JP2009059910A - Lead, wiring member, package component, metal component with resin and resin sealed semiconductor device, and manufacturing method of them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To easily remove resin burrs of a semiconductor device having a lead resin-molded without damaging a resin body covering the lead. <P>SOLUTION: In the semiconductor device 10, the lead 11 is formed by coating an external surface of a metal thin plate material with a metal coating, and a semiconductor element 12 is fitted. A peripheral portion 15 of the lead 11 is covered with a coating including a purine skeleton. The coating is formed by making functional organic molecules being constituted of the purine skeleton having at an end a functional group with a bonding property to metal, self-organize to the lead 11. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a wiring member, a package component, a resin-attached metal component, a resin-encapsulated semiconductor device, and a manufacturing method thereof, and more particularly to a technique for removing a resin burr generated when a lead is resin-molded.

Leads made of metal plates are used as parts for electrical connection with semiconductor elements such as LEDs and LSIs. The lead electrically connected to the semiconductor element is commercialized with the semiconductor element covered with a coating resin.
Specifically, the semiconductor element and the lead are integrally molded with a coating resin. The integral molding is performed by inserting a lead to which a semiconductor element is fixed into a mold and then injection-molding a thermosetting resin in the mold (see, for example, Patent Document 1).

  FIG. 7 is a diagram showing a manufacturing process in which a part of the lead 102 and the semiconductor element 106 are coated with a resin. FIG. 7A shows the lead 102. FIG. 7B shows a state in which the semiconductor element 106 is fixed on the lead 102 and electrically connected to the lead 102. The semiconductor element 106 is fixed on the lead 102 by die bonding, and the lead 102 and the semiconductor element 106 are connected by an electric connection wire 108 by wire bonding.

  FIG. 7C shows a state in which the semiconductor device intermediate including the lead 102 in the state of FIG. 7B is mounted on a mold for resin coating. The semiconductor device intermediate is molded with a coating resin body 160 (see FIG. 7D) using the molds 100 and 110. The coating resin body 160 is molded by injecting a coating resin from the resin inlet 120 and extracting air from the air outlet 140.

FIG. 7D shows the semiconductor device intermediate body after the coating resin body 160 is molded.
The central portion of the lead 102 is covered with a resin body 160, but a resin burr is formed in the peripheral portion 102a outside the lead 102 by a coating resin that leaks through a gap formed between the upper and lower molds 100 and 110. The
If a resin burr is formed, the electrical connection between the semiconductor element and the lead is hindered, and the solderability and appearance of the lead are remarkably impaired. For example, in order to eliminate the resin burr, a part where the resin burr is formed A method of spraying a liquid at a high pressure and a method of forming irregularities on a burr surface by roughening a part of a mold to a specific surface roughness to facilitate peeling of the burr (for example, (See Patent Document 3).

FIG. 21 is also a diagram showing a manufacturing process of a resin-sealed QFP (Quad Flat Package) type semiconductor device.
A semiconductor chip 94 is mounted on the die pad 93 b of the wiring lead 93 (die pads 93 a and 93 b), and the semiconductor chip 94 and the die pads 93 a and 93 b are connected by a wire 95. Thereafter, the wiring lead 93 is placed on the fixed mold 92 (FIG. 21A).

Next, the movable die 91 is pressed against the fixed die 92, and a thermosetting resin is injection-molded into the cavity 97 through the gate 96 provided on the movable die 91, thereby sealing the semiconductor chip 94 with the resin. It stops (FIG. 21B).
After the resin is cured, the mold is opened, and the resin molded product 9z is extruded with an ejector pin (not shown).
Then, by bending the outer lead 931a of the resin molded product 9z, the semiconductor device 9 is completed (FIG. 21 (c)).

When the semiconductor device 9 is mounted, the outer leads 931a are joined to the substrate 99 via the solder 90 (FIG. 21D).
In addition to the above, as a semiconductor device, for example, there is a light emitting diode (LED) device. This is because, for example, a substrate formed so that a part of the wiring lead is exposed inside the scalloped reflector, a light emitting diode element is mounted and connected to the wiring lead inside the reflector, and then the inside of the reflector It is manufactured by filling a transparent sealing resin.

As the sealing resin, a silicone resin having a higher light transmittance is now widely used in place of the epoxy resin.
Furthermore, in film carrier tapes such as TAB (Tape Automated Bonding) tape, T-BGA (Tape Ball Grid Array) tape, and ASIC (Application Specific Integrated Circuit) tape used for mounting electronic parts such as IC and LSI, polyimide is used. An insulating film made of, etc., a wiring pattern layer made of Cu, and a solder resist layer are laminated in the same order, and a resin material is used for the insulating film and the solder resist layer.
JP-A-6-69366 Japanese Patent Laid-Open No. 2005-42099 JP-A-7-183416 Japanese Patent No. 2731123 Japanese Patent Laid-Open No. 10-329461 JP 2002-33345 A Patent No. 3076342

Thus, the semiconductor device, LED device, and film carrier tape manufactured by resin molding have the following problems.
The first problem is that the resin adheres to the region of the wiring lead that is not originally scheduled for resin molding in addition to the target resin molding at the time of injection molding of the sealing resin.
That is, in the step of injecting the resin into the mold, as shown in the P partial enlarged view of FIG. 21B, the gap 900 due to poor accuracy between the molds 91 and 92 is formed on the surface of the outer lead 931a of the wiring lead 93. Therefore, the resin flows out from the gap 900 and a resin burr 98a can be generated (FIG. 21 (c)).

If the resin burr 98a is present, problems occur in the bonding strength and electrical contact between the outer lead 931a and the substrate 99 in the next step.
If the gaps 900 are eliminated by machining the molds 91 and 92 with high accuracy, the generation of resin burrs can be prevented. However, it is very expensive to machine the molds with high accuracy. Since it is difficult to eliminate completely, it is actually impossible to completely prevent the generation of resin burrs.

Accordingly, a process for removing the resin burr 98a is required prior to the bonding process to the substrate, leading to a decrease in manufacturing efficiency and an increase in manufacturing cost.
In addition, if the high-pressure liquid is sprayed on the portion where the resin burr is formed in order to remove the resin burr, a crack is likely to occur in the resin body. Also, in the method of roughening treatment, the coating resin penetrates into the surface irregularities of the roughened mold due to capillary action, resulting in poor mold releasability and mold cleaning cycles. There is a problem of shortening.

In addition to this, there are techniques as proposed in Patent Documents 4 to 6 as measures for preventing gaps between molds. Patent Documents 4 and 5 strengthen the pressing force on the wiring leads of the molds. Technology is disclosed.
However, this method has a risk of applying excessive deformation stress to the wiring lead, and may cause damage to the mold and the wiring lead.

Patent Document 6 discloses a technique for preliminarily attaching a tape to a gap generating portion between molds to achieve sealing, but the injection molding process is performed at a relatively high temperature, Since the mechanical frictional force is also exerted, even if such a tape is used, in reality, the tape is easily peeled or damaged, and there are problems in terms of manufacturing efficiency and manufacturing cost because the tape is provided.
The second problem is a problem when a silicone resin is used as the sealing resin for the LED device.

  Silicone resin can ensure high transparency, but has a higher coefficient of linear expansion than epoxy resin. For this reason, in the process of injection-molding the silicone resin on the substrate, the silicone resin can be thermally contracted due to a thermal change (so-called thermal history) received by the resin material. As a result, peeling occurs between the silicone resin and the wiring lead, which may cause problems such as performance deterioration due to poor contact or insufficient bonding strength.

  In addition, in a lead for LED, a silver coating having a high reflectance in the visible light region is applied to the surface of a metal plate body that is a lead body, and is often coated with a highly transparent addition polymerization type silicone resin. Since a chloroplatinic acid compound is generally used as a reaction catalyst for the addition polymerization type silicone resin, the silver coating undergoes a substitution reaction with the platinum chloride compound to form silver chloride, which changes to black due to light emission of the LED. Thus, the problem that the silver coating is discolored has also arisen.

  As a third problem, there is also a problem related to the Ag plating film provided on the wiring lead. It is known that Ag material can increase the reflectivity of visible light in the long wavelength region, and contributes to the improvement of the light emission efficiency in the LED device, but is relatively reflective to the light in the short wavelength region (about 500 nm or less). The rate is low. Therefore, when a diode for blue light emission, purple light emission, ultraviolet light emission or the like is mounted on the LED device, a sufficient reflectance cannot be obtained, and a problem that the light emission efficiency cannot be obtained may occur.

A 4th subject is a subject at the time of giving Sn plating to a wiring pattern layer in a film carrier tape.
The surface of the wiring pattern layer is pre-coated with an Sn plating layer to be connected to the mounting component by soldering. In this plating process, the end of the solder resist layer is turned up by the heating atmosphere, and the solder that has been turned up. There is a problem that a local battery is generated due to a difference in ionization tendency of Sn ions and Cu ions between the resist layer and the surface of the wiring pattern layer and between the surface regions of other wiring pattern layers (FIG. 22 ( a)). When a local battery is generated, an erosion region due to Cu ions eluted on the surface of the wiring pattern layer is generated. For this reason, the mechanical strength of the film carrier tape after Sn plating is lowered, and there is a problem that uniform plating cannot be performed.

In view of the above problems, the present invention firstly prevents lead discoloration in a lead and a lead manufacturing method, a package component in which a lead is resin-molded, a package component manufacturing method, a semiconductor device, or a semiconductor device. The purpose of this is to suppress the generation of resin burrs.
Secondly, in LED devices, by improving the adhesion between the silicone resin and the wiring lead, it exhibits good light-emitting characteristics, and when the silver film is formed on the lead body, the corrosion resistance is improved. The purpose is to let you.

Thirdly, an object of the present invention is to provide an LED device that exhibits excellent luminous efficiency by providing sufficient reflectance even when emitting light in a relatively short wavelength region.
Fourthly, in the film carrier tape, while maintaining good manufacturing efficiency, it avoids damage to the wiring pattern layer during the Sn plating step, and provides excellent formation of the Sn plating layer, mechanical strength, and bondability. The purpose is to provide things.

In order to achieve the above object, according to the present invention, in a lead that is partially coated with a resin body and used for a package component, a semiconductor device, etc., a metal plate material that is a lead body is coated with a coating containing a compound having a purine skeleton It was decided to.
Here, the metal plate material is composed of a conductive plate body, and a metal such as nickel, palladium, tin, copper, silver, or gold is exposed on the surface thereof.

Here, it is preferable to coat at least a portion other than the portion covered with the resin body with a coating containing a compound having a purine skeleton.
The film containing the compound having a purine skeleton is preferably formed of a purine skeleton compound having a polar group, and is coated so as to bind the polar group to the surface of the metal plate material.
The polar group of the above compound is preferably a nitrogen-containing heterocyclic ring or a thiol group.

  As the purine skeleton compound, a compound represented by the following general formula 7 or 8 or a derivative thereof is preferable.

(但し、R1、R2、R3、R4のいずれかに、極性基を有し、その他は、水素、アミン、水酸基、ケトン、アルデヒド、カルボン酸、スルホ化合物ン酸、アミド、ヒドラジド、ヒドラジン、アミジン、エーテル、ハロゲン、ニトリル、メチレン、アリール、シロキサン、グリコール表す。)
また上記目的を解決するため、本発明の樹脂付金属部品の製造方法では、プリン骨格の一端に金属に対する結合性を有する第一官能基、他端に所定の特性を持つ第二官能基を備える機能性有機分子を含む材料を、金属材料からなる配線リードに被着させ、当該配線リードを構成する金属原子に前記第一官能基を結合させた状態で各機能性有機分子を自己組織化させることによって有機被膜を形成する有機被膜形成工程と、有機被膜形成工程後に、有機被膜を配した配線リードの所定表面領域にわたり樹脂を固着させる樹脂固着工程とを経ることとした。

(However, any of R1, R2, R3, R4 has a polar group, others are hydrogen, amine, hydroxyl group, ketone, aldehyde, carboxylic acid, sulfo compound acid, amide, hydrazide, hydrazine, amidine, (Denotes ether, halogen, nitrile, methylene, aryl, siloxane, glycol)
In order to solve the above-mentioned object, in the method for producing a metal part with a resin according to the present invention, a first functional group having a metal binding property is provided at one end of the purine skeleton, and a second functional group having predetermined characteristics is provided at the other end. A material containing a functional organic molecule is deposited on a wiring lead made of a metal material, and each functional organic molecule is self-assembled in a state where the first functional group is bonded to a metal atom constituting the wiring lead. Thus, an organic film forming process for forming the organic film and a resin fixing process for fixing the resin over a predetermined surface region of the wiring lead provided with the organic film after the organic film forming process are performed.

Here, the predetermined characteristics possessed by the second functional group are a characteristic for curing the resin, a characteristic for promoting the curing of the resin, and the like.
Examples of the compound having a purine skeleton include compounds represented by general formula 7 or 8 or derivatives thereof, and examples of the first functional group include thiol compounds, sulfide compounds, and nitrogen-containing heterocyclic compounds. It is done.

  It is preferable to use a thermosetting resin as the resin, and as the thermosetting resin, epoxy resin, phenol resin, acrylic resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyimide resin, polyamide resin, polyether Resin. In this case, as the second functional group, hydroxyl group, carboxylic acid, acid anhydride, primary amine, secondary amine, tertiary amine, amide, thiol, sulfide, imide, hydrazide, imidazole, diazabicycloalkene, An organic phosphine or boron trifluoride amine complex may be used.

In the organic film forming step, the organic film is preferably formed on the surface of the wiring lead over an area larger than a predetermined surface region of the wiring lead to which the resin is to be fixed in the resin fixing step.
When a silicone resin is used as the thermosetting resin, a compound containing a vinyl group and an organic hydrogen silane may be used as the second functional group.

In addition, when using a silicone resin containing either or both of an epoxy group and an alkoxysilyl group as a thermosetting resin, a hydroxyl group, a primary amine, a secondary amine, and an acid anhydride are used as the second functional group. You may use the compound containing.
When a silicone resin is used as the thermosetting resin, a metal complex containing one or more selected from platinum, palladium, ruthenium, and rhodium may be used as the second functional group.

In the case where the silicone resin is fixed in the resin fixing step, a silicone resin-containing conductive paste (die bonding agent) may be used.
As the second functional group, a fluorescent compound or a phosphorescent compound can be used.
In addition, the organic film forming step includes a dispersion preparation substep for preparing an organic molecule dispersion by dispersing functional organic molecules in a solvent, and a predetermined surface of the wiring lead to which the resin is to be fixed among the wiring lead surface. It can be carried out by an immersion sub-process in which the wiring lead is immersed in the organic molecular dispersion over an area larger than the region.

In the method for manufacturing a semiconductor device of the present invention, the metal part with resin is manufactured by using the method for manufacturing the metal part with resin of the present invention, and the wiring lead is formed between the organic film forming step and the resin fixing step. In the resin fixing step, resin molding is performed so that the semiconductor element is included and a part of the wiring lead is exposed to the outside.
In addition, the wiring member of the present invention is configured by depositing an organic coating by self-organization of functional organic molecules on the surface of a wiring lead made of a metal material, and the functional organic molecules are attached to one end of the purine skeleton. A first functional group exhibiting at least one of a hydrogen bond or a coordinate bond is arranged on the metal of the wiring lead, and a second functional group exhibiting resin curing property or resin curing acceleration property is provided at the other end. Using the one having the arranged chemical structure, the first functional group was bonded to the wiring lead.

The metal part with resin of the present invention has a configuration in which a resin is fixed to a part of the wiring member of the present invention and an organic coating is deposited over an area larger than the surface area of the wiring member to which the resin is fixed.
The resin-encapsulated semiconductor device of the present invention is a region in which a semiconductor element is electrically connected to a wiring lead to the wiring member of the present invention, a part of the wiring member is exposed to the outside, and an organic film is formed. The semiconductor element was sealed with resin.

  The film carrier tape of the present invention has a structure in which an organic film and a solder resist layer are sequentially laminated on the surface of a wiring pattern layer made of a metal material, and the organic film is formed by self-organization of functional organic molecules. In the organic molecule, one end of the purine skeleton is provided with a first functional group having a binding property to the metal of the wiring pattern layer, and the other functional group is provided with a second functional group having a chemical binding property with the solder resist layer. The first functional group was bonded to the wiring pattern layer, and the second functional group was bonded to the solder resist layer.

  In the method for producing a film carrier tape, a wiring pattern layer comprising a material containing a functional organic molecule having a first functional group having a binding property to a metal at one end of a purine skeleton and a second functional group having a predetermined property at the other end An organic film forming step of forming an organic film by attaching a first functional group to a metal atom constituting a wiring lead and self-organizing each functional organic molecule; A solder resist layer forming step of applying a solder resist material to form a solder resist layer so as to be chemically bonded to the second functional group of the functional organic molecule is provided.

Here, it is preferable to use a second functional group that exhibits at least one of resin curability and photopolymerization initiating upon chemical bonding with the solder resist material.
Moreover, what contains 1 or more types selected from an acid anhydride and a primary amine compound may be used for the 2nd functional group using what exhibits resin curability.
Further, as the second functional group, those exhibiting photopolymerization initiating properties, specifically, benzophenones, acetophenones, alkylphenones, benzoins, anthraquinones, ketals, thioxanthones, coumarins, halogenated triazines, Halogenated oxadiazoles, oxime esters, acridines, acridones, fluorenones, fluorans, acylphosphine oxides, metallocenes, polynuclear aromatics, xanthenes, cyanines, squaliums, acridones, titanocenes In the solder resist layer forming step, the second functional group is excited by light irradiation and a solder resist material is applied on the organic film, and the resist material is a resist material that contains at least one selected from tetraalkylthiuram sulfides. Photopolymerize It is also preferred.

  In the organic film forming process, an organic film is formed using functional organic molecules having a photopolymerization-initiating second functional group. In the solder resist layer forming process, the wiring pattern layer formed with the organic film is photopolymerized. In addition to being immersed in a dispersion solution in which the functional molecules are dispersed, and applying a predetermined pattern mask to the wiring pattern layer and irradiating with light in the dispersion solution, a polymerization reaction is caused to the second functional group and a predetermined pattern is generated. A patterned solder resist layer may be formed by polymerization.

  In addition, an Sn plating layer forming step of forming a wiring pattern layer with a Cu material and forming an Sn plating layer on a predetermined surface of the wiring pattern layer other than the region where the solder resist layer is formed after the deposition solder resist layer forming step. May be provided.

  As described above, the lead according to the present invention covers the metal plate material, which is a lead body, with a coating containing a compound having a purine skeleton. Therefore, when a silver thin film is formed on the surface of a metal plate that is a lead body like an LED and is coated with an addition polymerization type silicone resin, the substitution reaction between the silver coating and the platinum chloride compound catalyst in the silicone resin. Since the formation of silver chloride due to is suppressed, the effect of preventing discoloration of the silver coating film is exhibited.

The purine skeleton is a nitrogen-containing condensed heterocyclic ring having a planar structure composed of a condensed ring of an aromatic pyrimidine ring and an imidazole ring, and the purine skeletons are bonded to each other by a carbon π electron and a nitrogen n electron in the structure. In the meantime, the dispersion force of London works to produce a stacking effect. Therefore, the self-assembled film made of a compound having a purine skeleton is very stable.
Therefore, even if there is a high-temperature process (for example, about 300 to 360 ° C. in the case of gold-tin eutectic solder bonding) in the semiconductor element mounting process, the film is difficult to be decomposed, and the function as a lead surface protective film is sufficient. Can be maintained.

In addition, not only the purine skeleton but also a condensed aromatic heterocycle or a compound having another aromatic ring also exhibits a stacking effect due to the London dispersion force, but among the condensed aromatic heterocycles, the purine ring is also Since the skeleton is very stable and the coating itself improves the “heat resistance”, it is preferable.
According to the method for manufacturing a metal part with resin according to the present invention, an organic film formed by self-organization of the functional organic molecules is disposed on the surface of the wiring lead made of a metal material in the organic film forming step. However, the functional organic molecule has a first functional group exhibiting a binding property to a metal at one end of the purine skeleton and a second functional group having a predetermined property at the other end. Are self-organized on the surface of the wiring lead, the first functional group is aligned with the surface of the wiring lead and the second functional group is aligned with the top surface. The second functional group is exposed on the surface of the organic coating.

Therefore, when the resin material is fixed in the resin fixing step, a chemical action corresponding to the characteristics of the second functional group is exerted between the second functional group on the surface of the organic coating and the resin material. The problem can be solved.
That is, when the second functional group has a binding property that chemically bonds to the resin material, the binding force between the resin material fixed on the organic coating and the organic coating is increased.

  Moreover, when it has the sclerosis | hardenability which hardens a resin material, or the effect acceleration property which accelerates | stimulates hardening of a resin material, a resin material can be hardened rapidly. As a result, the resin material filled in the cavity is quickly cured on the organic coating, and even if there is an unnecessary gap in the mold during injection molding, it instantly cures when the resin material tries to flow through the gap. As a result, leakage of the resin from the gap is suppressed.

Therefore, an extra step of removing the resin burr after the resin molding becomes unnecessary.
The effects of the present invention can be obtained without modifying the injection molding apparatus or adding a separate apparatus. Therefore, according to the present invention, it is possible to realize a semiconductor device having good electrical connectivity at low cost and with excellent manufacturing efficiency.
Specifically, when a compound containing a vinyl group or organic hydrogen silane is used as the second functional group, a strong chemical bond can be obtained between the organic coating and the silicone resin.

  In addition, when using a silicone resin-containing silicone resin containing either or both of an epoxy group and an alkoxysilyl group as the thermosetting resin, the secondary functional group includes a hydroxyl group, a primary amine, a secondary amine, an acid. By using an anhydride, it is possible to obtain a strong chemical bond with either or both of the epoxy group and alkoxysilyl group in the silicone resin.

Therefore, if an organic coating composed of such functional organic molecules is formed on the wiring lead of the LED device, peeling or cracking between the silicone resin and the wiring lead, or contact at a high temperature Generation | occurrence | production of problems, such as performance degradation by a defect and insufficient joint strength, can be suppressed, and the luminous efficiency of an LED apparatus can be stabilized.
Further, in the LED device, if a functional organic molecule having a platinum complex as the second functional group and an organic film is disposed on the surface of the wiring lead, the silicone resin filled thereon is cured very quickly.

Therefore, even if there is an unnecessary gap at the boundary between the reflector and the wiring lead, the silicone resin is prevented from flowing into the gap.
In addition, when using a silicone resin-containing conductive paste (die bonding agent such as an Ag paste) in the resin fixing step, a semiconductor chip such as an LED and a die pad are firmly bonded by die-bonding the silicone resin-containing conductive paste. It is possible to make it. When the silicone resin-containing conductive paste is used, since the deterioration is less than that of the conventional epoxy resin-containing conductive paste, it is possible to achieve stabilization of conductivity and thermal conductivity.

Further, when Ag particles are used in the silicone resin-containing conductive paste, an organic coating may be applied to the Ag particles. Thereby, it is also possible to suppress discoloration of Ag particles in the conductive paste.
Further, in the LED device, when the Ag plating film is applied to the wiring lead, the reflection efficiency in the short wavelength region due to the Ag plating film tends to be low, but a fluorescent compound or a phosphorescent compound is used as the second functional group. When an organic film is formed on the wiring lead with functional organic molecules, the reflectance with respect to short-wavelength light in the ultraviolet light or visible light region is improved, so that good luminous efficiency can be expected as the whole device.

  In addition, in the film carrier tape, the surface of the wiring pattern layer made of a metal material has a structure in which an organic film and a solder resist layer are sequentially laminated, and has a first functional group that exhibits binding properties to the metal of the wiring pattern layer, If an organic film is formed using a functional organic molecule having a second functional group having a binding property to the solder resist layer, the layer structure of the wiring pattern and the solder resist layer can be stably maintained.

Therefore, even when Sn plating is performed thereafter, the end of the solder resist layer is prevented from turning up from the wiring pattern, and the generation of local batteries is suppressed. Therefore, a high quality film carrier tape can be manufactured.
The organic film formed by self-organization of functional organic molecules as described above is basically a monomolecular film, and the film thickness is a monomolecular level, so it occupies almost no space. Bondability to the lead is extremely excellent, and the anticorrosion, rust prevention, and insulation resistance of the wiring lead region coated with the organic coating can be enhanced. Further, it is not necessary to remove the organic coating after the resin is fixed.

  As described above, the present invention is completely different from general surface treatment agents, surfactants, paints and the like in terms of functionality and configuration.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. However, the present invention is not limited to these embodiments, and may be modified as appropriate without departing from the technical scope of the present invention. Can be implemented.
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[Embodiment 1]
<Configuration>
FIG. 1 is a cross-sectional view of a semiconductor device 10 according to the present embodiment. This semiconductor device 10 is a surface mount type semiconductor device used for IC, LSI, etc., and as shown in the figure, is composed of a lead 11, a semiconductor element 12, an electric connection wire 13, and a covering resin body 14. Yes.
(Lead 11)
The lead 11 is configured such that the surface of a thin metal plate material 11a such as copper, copper alloy, iron, or iron alloy is covered with a metal coating 21 (see FIG. 2).

The metal coating 21 is made of, for example, a metal such as nickel, palladium, tin, copper, silver, or gold, and is formed by wet plating or dry plating on the surface of the lead.
The outermost surface of the metal coating 21 is preferably silver, gold or copper.
(Semiconductor element 12)
The semiconductor element 12 is die-bonded and fixed onto the lead 11 and is wire-bonded to the connection portion of the lead 11 with an electric connection wire 13.
(Electric connection wire 13)
The electrical connection wire 13 electrically connects the semiconductor element 12 and the lead 11.

As the electrical connection wire 13, it is desirable to have good ohmic properties, mechanical connectivity, electrical conductivity and thermal conductivity with the connection portion. For example, a conductive wire using gold, copper, platinum, aluminum, or the like or an alloy thereof can be used. Such a conductive wire can be easily connected to the connecting portion by a wire bonding apparatus.
(Coating resin body 14)
The covering resin body 14 is formed so as to cover a part of the lead 11 together with the semiconductor element 12 and seals them.

The covering resin body 14 is formed of, for example, an epoxy resin, a silicone resin, a melamine resin, a phenol resin, a polyphthalamide resin, a liquid crystal polymer, or the like.
(A peripheral portion of the coating resin body 14)
In FIG. 1, a portion (peripheral portion) of the lead 11 that is not covered with the covering resin body 14 is indicated by reference numeral 15. As described in “Background Art”, the peripheral portion 15 is a portion where resin burrs are generated.

In the peripheral portion 15 of the lead 11, the surface of the metal coating 21 is covered with a coating 22 made of a compound having a purine skeleton.
FIG. 2 is a cross-sectional view showing the structure of the peripheral portion 15 in the lead 11. As shown in the drawing, in the peripheral portion 15 of the lead 11, the outer surface of the thin metal plate 11 a is covered with a two-layer film of a metal film 21 and a film 22 made of a compound having a purine skeleton.

(Structure of the coating film 22 containing a compound having a purine skeleton)
The film 22 containing a compound having a purine skeleton is formed of a film agent made of a purine skeleton compound or a derivative thereof.
The purine skeleton compound herein is a compound containing a polar group (for example, thiol, sulfide, disulfide, thiol derivative, nitrogen-containing heterocyclic compound, etc.) capable of binding to a metal and a purine skeleton.

  Specific examples of the purine skeleton compound include compounds represented by general formula 9 or 10 or derivatives thereof. (However, any of R1, R2, R3, R4 has a polar group, others are hydrogen, amine, hydroxyl group, ketone, aldehyde, carboxylic acid, sulfonic acid, amide, hydrazide, hydrazine, amidine, ether, (Represents halogen, nitrile, methylene, aryl, siloxane, glycol)

上記極性基は、プリン骨格化合物の末端にあって、金属被膜２１と結合するカップリング剤として機能する基である。
極性基としては、ＳＨ基をはじめ、含窒素複素環化合物でもよく、例えば、イミダゾール化合物、トリアゾール化合物、テトラゾール化合物、ジアジン化合物、トリアジン化合物、テトラジン化合物で形成しても良い。又、含窒素複素環化合物にチオールまたはチオール塩を修飾した化合物で形成してもよい。

The polar group is a group that functions as a coupling agent bonded to the metal coating 21 at the end of the purine skeleton compound.
The polar group may be an SH group or a nitrogen-containing heterocyclic compound, and may be formed of, for example, an imidazole compound, a triazole compound, a tetrazole compound, a diazine compound, a triazine compound, or a tetrazine compound. Moreover, you may form with the compound which modified the thiol or thiol salt to the nitrogen-containing heterocyclic compound.

Since the purine skeleton compound is a functional organic molecule having a polar group capable of binding to a metal, the purine skeleton compound is deposited on the surface of the metal coating 21, and is formed on the surface of the metal coating 21. Form.
Specifically, when the polar group is a thiol group (X-SH, where X is a purine skeleton or a derivative thereof), a metal atom that can be a monovalent or higher cation such as gold (Au) or silver (Ag) Coordinates and binds to the surface of the metal coating 21 by a covalent bond such as Au—S—X or Ag—S—X.

Similarly, when the polar group is a disulfide group (X1-SS-X2), sharing of Au (-S-X1) (-S-X2) or Ag (-S-X1) (-S-X2), etc. The bond forms a strong bond structure.
When the polar group contains a nitrogen-containing heterocyclic compound such as an azole compound or an azine compound, the unshared electron pair of the nitrogen atom in the molecule forming the compound is coordinated to a metal that can be a divalent or higher cation. Can be combined. For example, an imidazole compound, a benzotriazole compound, a triazine compound, and the like are preferable because they easily form a coordinate bond with a metal such as Cu.

FIG. 3 is a diagram schematically illustrating an example in which a self-assembled monolayer is formed on the surface of the metal coating 21 by a compound having a purine skeleton constituting the coating 22.
In FIG. 3, a compound containing a thiol or a thiol derivative is bonded to a metal on the surface of the metal coating 21 via a thiol (SH) group (indicated by reference numeral 40), and accordingly, the purine skeleton 41 faces outward. They are arranged on the surface of the metal coating 21 in a state.

Here, the dispersion force (arrow 42) acts between the adjacent purine skeletons 41 due to carbon π electrons and nitrogen n electrons in the structure of the compound, thereby producing a stacking effect and bonding to each other. is doing.
As described above, in the peripheral portion 15 of the lead 11, the coating 22 made of a monomolecular film is formed on the surface of the metal coating 21, and the purine skeleton 41 is densely arranged on the surface of the coating 22. This suppresses the intrusion of moisture and noble metal ions into the metal coating 21, and has a high antirust effect and discoloration prevention effect.

It should be noted that the compound constituting the film 22 is not limited to a compound having a purine skeleton, but using a condensed aromatic heterocyclic ring or a compound having another aromatic ring also exhibits a stacking effect due to London dispersion force. Among the condensed aromatic heterocycles, the purine ring is preferable in that the skeleton is very stable and the heat resistance of the coating itself is improved.
FIG. 4 shows a platinum-based metal catalyst (H ₂ PtCl ₆ · m H ₂ O, K ₂₎ contained in a light-transmitting addition polymerization type silicone resin depending on the presence or absence of the coating 22 made of a compound having a purine skeleton. _{P t C l 6, K H} P t C l 6 · m H 2 O, K 2 P t C l 4, K 2 P t C l 4 · m H 2 O, (m is a positive integer), and the like It is a schematic diagram which shows a mode that the effect | action which gives discoloration to the silver metal film 21 differs.

FIG. 4A shows a case where the film 22 made of a compound having a purine skeleton does not exist. In this case, when the platinum-based metal catalyst 51 approaches the surface of the metal coating 21, the platinum 52 causes a substitution reaction with the metal on the surface of the silver metal coating 21.
As a result, platinum metal 53 is formed on the silver metal, and at the same time, silver chloride 54 is generated.
Since this silver chloride has the property of being easily black-discolored by light energy (hν), the coating 21 is discolored.

  FIG. 4B shows a case where a film 22 made of a compound having a purine skeleton is present. The surface of the metal film 21 is occupied by thiol groups 40 contained in the film 22, and the purine skeleton 41 is formed by the film 22. It is expressed on the surface side. In this case, even if each platinum-based metal catalyst 51 approaches as indicated by an open arrow, the presence of the purine skeleton 41 suppresses the platinum 52 of the platinum-based metal catalyst 51 from contacting the silver metal coating 21. The substitution reaction with silver atoms on the surface of the silver metal film 21 is impossible. As a result, the generation of silver chloride is suppressed and the discoloration of the silver metal coating 21 is suppressed.

In order to simplify the manufacturing process of the lead 11, the coating 22 containing a compound having a purine skeleton may be formed not only on the peripheral portion 15 but also on the entire lead 11.
<Production method>
(Lead 11 coating process)
A lead 11 is formed by pressing or etching a thin metal plate material such as copper, copper alloy, iron, or iron alloy, and the surface of the lead 11 is subjected to metal plating with a metal such as nickel, palladium, silver, or gold. Then, the metal film 21 is formed.

Next, a coating agent containing any of the compounds having a purine skeleton shown above is coated on the metal coating 21 under the following conditions to form a coating 22 containing a compound having a purine skeleton. Then, the coating process of the lead 11 is completed by removing the coating film 22 containing an excess purine skeleton by washing with a solvent such as water or alcohol.
The coating solution used for the coating treatment is prepared by dissolving a film agent in a solvent. The concentration of the coating agent at that time varies depending on the type of the coating agent, but is preferably prepared within a range of about 0.1 mg / L to 100 g / L. If this concentration is too low, it takes time for the treatment, and if it is too high, a certain effect cannot be expected. If a short molecular film is formed, the film formation reaction does not proceed any further.

As a solvent for dissolving the film agent, water, alcohols (for example, methanol, ethanol, propanol, butanol), and ketones (for example, acetone, methyl ethyl ketone) can be used.
In order to stably form a film on the metal, an organic acid-based, boric acid-based, or phosphoric acid-based pH buffering agent may be added as necessary. Furthermore, in order to improve the solubility and dispersibility of the coating agent, an anionic, cationic or nonionic surfactant or a mixture thereof may be added as necessary.

The coating treatment may be performed by immersing the lead 11 in a solution obtained by dissolving a film agent containing a compound having a purine skeleton in a solvent for a predetermined time. The solution may be applied to the lead 11 or sprayed. It may be done by doing.
For example, a coating containing a compound having a purine skeleton can be formed only on the peripheral portion 15 by applying or spraying a coating agent on the peripheral portion 15 of the lead 11 after the metal plating process.
(Packaging process)
The semiconductor element 12 is bonded to the lead 11 after the coating process with a conductive paste (silver paste, gold-tin eutectic solder, etc.). Then, the wire 13 is electrically bonded to the connection portion of the lead 11 by using a wire bonding apparatus, thereby electrically connecting the semiconductor element 12 and the connection portion. And the coating resin body 14 is shape | molded so that the semiconductor element 12 and the lead | read | reed 11 may be covered using a shaping | molding die.

After the resin molding, the semiconductor device 10 is completed by performing a process of removing the resin burr using a dry or wet blasting apparatus or a water jet process.
<Supplement>
(1) The lead 11 covered with the coating 22 containing a compound having a purine skeleton can also be applied to a hollow resin encapsulated semiconductor device as shown in FIG.

Specifically, a hollow resin encapsulated semiconductor device can be manufactured through the following steps (a) to (e).
(A) The peripheral portion (portion denoted by reference numeral 61) of the portion of the lead 11 where the resin sealing coating is performed is coated in the same manner as the lead 11 coating step in the semiconductor device 10 to form a compound having a purine skeleton. A coating film 22 is formed.

(B) The lead 11 after the coating treatment is inserted between the dies 31 and 32 shown in FIG. 5B, and a mold resin is injected from the resin injection port 30 to obtain the resin as shown in FIG. Mold resin 33 is molded on leads 11 to produce a resin body.
(C) Remove resin burrs by dry or wet blasting equipment or water jet treatment.

(D) As shown in FIG. 5D, the semiconductor element 12 is fixed to the lead 11 with a conductive paste (for example, silver paste, gold-tin eutectic solder, etc.) and electrically connected using a wire bonding apparatus. The wire 13 is wire-bonded to the connection portion of the lead 11 to electrically connect the semiconductor element 12 and the connection portion.
(E) Finally, as shown in FIG. 5E, the upper opening is covered with a resin lid 34.

Moreover, the lead 11 can be covered with a resin body to produce an optical semiconductor device such as an LED.
In the case of an optical semiconductor device, the light emitting element can be fixed to the lead 11 and then the opening can be coated with a transparent resin such as an epoxy resin or a silicone resin.
When applied to an optical semiconductor device, the following effects are also achieved.

In the case of an optical semiconductor, it is preferable to apply a silver coating as the metal coating 21 in order to improve the light reflectivity on the lead surface. However, if a silver coating is formed, silver sulfidation or chlorination in the silicone resin is performed. Blackening is facilitated by the substitution reaction with the platinum compound catalyst to produce silver chloride.
On the other hand, if the silver film is coated with a film containing a compound having a purine skeleton as described above to protect the silver film, it is caused by the sulfurization of the silver film or the substitution reaction between the silver film and the platinum chloride compound. The production of silver chloride can be suppressed, and this also has the effect of preventing discoloration of the silver coating.

  The purine skeleton is a nitrogen-containing condensed heterocyclic ring having a planar structure composed of a condensed ring of an aromatic pyrimidine ring and an imidazole ring. By the π electron of carbon in the structure and the n electron of nitrogen in the structure, London dispersive power works between adjacent pudding skeletons and has a stacking effect. Therefore, the coating containing the compound having a purine skeleton is extremely stable. For this reason, the function of the lead surface protection film is sufficiently maintained without being decomposed even when the temperature is high (for example, about 300 to 360 ° C. in the case of gold-tin eutectic solder bonding, etc.) in the semiconductor element mounting process. As a result, a strong bondability between the optical semiconductor element and the lead can be ensured, so that an optical semiconductor device having high luminance reliability over a long period can be produced.

In addition, after the resin deburring step (c) and before the semiconductor element connecting step (2), a plating process step of plating the portion covered with the coating 22 of the lead 11 with a metal such as silver or gold is performed. It may be inserted. Thereby, the solderability of the part coat | covered with the film 22 of the lead 11 can be improved, and fixation to a printed circuit board can be performed easily.
Moreover, you may perform the coating process of the film containing the compound which has a purine skeleton after a plating process process. As a result, the corrosion resistance and discoloration resistance of the plating film can be improved.

Further, in the above description, the region for forming the coating 22 containing the compound having a purine skeleton is formed only in the peripheral portion 15. However, in order to simplify the manufacturing process of the lead 11, the coating 22 is formed on the entire lead 11. May be.
(2) The coating film 22 containing the compound having the purine skeleton described above can also be applied to a semiconductor device having a heat sink.

FIG. 6 is a diagram showing a manufacturing process of a hollow resin encapsulated semiconductor device having a heat sink coated with a coating 22 containing a compound having a purine skeleton (hereinafter referred to as “hollow semiconductor device with a heat sink”). . Hereinafter, with reference to FIG. 6, the manufacturing method of the hollow semiconductor device with a heat sink is demonstrated.
As shown in FIG. 6A, the heat sink 72 is bonded to the lead 11 before the coating process by using silver paste, silver brazing, caulking, or the like, and the lead-heat sink combined body (hereinafter referred to as “combined body”). Form. Then, the coating process is performed on the portion (part of the lead 11 indicated by reference numeral 71 and the heat sink 72 portion) where the resin sealing is performed with the thermoplastic resin, similarly to the coating process of the lead 11 in the semiconductor device 10. Thus, the film 22 containing the compound having a purine skeleton is formed.

Note that the lead-heatsink combination may be formed by rolling, pressing, or etching using a material stepped before lead formation.
The manufacturing process after the coating 22 is formed is the same as the manufacturing process described in (b) to (e) of the supplement (1), as shown in FIGS. 6 (b) to 6 (e). Is omitted.
In addition, not only in the hollow resin-coated semiconductor device, but also in the optical semiconductor device such as the LED described in the supplement (1) and the semiconductor device 10 described in the embodiment, the heat sink is similarly bonded to the coating resin 22. The same effect can be obtained by coating with.

Also in a semiconductor device provided with such a heat sink, as described in supplement (1), when the silver coating is applied as a metal coating on the lead surface, the compound having a purine skeleton in the silver coating is used. If the coating film is coated, the production of silver chloride can be suppressed, and the effect of preventing discoloration of the silver coating film is exhibited.
In addition, since the film made of a compound having a purine skeleton is stable, the function as a surface protective film of the lead is sufficiently maintained without the film being decomposed in a high temperature process in the mounting process of the semiconductor element. In addition, since it is possible to secure strong bonding between the optical semiconductor element and the lead, it is possible to create an optical semiconductor device with high luminance long-term reliability.

[Embodiment 2]
1. Configuration of Semiconductor Device FIG. 8A is an external perspective view showing the configuration of the semiconductor device 10 according to the present embodiment. FIG. 8B is a yz sectional view of the semiconductor device 10. FIG. 8C is a partially enlarged view of S1 in FIG.

This semiconductor device 10 is a surface mount semiconductor device (QEP; Quad Flat Package) used for IC, LSI, etc., as in the first embodiment, and includes a semiconductor chip 4, wiring leads 3, wires 5, squares. It consists of a resin body 121 or the like molded into a shape.
The wiring lead 3 is composed of die pads 3a and 3b obtained by punching a metal plate (for example, copper alloy plate) having excellent conductivity, and an outer lead 301a that is a part of the die pad 3a extends from the periphery of the resin body 121. Yes.

Inside the resin body 121, as shown in FIG. 8B, the semiconductor chip 4 is mounted on the die pad 3a and is connected to the die pads 3a and 3b via the electrode pads and wires 5 (not shown). The die pad 3b and the semiconductor chip 4 are joined with a conductive paste such as a silver paste.
Of the die pad 3a, a region sealed in the resin body 121 (121a, 121b) is an inner lead 302a, and a region exposed to the outside is an outer lead 301a. The outer lead 301a is bent into an S-shaped cross section.

In this semiconductor device 10, an organic coating 110 is formed on the surface of the boundary region (S1 portion in FIG. 8B) between the inner lead 302a and the outer lead 301a of the die pads 3a and 3b.
The organic coating 110 is formed by self-organizing functional organic molecules and will be described in detail below.

2. Configuration of Organic Film 110 FIG. 9 is a diagram schematically showing the structure of the functional organic molecule 111. The purine skeleton has a condensed ring structure of a five-membered ring and a six-membered ring, but is simply represented by a hexagon in the figure.
The functional organic molecule 111 is configured such that the first functional group A1 is bonded to one end of the purine skeleton B1 and the second functional group C1 is bonded to the other end, and the general formula is represented by A1-B1-C1. The

  The compound having the purine skeleton B1 is a compound represented by the general formula 9 or 10 (provided that any one of R1, R2, R3, and R4 has a first functional group and a second functional group). , And others represent hydrogen, amine, hydroxyl group, ketone, aldehyde, carboxylic acid, sulfonic acid, amide, hydrazide, hydrazine, amidine, ether, halogen, nitrile, methylene, aryl, siloxane, glycol), or their fluorine. Or a derivative in which a side chain or the like is appropriately bound thereto.

The first functional group A1 is a structural part exhibiting a binding property to a metal, and is composed of one or more selected from a thiol compound, a sulfide compound, and a nitrogen-containing heterocyclic compound, or a compound or chemical structure containing it. ing.
The second functional group C1 is a structural part that exhibits an action of curing or accelerating the curing of the thermosetting resin, and includes, for example, a hydroxyl group, a carboxylic acid, an acid anhydride, a primary amine, a secondary amine, and a tertiary. It is composed of one or more selected from amine, amide, thiol, sulfide, imide, hydrazide, imidazole, diazabicycloalkene, organic phosphine, boron trifluoride amine complex, or a compound or chemical structure containing it.

  As shown in FIG. 8C, each of such functional organic molecules 111 is densely arranged in a state where the first functional group A1 is bonded to the surface of the die pad 3a made of a metal material by self-assembly. Therefore, the organic coating 110 is formed of a monomolecular film. Accordingly, the second functional group C1 disposed at the other end of the purine skeleton B1 is directed to the outer surface side of the organic coating 110, so that the second functional group C1 is exposed on the surface of the organic coating 110, The surface of the organic coating 110 has characteristics of the second functional group.

The film thickness of the organic coating 110 depends on the size of the functional organic molecules 111, but is formed, for example, on the order of nm (several nm).
Thus, since the organic coating 110 densely protects the surface of the die pad 3a with a single molecule size, it exhibits a function of preventing corrosion due to oxygen gas and moisture adhesion and a function of preventing replacement with a noble metal salt.

  In the semiconductor device 10, the semiconductor element 4 needs to be electrically connected to the outer lead 301 a by wire bonding, die bonding, or the like. Therefore, in order to ensure conductivity, the connection area between the die pad and the lead 3 is made of metal plating or the like. A film may be formed. In this metal plating step, the metal component of the die pad 3a may be ionized and eluted into the plating solution. However, if the organic coating 110 is formed on the surface of the die pad 3a that is not plated, the metal component Elution can be suppressed.

Hereinafter, the detail of the chemical structure which can be taken as the functional organic molecule 111 is demonstrated.
(First functional group A1)
The first functional group A1 is required to have a chemical structure having an affinity and a binding property (including a coordination bond) to the metal material and having this characteristic.
For example, if it is a thiol and a thiol compound containing this, a sulfide compound (disulfide compound etc.), a nitrogen-containing heterocyclic compound (azole compound, azine compound etc.), or a compound, chemical structure or derivative containing one or more of these, It is preferable because it has hydrogen bonding or coordination bonding with a metal atom.

  When the first functional group A1 contains a thiol group (X-SH, where X is a purine skeleton or a derivative thereof), it is arranged on a metal atom that can be a monovalent or higher cation such as gold (Au) or silver (Ag). The functional organic molecules 111 are attached to the die pad 3a by covalent bonds such as Au—S—X or Ag—S—X. Similarly, when the first functional group A1 contains a disulfide group (X1-SS-X2), Au (-S-X1) (-S-X2) or Ag (-S-X1) (-S- A covalent bond such as X2) is made to form a strong bond structure.

When 1st functional group A1 contains an azole compound and an azine compound, the unshared electron pair of the nitrogen atom in the said compound can be coordinated to the metal which can become a cation more than bivalence. For example, an imidazole compound, a benzotriazole compound, and a triazine compound are preferable because they easily coordinate to a metal such as Cu.
Note that, depending on the type of the compound, a covalent bond, a coordination bond, a hydrogen bond, or the like can be formed at the same time, but a stronger bond structure can be expected by forming a plurality of types of bonds.

(Purine skeleton B1)
The purine skeleton has a condensed ring structure of a 5-membered ring and a 6-membered ring as listed above.
When the purine skeleton B1 forms a fluoride, the hydrophobicity is strong, so that moisture can be prevented from entering between the wiring lead 3 and the coating after the organic coating is formed. As a result, the organic coating and the wiring lead Of the organic film is kept good, and the organic film is hardly peeled off due to the thermal history.

When a siloxane chain is added to the purine skeleton B1, the characteristics excellent in heat resistance and weather resistance are exhibited. For this reason, for example, even when the organic coating is exposed to a relatively high temperature environment in a mounting process of a semiconductor element or the like, the alteration or damage of the coating itself can be prevented.
(Second functional group C1)
The second functional group C1 is required to have a function of curing a thermosetting resin or a function of promoting curing, and may be a chemical structure having such a function.

  For example, hydroxyl group, carboxylic acid, acid anhydride, primary amine, secondary amine, tertiary amine, quaternary ammonium salt, amide group, imide group, hydrazide group, imine group, amidine group, imidazole, triazole , Tetrazole, thiol group, sulfide group, disulfide group, diazabicycloalkene, organic phosphine, organic phosphine, boron trifluoride amine complex, or a compound provided with these.

When the thermosetting resin comes into contact with these second functional groups C1, a curing reaction occurs instantaneously, and the second functional group C1 and the resin are bonded.
When the second functional group C1 is a primary amine, it acts as a curing agent for curing the epoxy resin when it comes into contact with the epoxy resin, and bonds to the epoxy group in the epoxy resin by crosslinking polymerization.

In the case of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) in which the second functional group C1 is a compound having a diazabicycloalkene, the epoxy group and the hydroxyl group or acid anhydride in the epoxy resin It acts as an accelerator that promotes curing with the like, and accelerates the polymerization reaction of epoxy groups with hydroxyl groups, acid anhydrides, and the like.
3. Manufacturing Method of Semiconductor Device A manufacturing method of the semiconductor device 10 according to the present embodiment will be described.

The semiconductor device 10 is manufactured through an organic film forming process for depositing the organic film 110 on a predetermined surface of the die pad 3a and a resin fixing process for resin-sealing the die pad 3a and the semiconductor element 4 and the like.
[Organic film forming process]
In the organic film forming step, the dispersion adjusting sub-step, the film forming sub-step, and the cleaning sub-step are performed in this order (FIG. 10A).

(Dispersion adjustment sub-process)
The functional organic molecules 111 are dispersed in a predetermined solvent to prepare a dispersion. As the solvent, an organic solvent, water or a mixture thereof is used. When water is used as the solvent, it is preferable to add an anionic, cationic or nonionic surfactant as necessary in order to obtain dispersibility of the functional organic molecules 111. Further, in order to stabilize the functional organic molecule 111, a pH buffer such as boric acid or phosphoric acid may be added.

(Deposition sub-process)
Next, the predetermined surface of the die pad 3a is immersed in the dispersion liquid produced above.
In the dispersion, each functional organic molecule 111 has a relatively high Gibbs free energy, and has a random motion (so-called Brownian motion) by interacting so that each single molecule repels each other. .

When the die pad 3a made of a metal material is immersed in this dispersion, each functional organic molecule tries to move to a more stable state, and the first functional group binds to the metal of the die pad 3a. The molecule 111 is stabilized in a state where the purine skeleton B1 and the second functional group C1 are aligned in the same order. (FIG. 10 (b)).
Based on the above principle, the functional organic molecules 111 are self-organized to form a monomolecular film. Therefore, when the organic molecules 110 are pulled up from the dispersion, the members having the organic coating 110 formed on the leads 3a (hereinafter referred to as “wiring members 10x”). Is obtained).

For illustration purposes, FIG. 10 illustrates the case where the organic coating 110 is formed on the entire surface of the die pad 3a. Of course, a pattern mask having an opening of a predetermined shape is provided on the surface of the lead 3a in advance. Alternatively, the organic coating 110 may be formed only on the surface of the lead 3a corresponding to the opening.
In addition, although the immersion method using a dispersion liquid was illustrated to form the organic coating 110, it is not limited to this, For example, the same organic coating 110 can be formed even if it uses other methods, such as spraying.

(Washing sub-process)
For the wiring member 10x, the excess functional organic molecules 111 are removed using an organic solvent, water or a mixture of both as a cleaning medium. By this cleaning treatment, the functional organic molecules 111 in which the first functional group A1 is not bonded to the metal of the lead 3a can be easily removed. The organic film forming step is thus completed.

[Resin fixing process]
In the resin fixing process, a wiring member placement sub-process and a resin filling sub-process are sequentially performed. Each sub-process will be described with reference to the schematic process diagram of FIG.
(Wiring member placement sub-process)
The wiring member 10x and the die pad 3b produced above are used. First, the semiconductor chip 4 is mounted on the die pad 3b. Then, the semiconductor chip 4 and the wiring member 10x are connected via the wire lead 5 or the like, and the obtained chip-attached wiring member 10y is placed on the fixed mold 2 (FIG. 11 (a)).

Next, the movable mold 1 is moved in the direction of the arrow, and the molds 1 and 2 are closed.
At this time, a dense organic film 110 having a monomolecular thickness H1 is formed on the surface of the wiring pattern 3 of the wiring member with chip 10y with the second functional group C1 of the functional organic molecule 111 oriented outward. The film is formed (the S4 partial enlarged view of FIG. 11A). The formation region of the organic coating 110 includes a region that does not directly face the cavities 1x and 1y (internal space) secured between the molds 1 and 2. That is, the area of the organic coating 110 is a region wider than a region to be resin-sealed later.

(Resin filling sub-process)
With the molds 1 and 2 closed, the molds 1 and 2 are heated, and a thermosetting resin material in a fluid state is injected (injected) into the cavities 1x and 1y from the outside with a constant pressure through the gate 6. Molding). The resin material is densely filled into the cavities 1x and 1y around the region including the semiconductor chip 4 of the wiring member with chip 10y, and is cured by receiving heat from the molds 1 and 2 (FIG. 11B). If the resin material is completely cured after a certain time, the formation of the sealing resin is completed, and the semiconductor device 10z is obtained. Thereafter, the outer lead 301a is bent to complete the semiconductor device 10.

In this step, the resin material injected into the cavities 1x and 1y (“in the molding region” in FIG. 11B) has a second functional group C1 action (resin hardening action or It is cured relatively quickly by the resin curing acceleration action).
Because of this action, even if there is a gap at the joint between the cavities 1x and 1y of the molds 1 and 2 ("outside the molding area" in FIG. 11B), the resin material is not leaked into the gap. To harden. Therefore, it is suppressed that resin flows into the gap and the resin burr is generated (S5 partial enlarged view of FIG. 11B).

Thereby, generation | occurrence | production of the resin burr | flash can be suppressed very low in the outer lead 301a of the semiconductor device after sealing resin formation. Therefore, a separate post-processing step for removing the resin burr is not required, and the semiconductor device can be quickly transferred to a process such as connecting to another substrate, so that it can be efficiently manufactured.
Further, the semiconductor device 10 manufactured in this way has strong adhesion between the die pad 3a and the molded resin body. Therefore, when the semiconductor device 10 is connected to another substrate, even if it is affected by heat due to soldering or the like, the resin may be thermally damaged and peeled off from the wiring lead, or may be cracked or destroyed. Absent.

Further, since the organic coating 110 is a monomolecular film, even if it is provided, the thickness of the semiconductor device hardly increases, and the organic coating occupies a volume in the cavity and the filling amount of the resin material is not insufficient. . Therefore, the said effect can be acquired, using the manufacturing equipment similar to the past.
[Embodiment 3]
In the present embodiment, an LED device including a light emitting diode element (LED) will be described.

FIG. 12 is a schematic cross-sectional view illustrating configurations of the wiring lead portion 35 and the reflector 122 of the LED device unit 36 x according to the third embodiment.
The device unit 36x has a configuration in which a wiring lead part 35 is disposed at the bottom of a reflector 122 having a bowl-shaped cross section. The reflector 122 is formed by molding a thermosetting resin material (epoxy resin or the like).

  Even in such an apparatus unit 36x, a problem of resin burrs may occur. That is, in the wiring lead portion 35, the regions 301 and 302 exposed at the bottom of the reflector 122 need to retain conductivity because the LED chip 42 will be mounted later (see FIG. 13B). ), The resin material may flow from the bottom of the reflector 122 through the gap between the molds, and a resin burr may be generated.

When the resin burrs are generated, it is necessary to separately remove the resin burrs, and the LED chips cannot be mounted with good manufacturing efficiency.
On the other hand, by forming the organic coating 110 made of the functional organic molecules 111 over at least the exposed regions 301 and 302 of the wiring lead portion 35 before the resin fixing step, the thermosetting property at the time of resin molding. The resin material can be quickly cured. As a result, the resin material is prevented from leaking from the bottom of the reflector 122, and the occurrence of resin burrs is suppressed.

[Modifications of Embodiments 2 and 3]
A fine resin pattern can be firmly formed by using the hardening accelerating action of the organic coating film 110 described in the second and third embodiments.
For example, in a technical field in which resin molding is locally performed on a part of the surface of the wiring board using an inkjet method or the like, precise resin molding may be required. In this case, compared with the case where resin molding is directly performed on the wiring lead portion 35, the resin molding can be performed more quickly by performing the resin molding after forming the organic coating. In this case, since the time until curing is short, it is difficult for the resin to sag and lose its shape after application, and the resin can be molded in accordance with the designed precision pattern.

In the second and third embodiments, the organic coating 110 is formed directly on the die pad or the wiring lead portion. However, the present invention is not limited to this. For example, a plating coating is previously formed on the surface of the die pad or the wiring lead portion. Alternatively, an organic film may be formed thereon. However, in this case, it is necessary to select the first functional group A1 that can be bonded to the plating film.
[Embodiment 4]
The fourth embodiment will be described focusing on differences from the third embodiment.
(Configuration and effect of LED device)
FIG. 13 is a cross-sectional view showing the configuration and manufacturing process of the LED device 36.

This LED device 36 basically has the device unit 36x of the third embodiment, and further, as shown in FIG. 13B, on the wiring lead portion 35 surrounded by the reflector 122 via the paste 42a. The LED chip 42 is joined. The LED chip 42 is connected to the wiring lead part 35 via the wire 53.
A transparent sealing resin 82 is filled in the reflector surface 201 and the exposed regions 301 and 302 in the reflector 122 so as to seal the LED chip 42 and the like.

Here, the sealing resin 82 uses a silicone resin as an example of a thermosetting resin.
An organic coating 120 made of a monomolecular film is formed on the exposed surfaces 301 and 302 of the wiring lead portion 35 by self-organization of the functional organic molecules 112. This functional organic molecule 112 has a first functional group A2 having a binding property to a metal at one end of the purine skeleton B2, and a second functional group C2 having a resin binding property to a silicone resin at the other end ( FIG. 13 (c)).

In general, silicone resin is superior in fading resistance and transparency as compared with epoxy resin or the like, but has a high coefficient of thermal expansion, so it is likely to be deformed at high temperature and may be peeled off or detached from the wiring lead part 35 due to the deformation. is there.
On the other hand, in the present embodiment, the organic coating 120 composed of the functional organic molecules 112 is interposed between the wiring lead portion 35 and the silicone resin, thereby allowing the adhesion between the wiring lead portion 35 and the silicone resin. Since the silicone resin is greatly improved, peeling of the silicone resin is prevented, and even if the silicone resin undergoes some thermal deformation or the like, peeling or detachment does not occur.

Therefore, the performance of the LED device 36 is stably exhibited even in an environment where the temperature tends to be high or a long-time driving condition.
In place of the above-described silicone resin, a silicone resin-containing conductive paste (a die bonding agent such as an Ag paste) may be used. By die-bonding using a silicone resin-containing conductive paste, it becomes possible to firmly bond a semiconductor chip such as an LED and a die pad. Since the silicone resin-containing conductive paste is less deteriorated than the conventional epoxy resin-containing conductive paste, stable conductivity and thermal conductivity can be secured.

Further, when Ag particles are used in the silicone resin-containing conductive paste, an organic coating may be applied to the Ag particles. Thereby, it is also possible to suppress discoloration of Ag particles in the conductive paste.
(Configuration and production method of functional organic molecule 112)
As the first functional group A2 in the functional organic molecule 112 of the present embodiment, the same functional group as the first functional group A1 of the second embodiment can be used, and the purine skeleton B2 is also the same as that of the second embodiment. The same as the purine skeleton B1 can be used.

For the second functional group C2, a compound, chemical structure or derivative exhibiting curability for a thermosetting resin, particularly a silicone resin, is used. Specifically, a compound, chemical structure or derivative containing one or more of a vinyl group and an organic hydrogen silane can be used.
(Manufacturing method of LED device)
The LED device can be manufactured by sequentially performing the following steps. In addition, the manufacturing method of a well-known LED apparatus is employable except an organic film formation process.

[Organic film forming process]
The organic coating 120 is formed by self-organizing the functional organic molecules 112 on the surface of the wiring lead portion 35 by the same method as the organic coating formation step of the second embodiment. Thereby, the wiring lead part 35 in which the organic film is formed as a monomolecular film is obtained.
[Resin fixing process]
A thermoplastic resin material such as polyphthalamide resin is injection-molded on the wiring lead 35 using the wiring lead 35 having the organic coating 120 formed thereon in the same procedure as the injection molding shown in FIG. Thereafter, the resin is cooled in a certain temperature range in order to cure it. Thereby, the reflector 122 is formed, and the LED device unit 36x is obtained.

The LED chip 42 is mounted on the wiring lead part 35 via the paste 42 a, and the wiring lead part 35 and the LED chip 42 are bonded to each other with a wire 52.
Thereafter, the silicone resin material in a fluidized state is filled in the reflector 122 and thermally cured, whereby the LED device 36 is obtained.
[Embodiment 5]
The fifth embodiment will be described focusing on differences from the fourth embodiment.

In the fourth embodiment, a functional group having a chemical bonding property with a silicone resin is selected as the second functional group C2 of the functional organic molecule 112 constituting the organic coating 120. However, in this embodiment, a functional organic molecule is selected. An instantaneous curable functional group is used as the second functional group C2 ′ of the molecule 112a (S7 partial enlarged view 14 (b)).
Specifically, as the second functional group C2 ′, one or more of platinum complexes, palladium complexes, ruthenium complexes, and rhodium complexes, or a compound or chemical structure containing them is used.

The LED device 36 according to the present embodiment can be manufactured in the same manner as the LED device according to the fourth embodiment. However, the reflector 122 is manufactured by injection molding a thermoplastic resin such as a polyphthalamide resin.
By the way, if the thermoplastic resin is cooled and cured at this time, the volume of the resin contracts, and a gap 72 may be formed between the wiring lead portion 20 and the reflector (FIG. 14B).

  When such a gap 72 is generated, the leakage resin 82a is generated when the silicone resin is filled, and the resin material is wasted. Moreover, since the leaked resin 82a leads to deterioration of the electrical bonding property of the outer lead in the wiring lead part 35, a separate removal process is required later, which leads to a decrease in manufacturing efficiency. Furthermore, if the leakage resin 82a enters between the LED device 36 and the heat sink (not shown) attached to the back surface, the heat dissipation performance is impaired, which is not preferable.

  On the other hand, in the present embodiment, since the second functional group C2 'of the functional organic molecule 112a has instantaneous curability, the resin filled on the inner surface of the reflector 122 is cured immediately after filling with the silicone resin. As a result, a solid silicone resin is quickly formed on the bottom of the mortar-shaped reflector 122 to close the gap, so that the silicone resin material that is subsequently filled can be prevented from leaking out of the gap. Therefore, the step of removing the leakage resin 82a is not necessary, and the manufacturing efficiency can be improved accordingly.

Further, since the leakage resin 82a does not adhere to the outer lead in the wiring lead portion 35, the electrical conductivity with the outside through the outer lead is not hindered. Therefore, high reliability is obtained when the LED device 36 is electrically connected by soldering or the like.
Further, by preventing leakage of the silicone resin into the gap, it is possible to suppress the generation of voids (bubbles) in the resin in the gap, and it is possible to improve the sealing performance by the silicone resin.

  FIG. 14B is a partially enlarged view of S7. In order to obtain the above effect satisfactorily, it is preferable to dispose the organic coating 120a up to a region L22 corresponding to the gap 72 between the reflector 122 and the wiring lead portion 35, as shown in FIG. Then, even if the silicone resin 82 flows into the gap 72 to some extent, the resin is cured before the leakage expands, and further leakage can be prevented.

[Embodiment 6]
The sixth embodiment will be described focusing on differences from the fifth embodiment.
The LED device of the present embodiment is characterized in that a fluorescent or phosphorescent functional group is used as the second functional group C3 of the functional organic molecule 113, thereby improving luminous efficiency.
Conventionally, an Ag plating film 63 (FIG. 15A) may be formed on the surface of the wiring lead portion 35. By forming the Ag plating film in this way, the reflectance of the wiring lead portion is improved and the light emission of the LED chip 42 can be effectively used. However, the effective reflection wavelength of the Ag material is about 500 nm or more, It is difficult to obtain an effective reflectance with short wavelength light (blue light emission / ultraviolet light emission of about 380 to 500 nm).

On the other hand, in the present invention, on the Ag plating film 63 corresponding to the exposed regions 301 and 302 of the wiring lead part 35, the second functional group C3 has a functional group that receives short wavelength light and emits fluorescence and phosphorescence. The organic film 130 was formed with the conductive organic molecules 113 (S8 enlarged view 15 (b)). Thereby, the reflection efficiency of visible light by the Ag plating film 63 is complemented.
The first functional group A3 of the present embodiment is the same as the first functional group A1, and the purine skeleton B3 is the same as the purine skeleton B1.

  According to the LED device 36 having the above configuration, among the light emitted from the LED chip 42 during driving, long-wavelength light (wavelength light of about 500 nm or more) is effectively reflected directly on the front surface of the chip by the Ag plating film 63. Is done. At this time, the light passes through the organic film 130. Since the organic film 130 is a monomolecular film and has a molecular level thickness, the long wavelength light passes through the organic film 130 and is reflected by the Ag plating film 63.

  On the other hand, the short wavelength light (wavelength light of about 380 to 500 nm) emitted from the LED chip 42 has a higher energy level than the long wavelength light, and thus it is difficult for the light to travel through the organic coating 130. Is absorbed in the vicinity of the second functional group C3 of the functional organic molecule 113, and the second functional group C3 shifts to an excited state (E0 → E1) with the light energy (E = hν) of the short wavelength light, Fluorescence and phosphorescence are emitted from the second functional group C3. Thus, the short wavelength light from the LED chip 42 is converted into visible light by the second functional group C3.

As described above, in the LED chip 42, since light emission is effectively utilized over both the short wavelength and long wavelength ranges, the LED device 36 has superior light emission efficiency as compared with the related art.
Moreover, the light emission characteristic of the LED chip 42 can also be adjusted by blending the visible light directly reflected on the plating film and the light emission from the second functional group C3.

  In the LED device 36, a plating film may be formed of other materials instead of the Ag plating film 63. For example, when a gold plating film is formed, since the effective reflection wavelength is about 600 nm or more, visible light emission having a wavelength near 600 nm can be reflected. In addition, if the second functional group C3 emits red fluorescent / phosphorescent light having a wavelength of about 600 to about 700 nm, it is possible to specialize in improving the luminance of red.

(Second functional group C3)
As the second functional group C3, as described above, a compound or chemical structure having a characteristic of emitting fluorescence or phosphorescence when excited by short wavelength light is used. For example, stilbene derivatives such as bisstyryl biphenyl derivatives, azole-modified stilbene derivatives such as bis (triazinylamino) stilbene sulfonic acid derivatives, coumarin derivatives, oxazole derivatives, pyralizone derivatives, pyrene derivatives, porphyrin derivatives, and the like can be used.
(Modification of Embodiments 1 to 5)
When the above-described organic coating 110 or the like is formed on the surface of the die pad or the wiring lead portion, the following effects are further obtained.

The surface of the wiring lead in a semiconductor device such as an IC or LSI is subjected to a rough surface processing to improve the bite of the resin in order to improve the adhesion to the resin (epoxy resin or the like) fixed to the surface. May be.
On the other hand, an appearance inspection process is performed as quality control of the manufactured semiconductor device. A laser measurement method using a laser transmitter and a light receiving element is generally used for the inspection. However, when a roughened member is irradiated with laser, it is irregularly reflected, and the amount of light received by the light receiving element is reduced or unnecessary light is received, which may make accurate measurement difficult. In particular, this problem becomes significant when a fine external shape is inspected with a weak laser.

  On the other hand, if the organic coating 110 is applied to the surface of the die pad or the wiring lead portion subjected to the rough surface treatment, the irregular reflection of the laser due to the rough surface unevenness is absorbed by absorbing the laser light that can be irradiated with the functional organic molecules. Therefore, the appearance inspection process can be performed accurately and efficiently, and an improvement in manufacturing efficiency can be expected. Moreover, if the second functional group converts the irradiation energy into fluorescence or phosphorescence and emits light, it can be expected that the appearance inspection process is performed more efficiently.

[Embodiment 7]
In the seventh embodiment, a film carrier tape such as a TAB (Tape Automated Bonding) tape, a T-BGA (Tape Ball Grid Array) tape, an ASIC (Application Specific Integrated Circuit) tape or the like used for mounting electronic parts such as IC and LSI. In particular, the improvement of the adhesion of the solder resist layer applied to the tape will be described.

FIG. 16 is a cross-sectional view schematically showing a manufacturing process of the film carrier tape 40 according to the present embodiment.
As shown in FIG. 16D, the film carrier tape 40 is formed by laminating an insulating film 401 made of polyimide or the like, a wiring pattern layer 402 made of Cu, and a solder resist layer 403 in the same order.

The insulating film 401 and the solder resist layer 403 are disposed as an insulating means for preventing the wiring pattern layer 402 from being short-circuited, and are formed of an insulating resin material (for example, polyimide, epoxy, or urethane resin).
The surface of the wiring pattern layer 402 is coated with an Sn plating layer 404 in advance. Since the Sn material has characteristics such as solder wettability, flexibility, lubricity, etc., if the plating layer 404 is formed in this way, the film carrier tape can be connected to the mounting component by solder. It will be suitable.

  When the Sn plating layer 404 is formed on the film carrier tape 40, an insulating film 401, a wiring pattern layer 402, and a solder resist layer 403 are previously laminated in the same order, and this is heated to a constant temperature (for example, BF4 It is immersed in a Sn plating tank filled with a Sn-containing compound dissolved in a solvent, and an Sn plating step is performed by an electrolytic plating method or the like. Since the tin component does not adhere to the insulating material, the Sn plating layer 404 is selectively formed on the wiring pattern layer 402.

The present embodiment is characterized in that the organic coating 140 is formed on the wiring pattern layer 402 by self-organizing the functional organic molecules 114 prior to the Sn plating step.
As shown in FIG. 17A, the functional organic molecule 114 has a first functional group A4 having a binding property to a metal at one end of the purine skeleton B4 and a second functional group C4 at the other end. The second functional group C4 is a functional group having high adhesion to the solder resist layer 403. For example, an acid anhydride such as phthalic anhydride or pyromellitic dianhydride, or a primary amine compound Or a compound or chemical structure containing one or more of them.

  Since the organic coating 140 is deposited on the wiring pattern layer 402, the wiring pattern layer 402 and the solder resist layer 403 are firmly attached to each other through the organic coating 140 as shown in FIG. Is bound to. Therefore, even if immersed in a Sn plating bath heated to a predetermined temperature, the end portion of the solder resist layer 403 is not peeled off from the wiring pattern layer 402 during the Sn plating step, and peeling of the solder resist layer 403 is prevented. In addition, the Sn plating layer 404 can be formed satisfactorily.

Further, since the generation of so-called internal batteries is suppressed on the wiring pattern layer 402, the effect of preventing the surface of the wiring pattern layer 402 from being eroded is also achieved. The principle will be described with reference to a schematic partial enlarged view 22 (a) in the vicinity of the wiring pattern layer 402 and the solder resist layer 403 during the plating process.
The solder resist layer 403 and the wiring pattern layer 402 have a linear expansion coefficient specific to each material. When the solder resist is cured, the solder resist layer 403 is thermally contracted, and internal stress is generated in each layer.

The plating solution in the plating tank is heated to about 60 ° C.
When the wiring pattern layer 402 in which the solder resist layer 403 is laminated is put into this plating solution, the solder resist layer 403 having an internal stress higher than that of the wiring pattern layer 402 is pulled, and the end portion 403x of the solder resist layer 403 is The wiring pattern layer 402 may be turned up from the surface.

In that case, when the plating solution permeates between the end portion 403x and the wiring pattern layer 402, the end portion 403x is further lifted by the heat shrinkage force (internal stress) remaining in the solder resist layer 403, and the lifted end portion The plating solution enters between 403x and the wiring pattern layer 402, and the solvent region 500 is formed.
Due to the difference in the ionization tendency of Sn and Cu, the Sn ion concentration in the solvent region 500 is lowered, and Cu ions are dissolved into the solution from the surface of the wiring pattern layer 402 to the solvent region 500.

Further, Cu dissolves in the solution, and electrons emitted into the wiring pattern layer 402 when Cu ions are generated are received by the Sn ions in the plating solution, so that the wiring near the end portion 403x of the solder resist layer 403 is provided. Sn is deposited on the pattern layer 402 to form a Sn deposition layer 408.
That is, a local battery with a series of tin and copper oxidation-reduction reactions is formed (refer to Japanese Patent No. 3073342 for the formation process of the local battery).

When this local battery reaction further proceeds, the portion where Cu has melted becomes an erosion region 406.
The erosion region 406 remains after being covered with the end portion 403x in appearance (FIG. 22B). Although the erosion region 406 is not conspicuous in appearance, if a tensile stress or the like is applied when the film carrier tape is used, problems such as breakage of the film carrier tape from the erosion region 406 may occur.

On the other hand, in the present embodiment, the solder resist layer 403 and the wiring pattern layer 402 are firmly bonded via the organic coating 140, so that the plating process is performed even if the solder resist layer 403 has some internal stress. Sometimes the end 403x does not turn up.
Therefore, the solder resist layer 403 is not peeled off from the wiring pattern layer 402, and the occurrence of the eroded area 406 can be avoided.

Therefore, according to the present embodiment, it is possible to realize a film carrier tape in which the Sn plating layer 404 can be satisfactorily formed and the mechanical strength is excellent.
It should be noted that the internal stress remaining in the solder resist layer 403 can be reduced by performing post-treatment such as normal annealing after the plating step.
Incidentally, in Japanese Patent No. 3073342, as shown in FIG. 23, a first Sn plating layer 402x containing a Cu component is formed in advance on the surface of the wiring pattern layer 402 before forming the solder resist layer 403, and then the solder A technique for forming the resist layer 403 and the second Sn plating layer 407 is disclosed, which can prevent the occurrence of an erosion region, but the plating process has been performed twice. On the other hand, in this embodiment, since it is not necessary to carry out the plating process twice, the manufacturing process is simpler and the amount of plating solution used and the amount of drainage are small. In addition, manufacturing costs and environmental problems can be expected.

(Film carrier tape manufacturing method)
A method for manufacturing the film carrier tape 40 will be described.
First, a wiring pattern layer 402 (Cu foil) having a predetermined shape is formed on the insulating film 401 by using a photoetching method or the like (FIG. 16A).
Next, as an organic film forming step, the organic film 140 made of a monomolecular film is formed on the wiring pattern layer 402 by attaching the functional organic molecules 114 while self-organizing (FIG. 16B). S8 enlarged view 17 (a)).

Next, as a solder resist layer forming step, a solder resist layer 403 is formed on the organic coating 140 by applying a solder resist material paste using a printing method or the like (FIG. 16C). At this time, the second functional group C4 cures the solder resist material and chemically bonds to each other (S9 enlarged view 17 (b)).
Next, a film portion provided in a region other than the region where the solder resist layer 403 is formed in the organic coating 140 is peeled off. Instead of performing such a peeling process, the organic coating 140 may be formed after masking in advance.

Next, it is put into an Sn plating tank, and an Sn plating layer is formed in a predetermined region of the wiring pattern layer 402 (FIG. 16D). By using the electroless displacement plating method, the Sn plating layer is formed only on the surface of the conductive material. Thus, the film carrier tape 40 is completed.
[Embodiment 8]
(Configuration and effect of film carrier tape)
The film carrier tape 40 according to the eighth embodiment will be described focusing on differences from the seventh embodiment.

As shown in FIG. 18 (d), the film carrier tape 40 of this embodiment has a function having a second functional group C5 that exhibits a photopolymerization initiating property or a photosensitizing property for the wiring pattern layer 402 and the solder resist layer 403. It has a feature in that it is bonded with the organic molecule 115 (S11 enlarged view 19 (b)).
Examples of the second functional group C5 include benzophenones, acetophenones, alkylphenones, benzoins, anthraquinones, ketals, thioxanthones, coumarins, halogenated triazines, halogenated oxadiazoles, oxime esters, Acridines, acridones, fluorenones, fluorans, acylphosphine oxides, metallocenes, polynuclear aromatics, xanthenes, cyanines, squaliums, acridones, titanocenes, tetraalkylthiuram sulfides, You may use the compound and chemical structure containing these 1 or more types.

In addition to those listed above, any one having photoexcitation polymerization initiation or photosensitization can be used.
According to the present embodiment, as in the seventh embodiment, the plating process is performed in a state where the wiring pattern layer 402 and the solder resist layer 403 are bonded with the functional organic molecules 115. The effect which prevents peeling is produced.

In addition, by applying the solder resist material while exciting the photopolymerization initiator, the resist material can be rapidly cured to form the solder resist layer. As a result, the occurrence of dripping and loss of shape can be prevented, and the solder resist layer 403 can be formed with an accurate and precise pattern.
That is, the solder resist material paste is adjusted to a predetermined viscosity and applied along a pattern mask previously arranged on the wiring pattern layer 402. Then, the mask is removed after a certain amount of drying, but after that, the applied paste tends to diffuse slightly. For this reason, even if the diffusion scale is anticipated in advance and the paste is applied to an area slightly smaller than the patterning mask, the end of the applied paste has an acute angle, and the portion is easily peeled off during the plating process. is there.

  On the other hand, in the present embodiment, the applied paste is brought into an early stage by irradiating the organic film with ultraviolet rays and giving light energy (E = hν) to the second functional group C5 immediately before applying the paste. Heat cured. Accordingly, the above-mentioned acute angle end portion does not occur, and the paste flow is small, so that the paste can be applied accurately according to the pattern mask, and the shape of the solder resist layer can be formed with high accuracy.

(Film carrier tape manufacturing method)
A predetermined wiring pattern layer 402 (Cu foil) is formed on the insulating film 401 by using a photoetching method or the like (FIG. 18A). Next, the functional organic molecules 115 are self-assembled and attached onto the wiring pattern layer 402 to form an organic coating 140 made of a monomolecular film (FIG. 18B, S10 enlarged view 19A).

  Next, the organic coating 140 is irradiated with ultraviolet rays having a predetermined wavelength (for example, about 340 nm or more) from the outside. As a result, the second functional group C5 present on the surface of the functional organic molecule is transferred from the ground state to the excited state (E0 → E1). And the paste material used as the material of a soldering resist layer is apply | coated by predetermined thickness using the blade BL within the period with which an excited state is maintained (FIG.18 (c)).

Thereby, the excitation energy of the second functional group is transmitted to the solder resist as thermal energy, the solder resist is thermally cured, and the film carrier tape 40 is manufactured (FIG. 18D).
[Embodiment 9]
The ninth embodiment will be described focusing on differences from the seventh and eighth embodiments.

An organic film is formed on the wiring pattern layer 402 using the same functional organic molecules 115 as in the eighth embodiment. In this embodiment, a batch method is used to form the solder resist layer 403.
As a result, the bonding between the solder resist layer 403 and the wiring pattern layer 402 can be strengthened as in the eighth embodiment, and the thickness adjustment of the solder resist layer 403 can be performed over a wider range than when a general printing method is used. Can flexibly respond to design changes.

FIG. 20 is a diagram illustrating a process of manufacturing the film carrier tape 40 of the ninth embodiment.
First, the wiring pattern layer 402 is formed in a predetermined pattern on the insulating film 401 (FIG. 20A).
Next, as an organic film forming step, an organic film 150 is formed on the surface of the wiring pattern layer 402 to obtain an intermediate product (FIG. 20B). This film formation can be performed by a method almost similar to that of the second embodiment.

  Next, in the solder resist layer forming step, a resin dispersion liquid in which a photopolymerizable compound serving as a solder resist material is dispersed in a solvent is prepared to fill a batch. As a photopolymerizable compound, a compound having an acrylate group in the molecule, a compound having a methacrylate group in the molecule, a compound having an acrylamide group in the molecule, a compound having a urethane group in the molecule, and an isocyanate group in the molecule Examples thereof include compounds and compounds having a vinyl group in the molecule, and either monomers or oligomers may be used.

On the other hand, the intermediate product is subjected to a pattern mask PM that matches the region where the solder resist layer 403 is to be formed, and is immersed in a batch of resin dispersion to keep UV light from the outside while maintaining a stable state in the liquid. Irradiate (FIG. 20C). For the pattern mask PM, for example, a photoresist layer formed by a known exposure process is used.
The photopolymerizable compound dispersed in the liquid undergoes a polymerization reaction. At this time, the opening of the pattern mask PM (or the pattern gap when a photoresist layer is used) is centered on the second functional group C5 of the organic coating 150. The polymerization reaction starts. Therefore, if the ultraviolet irradiation time is made extremely short, the solder resist layer 403 is formed with a monomolecular thickness. On the contrary, if irradiation is performed for a long time, the thickness of the solder resist layer 403 can be increased, and theoretically, it can be formed to a thickness corresponding to the depth of the second functional group C5 in the liquid.

After the UV curing reaction, the intermediate product is taken out from the batch, and the mask is removed and washed appropriately (FIG. 20 (d)).
Thereafter, the film carrier tape 40 is manufactured by removing the film portion in the region other than under the solder resist layer 403 in the organic coating 150 and forming the Sn plating layer 404 (FIG. 20E). The

As described above, according to the manufacturing method of the present embodiment, the thickness of the solder resist layer 403 can be arbitrarily controlled.
In addition, since the solder resist layer 403 is rapidly cured, the solder resist layer 403 formed on the organic coating 150 is not deformed by receiving buoyancy due to the specific gravity difference from the dispersion liquid, and has a precise pattern shape and thickness. Can be formed.

Note that the thickness of the solder resist layer 403 can be controlled not only by the ultraviolet irradiation time but also by adjusting the dispersion concentration of the compound in the dispersion.
The specific gravity of the dispersion is preferably adjusted so that the photopolymerizable compound is well dispersed for a certain period.
In addition, when the photopolymerizable compound is polymerized around the second functional group, if the photopolymerizable compound is locally insufficient, the reaction is rate-determined, but the photopolymerizable compound gradually settles in the dispersion. If the specific gravity is adjusted as described above, it is possible to prevent local shortage of the photopolymerizable compound.

<Other matters>
In each of the embodiments described above, the organic coating is formed as a monomolecular film by self-organizing functional organic molecules, but a plurality of layers can be used as long as the adhesive strength to the substrate of the semiconductor device does not deteriorate. You may form by.
In the case of forming with a plurality of layers, the bonding between the second functional group of the adjacent molecule and the first functional group is required between the first layer and the second layer made of functional organic molecules. Therefore, as the first functional group, a compound / structure having a binding property to a metal and having a binding property to the second functional group, such as a wiring lead portion or a die pad, may be used.

  The present invention can be used for ICs, LSIs, VLSIs, etc., semiconductor devices packaged with a sealing resin, LED lighting devices mounted with LED elements, film carrier tapes used for flexible substrates, and the like.

1 is a cross-sectional view of a semiconductor device 10 according to a first embodiment. It is sectional drawing which shows the structure of the lead | read | reed 11 of the part covered with the film which consists of a compound which has a purine skeleton. FIG. 3 is a diagram schematically showing a specific example of a self-assembled monolayer formed on the surface of a metal coating 21 by a compound constituting the coating 22 containing a purine skeleton. It is a schematic diagram which shows the difference in the coupling | bonding mode of an epoxy resin molecule and the metal film 21 by the presence or absence of the film containing a purine skeleton. It is a figure which shows the manufacturing process of the semiconductor device of a hollow resin coating type. It is a figure which shows the manufacture process of the hollow semiconductor device with a heat sink. It is a figure which shows the process in which a lead is resin-sealing-coated. FIG. 4 is a diagram showing a configuration of a semiconductor device according to a second embodiment. FIG. 3 is a schematic diagram illustrating a configuration of a functional organic molecule according to Embodiment 2. FIG. 5 is a diagram illustrating a film forming process of an organic film according to a second embodiment. It is a figure which shows the resin adhering process which concerns on Embodiment 2. FIG. It is a figure which shows the structure of the LED apparatus which concerns on Embodiment 3. FIG. It is a figure which shows the structure and manufacturing process of the LED apparatus which concern on Embodiment 4. It is a figure which shows the structure etc. of the LED apparatus which concerns on Embodiment 5. FIG. It is a figure which shows the structure of the LED apparatus which concerns on Embodiment 6. FIG. It is a figure which shows the manufacturing process of the film carrier tape which concerns on Embodiment 7. FIG. It is a block diagram around a functional organic molecule. It is a figure which shows the manufacturing process of the film carrier tape which concerns on Embodiment 8. FIG. It is a block diagram around a functional organic molecule. It is a figure which shows the manufacturing process of the film carrier tape which concerns on Embodiment 9. FIG. It is a figure which shows the process at the time of the injection molding of the semiconductor device which concerns on a prior art example. It is a figure which shows typically the structure of the film carrier tape concerning a prior art example, and the formation process of a local battery. It is a figure which shows the structure of the film carrier tape which gave the Sn plating layer concerning a prior art doubly.

Explanation of symbols

DESCRIPTION OF SYMBOLS 3 Wiring lead 3a, 3b Die pad 10 Semiconductor device 11 Lead 12 Semiconductor element 13 Wire 14 for electrical connection 14, 121 Resin body 21 Metal coating 22 Coating 31 containing a purine skeleton 31, 32 Mold 35 Wiring lead part 36 LED device 40 Film carrier tape 42 LED chip 63 Ag plating film 110, 120, 120a, 130, 140 Organic film 111-115, 112a Functional organic molecule 122 Reflector 401 Insulating film 402 Wiring pattern layer 403 Solder resist layer 404 Sn plating layer A1-A5 First functional Group B1-B5 purine skeleton C1-C5, C2 ′ second functional group

Claims (39)

A lead partially covered with a resin body,
A lead comprising: a metal plate which is a lead body, coated with a film containing a compound having a purine skeleton. The film containing the compound having a purine skeleton is composed of a compound having one or more polar groups in the structure,
2. The lead according to claim 1, wherein the metal group is covered with the polar group bonded to the surface of the metal sheet.   The lead according to claim 2, wherein the compound has a nitrogen-containing heterocyclic ring or a thiol, sulfide, or a derivative thereof as a polar group. The lead according to claim 2, wherein the compound is composed of one or more compounds represented by the following general formula 1 or 2 or a fluoride or a derivative thereof.

(However, any of R1, R2, R3, R4 has one or more of the polar groups, others are hydrogen, amine, hydroxyl group, ketone, aldehyde, carboxylic acid, sulfonic acid, amide, hydrazide, hydrazine, (Represents amidine, ether, halogen, nitrile, methylene, aryl, siloxane, glycol) A package part in which a part of the lead is coated with a resin body,
The lead is
Parts other than the part covered with the resin body in the metal plate material that is the lead body,
A package component characterized by being coated with a film containing a compound having a purine skeleton. A semiconductor device in which a semiconductor element and a part of a lead are covered with a resin body,
The lead is covered with a film containing a compound having a purine skeleton. A method of manufacturing a lead comprising a metal plate and partially covered with a resin body,
A method of manufacturing a lead, comprising: a coating step of coating a portion of the metal plate material other than the portion coated with a resin body with a coating containing a compound having a purine skeleton. A method of manufacturing a package component having a structure in which a lead is partially covered with a resin body,
A coating step of coating a part other than the part to be coated with the resin body in the metal plate with a film containing a compound having a purine skeleton,
And a resin body forming step of forming a resin body so as to cover the lead coated with the film. A material containing a functional organic molecule having a first functional group having a binding property to a metal at one end of a purine skeleton and a second functional group having a predetermined property at the other end is attached to a wiring lead made of a metal material, An organic film forming step of forming an organic film by self-organizing each functional organic molecule in a state where the first functional group is bonded to a metal atom constituting the wiring lead;
A method of manufacturing a metal part with resin, comprising: a resin fixing step of fixing a resin over a predetermined surface region of a wiring lead provided with the organic coating after the organic coating forming step. The functional organic molecule is composed of one or more compounds represented by the following general formula 3 or 4 or derivatives thereof,
The first functional group is
The method for producing a resin-coated metal part according to claim 9, comprising at least one selected from a thiol compound, a sulfide compound, and a nitrogen-containing heterocyclic compound.

(However, any of R1, R2, R3, R4 has a first functional group and a second functional group, and the others are hydrogen, amine, hydroxyl group, ketone, aldehyde, carboxylic acid, sulfonic acid, amide, hydrazide. , Hydrazine, amidine, ether, halogen, nitrile, methylene, aryl, siloxane, glycol)   The method for manufacturing a metal part with a resin according to claim 9 or 10, wherein the resin is a thermosetting resin. The thermosetting resin comprises at least one selected from an epoxy resin, a phenol resin, an acrylic resin, a melamine resin, a urea resin, an unsaturated polyester resin, an alkyd resin, a polyimide resin, a polyamide resin, and a polyether resin,
The second functional group is a hydroxyl group, carboxylic acid, acid anhydride, primary amine, secondary amine, tertiary amine, amide, thiol, sulfide, imide, hydrazide, imidazole, diazabicycloalkene, organic phosphine. The method for producing a resin-coated metal part according to claim 11, comprising at least one selected from boron trifluoride amine complexes.   12. The organic coating is formed on the surface of the wiring lead over an area wider than the predetermined surface area of the wiring lead to which the resin is to be fixed in the resin fixing step in the organic coating forming step. Of manufacturing metal parts with resin. The thermosetting resin is a silicone resin,
The method for producing a resin-coated metal part according to claim 11, wherein the second functional group includes one or more selected from a vinyl group and an organic hydrogen silane. The thermosetting resin is a silicone resin containing either an epoxy group or an alkoxysilyl group, or both,
The method for producing a resin-coated metal part according to claim 11, wherein the second functional group includes one or more selected from a hydroxyl group, an acid anhydride, a primary amine, and a secondary amine. The thermosetting resin is a silicone resin,
The second functional group is
12. The method for producing a resin-coated metal part according to claim 11, comprising a metal complex having at least one selected from platinum, palladium, ruthenium, and rhodium.   12. The method for producing a resin-coated metal part according to claim 11, wherein the second functional group includes one or more selected from a fluorescent compound and a phosphorescent compound. The organic film forming step includes
A dispersion preparation sub-process of preparing the organic molecule dispersion by dispersing the functional organic molecules in a solvent;
An immersion sub-step of immersing the wiring lead in the organic molecule dispersion over an area larger than the predetermined surface region of the wiring lead to which the resin is to be fixed, of the surface of the wiring lead. The manufacturing method of the metal part with resin in any one of Claims 9-17. A method for producing a greased metal part according to claim 9 is included in the process,
Between the organic film forming step and the resin fixing step, having a connecting step of electrically connecting a semiconductor element to the wiring lead,
In the resin fixing step, the semiconductor device is molded so that the semiconductor element is contained and a part of the wiring lead is exposed to the outside. An organic coating by self-organization of functional organic molecules is deposited on the surface of wiring leads made of metal materials,
The functional organic molecule is at one end of the purine skeleton,
A first functional group exhibiting at least one of a hydrogen bond and a coordinate bond is disposed on the wiring lead, and a second functional group exhibiting resin curability or resin curing acceleration is provided at the other end. Has a arranged chemical structure,
A wiring member, wherein the first functional group is bonded to a wiring lead. The functional organic molecule is
It consists of one or more compounds represented by the following general formula 5 or 6 or derivatives thereof,
The wiring member according to claim 20, wherein the first functional group includes one or more selected from a thiol compound, a sulfide compound, and a nitrogen-containing heterocyclic compound.

(However, any of R1, R2, R3, R4 has a first functional group and a second functional group, and the others are hydrogen, amine, hydroxyl group, ketone, aldehyde, carboxylic acid, sulfonic acid, amide, hydrazide. , Hydrazine, amidine, ether, halogen, nitrile, methylene, aryl, siloxane, glycol) Resin is fixed to a part of the wiring member according to claim 20 or 21,
The resin-coated metal part, wherein the organic coating is deposited over an area larger than the surface area of the wiring member to which the resin is fixed.   The resin-attached metal part according to claim 22, wherein the resin is a thermosetting resin. The thermosetting resin is at least one selected from epoxy resin, phenol resin, acrylic resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyimide resin, polyamide resin, polyether resin,
The second functional group is a hydroxyl group, carboxylic acid, acid anhydride, primary amine, secondary amine, tertiary amine, amide, thiol, sulfide, imide, hydrazide, imidazole, diazabicycloalkene, organic phosphine. 24. The resin-attached metal part according to claim 23, comprising at least one selected from boron trifluoride amine complexes. The thermosetting resin is a silicone resin,
24. The resin-attached metal part according to claim 23, wherein the second functional group includes at least one selected from a vinyl group and an organic hydrogen silane. The thermosetting resin is a silicone resin containing either an epoxy group or an alkoxysilyl group, or both,
The metal part with resin according to claim 23, wherein the second functional group includes one or more selected from a hydroxyl group, an acid anhydride, a primary amine, and a secondary amine. The thermosetting resin is a silicone resin;
The metal component with resin according to claim 23, wherein the second functional group is composed of a metal complex compound containing one or more selected from platinum, palladium, ruthenium, and rhodium.   21. The resin-attached metal part according to claim 20, wherein the second functional group contains one or more of a fluorescent compound and a phosphorescent compound. For the wiring member according to claim 20 or 21,
A semiconductor element is electrically connected on the wiring lead,
A resin-encapsulated semiconductor device, wherein the semiconductor element is resin-encapsulated in a region where the wiring member is partially exposed to the outside and the organic film is formed. A material containing a functional organic molecule having a first functional group having a binding property to a metal at one end of a purine skeleton and a second functional group having a predetermined property at the other end is attached to a predetermined surface of a wiring pattern layer, An organic film forming step of forming an organic film by bonding the first functional group to a metal atom constituting the wiring lead and self-organizing each functional organic molecule;
A solder resist layer forming step of forming a solder resist layer by applying a solder resist material so as to be chemically bonded to the second functional group of the functional organic molecule on the organic coating. Manufacturing method of film carrier tape. The second functional group is
31. The method for producing a film carrier tape according to claim 30, wherein the chemical bonding with the solder resist material exhibits at least one of resin curability and photopolymerization initiating property. The second functional group exhibits resin curability,
32. The method for producing a film carrier tape according to claim 31, comprising at least one selected from an acid anhydride and a primary amine compound. The second functional group exhibits photopolymerization initiation,
Benzophenones, acetophenones, alkylphenones, benzoins, anthraquinones, ketals, thioxanthones, coumarins, halogenated triazines, halogenated oxadiazoles, oxime esters, acridines, acridones, fluorenones, Including one or more selected from fluorans, acylphosphine oxides, metallocenes, polynuclear aromatics, xanthenes, cyanines, squaliums, acridones, titanocenes, tetraalkylthiuram sulfides,
In the solder resist layer forming step,
32. The method for producing a film carrier tape according to claim 31, wherein the second functional group is excited by light irradiation, a solder resist material is applied onto the organic coating, and the resist material is photopolymerized. In the organic film forming step,
An organic film is formed using a functional organic molecule having a photopolymerization-initiating second functional group,
In the solder resist layer forming step,
By immersing the wiring pattern layer on which the organic film is formed in a dispersion solution in which photopolymerizable molecules are dispersed, applying a predetermined pattern mask to the wiring pattern layer and irradiating with light in the dispersion solution, The method for producing a film carrier tape according to claim 30, wherein a polymerization reaction is caused on the bifunctional group to form a solder resist layer having a predetermined pattern. The wiring pattern layer is made of a Cu material,
32. A Sn plating layer forming step of forming an Sn plating layer on a predetermined surface of the wiring pattern layer other than the region where the solder resist layer is formed after the depositing solder resist layer forming step. Or the manufacturing method of the film carrier tape of 31. An organic film and a solder resist layer are sequentially laminated on the surface of the wiring pattern layer made of a metal material,
The organic coating is formed by self-organization of functional organic molecules,
In the functional organic molecule, a first functional group having a binding property to the metal of the wiring pattern layer is arranged at one end of the purine skeleton, and a chemical bonding property to the solder resist layer is provided at the other end. A bifunctional group,
The film carrier tape, wherein the first functional group is bonded to a wiring pattern layer, and the second functional group is bonded to a solder resist layer. The second functional group is
The film carrier tape according to claim 36, wherein the film carrier tape exhibits at least one of resin curability and photopolymerization initiating property when chemically bonded to the solder resist material. The second functional group exhibits resin curability,
38. The film carrier tape according to claim 37, comprising at least one selected from an acid anhydride and a primary amine compound. The second functional group exhibits photopolymerization initiation,
Benzophenones, acetophenones, alkylphenones, benzoins, anthraquinones, ketals, thioxanthones, coumarins, halogenated triazines, halogenated oxadiazoles, oxime esters, acridines, acridones, fluorenones, It includes at least one selected from fluorans, acylphosphine oxides, metallocenes, polynuclear aromatics, xanthenes, cyanines, squaliums, acridones, titanocenes, and tetraalkylthiuram sulfides. 38. A film carrier tape according to claim 37.

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