy plating solution 2

[0229] Potassium gold cyanide was 4.25 g / L in terms of gold

[0230] Potassium silver cyanide was 0.75 g / L in terms of silver (85 mass% gold, 15 mass% silver)

[0231] Potassium cyanide = 30 g / L

[0232] Potassium citrate = 80 g / L

[0233] Potassium phosphate = 50 g / L

[0234] pH 9.5.

[0235] Using the above plating solution, adjusting the plating time, electroplating was carried out under the conditions of a bath temperature of 30 °C and a cathode current density of 1 A / dm 2 , and a gold-silver alloy coating was formed. A platinum-coated titanium electrode was used as the anode.

[0236] As the outermost layer 1d in Examples 3, 6, 8, and 10, except that the gold plating layer became the plating thickness shown in Table 1, the same plating solution as in Example 1 was used, the plating time was adjusted, and the gold plating layer was formed under the same conditions as in Example 1 except for this.

[0237] As the gold-cobalt alloy plating layer of the outermost layer 1d in Example 9, a plating solution obtained by adding an appropriate amount of cobalt sulfate (1.0 g / L) to the gold plating solution in Example 1 was used, the plating time was adjusted, and the gold-cobalt alloy plating layer was formed under the same conditions as in Example 1 except for this.

[0238] Then, in Examples 2 and 8, they were immersed in an aqueous solution containing 0.02% by mass of polyallylamine polymer PAA-08 (registered trademark; weight-average molecular weight 8000) manufactured by Nittobo Medical Co., Ltd. and 0.2% by mass of trisodium 1,3,5-triazine-2,4,6-trithiolate (Santhiol N-W manufactured by Sankyo Kasei Co., Ltd.), washed with water, and then dried. It should be noted that the immersion conditions are shown in Table 1.

[0239] In addition, in Examples 3, 6, and 9, they were immersed in an aqueous solution containing 0.01% by mass of polyallylamine polymer PAA-15 (registered trademark; weight-average molecular weight 15000) manufactured by Nittobo Medical Co., Ltd. and 0.1% by mass of trisodium 1,3,5-triazine-2,4,6-trithiolate (Santhiol N-W manufactured by Sankyo Kasei Co., Ltd.), washed with water, and then dried. In Example 9, a heat treatment was further performed at 250 °C for 2 hours. It should be noted that the immersion conditions are shown in Table 1.

[0240] In addition, in Example 10, a treatment of immersing at 20 °C in an aqueous solution containing 0.5% by mass of polyallylamine polymer PAA-03 (registered trademark; weight-average molecular weight 3000) manufactured by Nittobo Medical Co., Ltd. for 20 seconds was performed, washed with water, and then dried. A heat treatment was further performed at 450 °C for 5 minutes. It should be noted that the immersion conditions are shown in Table 1.

[0241] Comparative Examples 1, 2 and 3

[0242] As Comparative Example 1, a metal structure having the same structure as that of Example 1 and having nickel and gold plating layers with thicknesses as shown in Table 1 was prepared, but it was not treated in a solution containing a polyallylamine polymer. As Comparative Examples 2 and 3, metal structures having the same structure as that of Example 10 and having nickel, palladium, and gold plating layers with thicknesses in the ratios shown in Table 1 were prepared, but they were not treated in a solution containing a polyallylamine polymer. Using this metal structure, lead frame 10 was prepared as a pair of lead frames.

[0243] Optical semiconductor device

[0244] Next, using the metal structures for optical semiconductor devices of the examples and comparative examples as lead frames, each optical semiconductor device having a structure substantially the same as that of the optical semiconductor devices shown in Figure 1 A and 1B was manufactured. Until the optical semiconductor device 100 was singulated, each process was carried out in an assembled state, which was an assembly obtained by molding a plurality of resin moldings 3 on a lead frame 10 in a state where a plurality of pairs of lead frames 10 were connected together. For convenience, one optical semiconductor device 100 (singular) shown in Figure 1 A and 1B will be described. Using this lead frame 10, each optical semiconductor device of the examples and comparative examples having a structure substantially the same as that of the optical semiconductor devices shown in Figure 1 A and Figure 1 B was manufactured.

[0245] The resin molding 3 has a recess, and the lead frame 10 is exposed on the bottom surface of the recess. On this lead frame 10, a light-transmissive resin was used as the bonding member 4, and a rectangular light-emitting element 2 having positive and negative electrodes on its upper surface was placed and bonded. Then, by the casting method, a YAG phosphor and a sealing material containing a light-transmissive resin were dropped into the recess to form a sealing member 5.

[0246] Presence or absence of solder intrusion and sealing member leakage in resin molded body 3

[0247] Each optical semiconductor device of the examples and comparative examples was placed on a printed circuit board coated with a lead-free solder (Sn - 0.3Ag - 0.7Cu) paste, and after being mounted at a reflow temperature of 260°C for 10 seconds, the reflowed optical semiconductor device was peeled off, and using a stereomicroscope at 40 times magnification, it was evaluated whether the solder had penetrated into the resin molding 3, and the presence or absence of leakage of the sealing member was also evaluated. The evaluation results are shown in Table 2.

[0248] Total luminous flux retention rate after sulfur resistance test

[0249] To evaluate the sulfidation resistance reliability, each optical semiconductor device of the examples and comparative examples was placed in an environment of a temperature of 40°C and a humidity of 75% RH, and in an atmosphere containing 2 ppm of H 2A mixed gas of S and 4 ppm of NO 2 The exposure treatment was carried out for 100 hours in the mixed gas. The total luminous flux of the light emitted from the optoelectronic device before and after the exposure treatment was measured using an integrating sphere spectroscope, and the ratio obtained by dividing the total luminous flux after the exposure treatment by the total luminous flux before the exposure treatment was used as the retention rate of the total luminous flux. The results are shown in Table 2.

[0250] [Table 1]

[0251]

[0252] [Table 2]

[0253]

[0254] Examples 12 to 22 and Comparative Examples 4 to 6

[0255] In Examples 12 to 22 and Comparative Examples 4 to 6, the base material 1a, the nickel or nickel alloy plating layer 1b, and the noble metal plating layer 1c1 and / or the gold or gold alloy plating layer 1c2 provided as the base layer 1c as required were formed in the same manner as in Examples 1 to 11 and Comparative Examples 1 to 3, respectively. Using the following silver plating solution, a silver or silver alloy plating layer 1d was further formed thereon as the outermost layer.

[0256] In Examples 12, 13, 15, 16, 17, 19, 20, and 22, a silver plating layer was formed as the outermost layer using the following silver plating solution.

[0257] [Silver Plating Solution]

[0258] Potassium silver cyanide is 40 g / L in terms of silver

[0259] Potassium cyanide = 120 g / L

[0260] Potassium carbonate = 40 g / L

[0261] Potassium selenocyanate = 3 mg / L.

[0262] Using the above plating solution, the plating time was adjusted, and electroplating was carried out under the conditions of a liquid temperature of 30 °C and a cathode current density of 5 A / dm 2 to form a silver plating layer. A silver electrode was used as the anode.

[0263] In addition, in Examples 14, 18, and 21, a silver-gold alloy plating layer was formed as the outermost layer using the following silver-gold alloy plating solution. Among them, the concentration of potassium gold cyanide was adjusted so as to achieve the silver-gold alloy ratio of each example in Table 3. In terms of gold, it was adjusted to 2.0 g / L in Example 14, 4.0 g / L in Example 18, and 10.0 g / L in Example 21.

[0264] [Silver-Gold Alloy Plating Solution]

[0265] Potassium silver cyanide contains 40 g / L of silver

[0266] Potassium gold cyanide contains 2.0, 4.0 or 10.0 g / L of gold

[0267] Potassium cyanide = 120 g / L

[0268] Potassium carbonate = 40 g / L

[0269] Potassium selenocyanate = 3 mg / L

[0270] Using the above plating solution, adjusting the plating time, electroplating was carried out at a liquid temperature of 25°C and a cathode current density of 1 A / dm 2 under the conditions, and a silver-gold alloy coating was formed. A platinum-coated titanium electrode was used as the anode

[0271] Then, in Examples 12 to 22, treatments using polyallylamine polymers and, if necessary, triazine compounds were carried out respectively in accordance with Examples 1 to 11. It should be noted that in Comparative Examples 4 to 6, like Comparative Examples 1 to 3, the treatment using polyallylamine polymers was not carried out. In addition, regarding Examples 12 to 22 and Comparative Examples 4 to 6, like Examples 1 to 11 and Comparative Examples 1 to 3, the presence or absence of solder intrusion and seal member leakage of the resin molded body 3 was evaluated respectively, and the total luminous flux retention rate after the sulfur resistance test was measured. The manufacturing conditions are shown in Table 3, and the results are shown in Table 4

[0272] [Table 3]

[0273]

[0274] [Table 4]

[0275]

[0276] Examples 23 to 28 and Comparative Examples 7 to 9

[0277] As Figure 2 shown in A, using each plating solution having the bath composition shown below, under each condition, a nickel coating as a nickel or nickel alloy coating 1b provided as needed, and a gold, silver or silver-gold alloy coating as the outermost layer 1d provided on the nickel or nickel alloy coating 1b were sequentially formed on the surface of the following base material 1a by electroplating, thereby forming a metal structure 1 for an optical semiconductor device. Then, for Examples 23 to 28, a process of immersing in a solution containing a polyallylamine polymer, a process of washing, and a process of drying were carried out. The thickness (μm) of each layer, the composition of the solution containing the polyallylamine polymer, and the treatment conditions in the examples and comparative examples are described in Table 5

[0278] [Base materials 1a for Examples 23 to 28 and Comparative Examples 7 to 9]

[0279] In Examples 23 to 28 and Comparative Examples 7 to 9, a pure copper plate (oxygen-free copper plate with a length of 90 mm × a width of 60 mm × a thickness of 0.5 mm) was used as the base material.

[0280] [Nickel or nickel alloy plating layer 1b of Examples 23 to 24 and Comparative Example 7]

[0281] As the nickel or nickel alloy plating layer 1b, a nickel plating layer was formed in Examples 23 to 24 and Comparative Example 7. It should be noted that in Examples 25 to 28 and Comparative Examples 8 to 9, the plating layer 1b was not formed.

[0282] The nickel plating layers in Examples 23 to 24 and Comparative Example 7 used the same plating solution as in Example 1, and the plating time was adjusted. Other than that, the nickel plating layers were formed under the same conditions as in Example 1.

[0283] [Outermost layer 1d of Examples 23 to 28 and Comparative Examples 7 to 9]

[0284] As the outermost layer 1d, a gold plating layer was formed in Examples 23 to 24 and Comparative Example 7, a silver plating layer was formed in Examples 25 to 26 and Comparative Example 8, and a silver-gold alloy plating layer was formed in Examples 27 to 28 and Comparative Example 9.

[0285] The gold plating layer as the outermost layer 1d in Examples 23 to 24 and Comparative Example 7 used the same plating solution as in Example 1, and the plating time was adjusted. Other than that, the gold plating layer was formed under the same conditions as in Example 1.

[0286] As the outermost layer 1d in Examples 25 to 26 and Comparative Example 8, the silver plating layer used the same plating solution as in Example 12, and the plating time was adjusted so as to achieve the plating thickness shown in Table 5. Other than that, the silver plating layer was formed under the same conditions as in Example 12.

[0287] The silver-gold alloy plating layer as the outermost layer 1d in Examples 27 to 28 and Comparative Example 9 used the same plating solution as in Example 18, and the plating time was adjusted so as to achieve the plating thickness shown in Table 5. Other than that, the silver-gold alloy plating layer was formed under the same conditions as in Example 18.

[0288] Then, in Examples 23 and 25, they were immersed in an aqueous solution containing 0.5% by mass of polyallylamine polymer PAA-08 (registered trademark; weight-average molecular weight 8000) manufactured by Nittobo Medical Co., Ltd. at 30 °C for 15 seconds, washed with water, and then dried.

[0289] In Example 27, it was immersed at 30°C in an aqueous solution containing 0.7% by mass of polyallylamine polymer PAA-03 (registered trademark; weight-average molecular weight: 3000) manufactured by Nittobo Medical Co., Ltd. for 15 seconds, washed with water, and then dried.

[0290] In addition, in Examples 24, 26, and 28, it was immersed at 30°C in an aqueous solution containing 0.05% by mass of polyallylamine polymer PAA-08 (registered trademark; weight-average molecular weight: 8000) and 0.2% by mass of trisodium 1,3,5-triazine-2,4,6-trithiolate (Santhiol N-W manufactured by Sankyo Kasei Co., Ltd.) for 15 seconds, washed with water, and then dried.

[0291] It should be noted that in Comparative Examples 7 to 9, similar to Comparative Examples 1 to 3, the treatment using the polyallylamine polymer was not carried out.

[0292] Evaluation of adhesion to resin material

[0293] After applying an epoxy resin to the outermost surface of the metal structure for the opto-semiconductor device obtained in Examples 23 to 28 and the outermost surface of the coating film obtained in Comparative Examples 7 to 9, respectively, it was die-cut into a size of 7 mm in diameter, and the resin in other parts was removed. Then, after curing the epoxy resin applied to the outermost surface of the metal structure for the opto-semiconductor device and the outermost surface of the coating film by heat treatment at 150°C for 4 hours, the shear strength between the outermost surface of each of Examples 23 to 28 and Comparative Examples 7 to 9 and the epoxy resin was measured 5 times, and the average value was calculated. Then, in Examples 23 and 24, the shear strength of Comparative Example 7 was set to 100, in Examples 25 and 26, the shear strength of Comparative Example 8 was set to 100, and in Examples 27 and 28, the shear strength of Comparative Example 9 was set to 100, and relative evaluations were carried out respectively. It should be noted that the shear strength was measured using a universal welding strength tester 4000PXY manufactured by Nordson DAGE Co., Ltd. The results are shown in Table 5.

[0294] [Table 5]

[0295]

[0296] In the opto-semiconductor devices of Examples 1 to 22, no solder intrusion into the resin molding 3 was observed, and no leakage of the sealing member from the resin molding 3 to the outside was observed, and the adhesion between the resin material and the lead frame 10 was good. In addition, the opto-semiconductor devices of Examples 1 to 22 maintained almost the same total luminous flux after the sulfurization test as before the sulfurization test. In addition, the adhesion between the metal structure for the opto-semiconductor device of Examples 1 to 22 and the resin material of the constituent members was good.

[0297] In the optical semiconductor devices of Comparative Examples 1 to 6, solder invaded into the resin molded body 3, and the sealing member leaked from the resin molded body 3 to the outside. Therefore, the adhesion between the resin material of the constituent member and the lead frame 10 was not improved. In addition, in the optical semiconductor devices of Comparative Examples 4 to 6, the total luminous flux retention rate in the sulfurization test was significantly reduced.

[0298] In addition, for the metal structures for optical semiconductor devices of Examples 23 to 28, compared with the metal structures for optical semiconductor devices of Comparative Examples 7 to 9, the shear strength can be increased, and the adhesion to the resin material is good. This effect is more remarkable in Examples 24, 26, and 28. In Examples 24, 26, and 28, a triazine compound is also used in combination in a solution containing a polyallylamine polymer.

[0299] As described above, the metal structure for an optical semiconductor device of the present application can easily manufacture a substrate having a polyallylamine polymer attached to its surface by impregnating or coating a solution containing a polyallylamine polymer on a substrate having a top surface layer having at least one selected from gold, silver, a gold alloy, and a silver alloy (preferably a plating material selected from at least one of gold, silver, a gold alloy, and a silver alloy). As a result, a metal structure for an optical semiconductor device with improved adhesion to a resin material can be manufactured.

Claims

1. A manufacturing method of a metal structure for an opto-semiconductor device, the method comprising: (1) A treatment step of immersing and / or coating a substrate having a topmost layer containing at least one plating material selected from gold, silver, gold alloy, and silver alloy on a part or the whole surface with a solution containing a polyallylamine polymer, The solution containing the polyallylamine polymer further contains a triazine compound.

2. The manufacturing method according to claim 1, wherein, Taking the total amount of the solution containing the polyallylamine polymer as 100% by mass, the content of the polyallylamine polymer is 0.01% by mass or more and 1.0% by mass or less.

3. The manufacturing method according to claim 1 or 2, wherein, Taking the total amount of the solution containing the polyallylamine polymer as 100% by mass, the content of the triazine compound is 0.01% by mass or more and 1.0% by mass or less.

4. The manufacturing method according to claim 1 or 2, wherein, The triazine compound is a triazine thiol compound.

5. The manufacturing method according to claim 1 or 2, wherein, When performing the step (1), the temperature of the solution containing the polyallylamine polymer is 15°C or more and 50°C or less.

6. The manufacturing method according to claim 1 or 2, wherein, The treatment time for performing the step (1) is 3 seconds or more and 60 seconds or less.

7. The manufacturing method according to claim 1 or 2, wherein, After the step (1), the following steps are sequentially included: (2) A step of cleaning the substrate that has undergone the step (1); and (3) A step of drying the substrate that has undergone the step (2).

8. The manufacturing method according to claim 7, wherein, After the step (3), the following step is included: (4) A step of heat-treating the substrate that has undergone the step (2).

9. The manufacturing method according to claim 1 or 2, wherein, The substrate has a base material containing copper or a copper alloy.

10. The manufacturing method according to claim 9, wherein, Between the topmost layer and the base material, at least one selected from a nickel or nickel alloy plating layer, a palladium or palladium alloy plating layer, a rhodium or rhodium alloy plating layer, and a platinum or platinum alloy plating layer is provided.

11. A manufacturing method of an opto-semiconductor device, the method comprising: A step of molding a resin molded body in such a manner that it is in contact with the substrate of the metal structure for an opto-semiconductor device manufactured by using the manufacturing method according to any one of claims 1 to 10.

12. A package, which includes a substrate and a resin molded body formed on the substrate, the substrate having a topmost layer containing at least one plating material selected from gold, silver, gold alloy, and silver alloy on a part or the whole surface, A film containing a polyallylamine polymer and a triazine compound is attached to the topmost layer of the substrate.

13. The package according to claim 12, wherein, The thickness of the film containing the polyallylamine polymer and the triazine compound is 10 nm or more and 500 nm or less.

14. The package according to claim 12 or 13, wherein, The triazine compound is a triazine thiol compound.

15. A solution containing a polyallylamine polymer and a triazine compound, which is used to improve the adhesion between a lead frame and an adjacent resin molded body in an optical semiconductor device, wherein the lead frame has a topmost layer containing at least one selected from gold, silver, gold alloy, and silver alloy on a part or the whole surface.

16. The solution according to claim 15, wherein, assuming the total amount of the solution containing the polyallylamine polymer is 100% by mass, the content of the polyallylamine polymer is 0.01% by mass or more and 1.0% by mass or less.

17. The solution according to claim 15 or 16, wherein, assuming the total amount of the solution is 100% by mass, the content of the triazine compound is 0.01% by mass or more and 1.0% by mass or less.

18. A method for manufacturing a metal structure for an optical semiconductor device, the method comprising the following processing steps: (1) Immersing and / or coating a substrate having a topmost layer containing at least one selected from gold, silver, gold alloy, and silver alloy on a part or the whole surface with a solution containing a polyallylamine polymer, wherein the solution containing the polyallylamine polymer further contains a triazine compound.

19. The manufacturing method according to claim 18, wherein, assuming the total amount of the solution containing the polyallylamine polymer is 100% by mass, the content of the polyallylamine polymer is 0.01% by mass or more and 1.0% by mass or less.

20. The manufacturing method according to claim 18 or 19, wherein, assuming the total amount of the solution containing the polyallylamine polymer is 100% by mass, the content of the triazine compound is 0.01% by mass or more and 1.0% by mass or less.

21. The manufacturing method according to claim 18 or 19, wherein, the triazine compound is a triazine thiol compound.

Images