JP2019153661A - Adhesive structure and semiconductor module - Google Patents

Abstract

To provide an adhesive structure that is stable even at high temperatures and a semiconductor module including the same.SOLUTION: An adhesive structure 2D includes: a noble metal of a noble metal layer 10; and an adhesive resin 18 bonded by interaction of the noble metal layer 10 with the noble metal. Here, the noble metal of the noble metal layer 10 and the adhesive resin 18 are bonded by σ donation in which electrons are donated from a part of the functional group constituting the adhesive resin 18 toward the noble metal of the noble metal layer 10 and π reverse donation in which electrons are donated from the noble metal of the noble metal layer 10 toward the functional group. The functional group constituting the adhesive resin 18 has both a lone electron pair and an empty antibonding π orbit (πorbit) and bonds by σ donation and π reverse donation can be formed.SELECTED DRAWING: Figure 1

Description

  The present embodiment relates to an adhesive structure and a semiconductor module.

  As an adhesion technique for semiconductor devices in electronics, solder and conductive adhesive are used in terms of electrical connection, heat resistance, and resistance to mechanical stress. Furthermore, the semiconductor device is generally fixed in a package with a sealing resin.

  On the other hand, molecular theoretic studies on adhesion at the metal / epoxy resin interface, studies on the adhesion mechanism at the metal / epoxy resin interface by the density functional method, and theoretical studies on the adhesion mechanism between the epoxy resin and the glass interface are also disclosed.

JP 2009-182159 A

Shigeru Kohinata “Electronic Components / Mounting Technology Basic Course“ Conductive Adhesive ”3rd Basics of Conductive Adhesive (Part 2)”, Journal of Japan Institute of Electronics Packaging Vol.9, No.7, 2006, pp. 581-586 Fumihiro Osako, Kazunari Yoshizawa “Molecular Theory on the Bonding of Metal / Epoxy Resin Interface”, Kobunshi Ronbunshu, Vol. 68, No.2, pp.72-80 (Feb., 2011) Takayuki Semoto, Yuta Tsuji, Kazunari Yoshizawa “Study on Bonding Mechanism of Metal / Epoxy Resin Interface by Density Functional Method”, Molecular Science Society, 5th Molecular Science Meeting (September 2011), 1P054 Chiaki Higuchi, Hiroyuki Murata, Takayuki Semoto, Hiromasa Tanaka, Kazunari Yoshizawa “Theoretical Study on Bonding Mechanism between Epoxy Resin and Glass Interface”, Molecular Science Society, 10th Molecular Science Meeting (September 2016), 1P070 Kazunari Yoshizawa, Takayuki Semoto, Seiji Hitaoka, Chisa Higuchi, Yoshihito Shiota, and Hiromasa Tanaka, "Synergy of Electrostatic and van der Waals Interactions in the Adhesion of Epoxy Resin with Carbon-Fiber and Glass Surfaces", BCSJ Selected Paper, Bull. Chem Soc. Jpn, 2017, 90, 500-505, 2017 The Chemical Society of Japan.

  Conventionally, it has been empirically known that a conductive adhesive does not easily adhere to gold (Au). As a countermeasure, adhesion is improved by plasma treatment or the like. The plasma treatment is expected to have effects such as surface cleaning, improvement of wettability, increase in surface roughness, and addition of OH groups, but is empirical and the detailed mechanism is unknown. As a bonding technique for semiconductor devices, stricter quality is required in terms of design and manufacturing.

  The inventors of the present invention have found an adhesion structure that can strongly interact in adhesion between a noble metal and a resin and is difficult to cut even at high temperatures by molecular simulation technology.

  The present embodiment provides an adhesive structure that is stable even at high temperatures, and a semiconductor module including the adhesive structure.

  According to one aspect of the present embodiment, it comprises a noble metal and a resin bonded by interaction with the noble metal, and the noble metal and the resin are converted from the functional group constituting the resin to the noble metal. An adhesion structure is provided that is bonded by σ donation to which electrons are donated toward and π reverse donation in which electrons are donated from the noble metal toward the functional group.

  According to the other aspect of this Embodiment, a semiconductor module provided with said adhesion structure is provided.

  According to another aspect of the present embodiment, the noble metal layer includes a noble metal layer, a conductive resin layer bonded to the noble metal layer by interaction, and a semiconductor device disposed on the conductive resin layer. Layer and the conductive resin layer are σ donation in which electrons are donated from a part of the functional group of the first adhesive resin constituting the conductive resin layer toward the noble metal of the noble metal layer, and from the noble metal to the above-mentioned A semiconductor module is provided that is bonded by π reverse donation, in which electrons are donated towards the functional group.

  According to another aspect of the present embodiment, the noble metal layer includes a semiconductor device, a noble metal layer electrically connected to the semiconductor device, and a mold resin layer bonded by interaction with the noble metal layer. And the mold resin layer includes a σ donation in which electrons are donated from a part of the functional group of the second adhesive resin constituting the mold resin layer toward the noble metal of the noble metal layer, and the noble metal to the functional group. A semiconductor module is provided which is bonded by π reverse donation where electrons are donated towards.

  According to the present embodiment, it is possible to provide an adhesive structure that is stable even at high temperatures, and a semiconductor module including the adhesive structure.

The typical cross-section figure (die bonding) of the adhesion structure concerning one embodiment to which this art is applied. (A) Typical cross-section figure of a semiconductor module provided with the adhesion structure concerning one embodiment to which this art is applied, (b) As a comparative example, the schematic of the semiconductor module of the poor adhesion state which has been partially peeled off Sectional structure diagram, (c) Typical sectional structure diagram of a semiconductor module in a poorly bonded state as a comparative example. The typical structure figure of a conductive resin layer. The typical cross-section figure (mold sealing) of the adhesion structure concerning one embodiment to which this art is applied. The typical cross-section figure of a semiconductor module provided with the adhesion structure concerning one embodiment to which this art is applied. The typical structure figure of a mold resin layer. (A) Example of molecular structure (molecular simulation model) of bisphenol A type epoxy resin using dicyandiamide as a curing agent applicable to the adhesive structure according to the embodiment, (b) As a comparative example, the curing agent was removed. Example of molecular structure of bisphenol A type epoxy resin. Example of polymerization structure of bisphenol A type epoxy resin (n = 0, 1,...). FIG. 8 shows an example of the molecular structure of bisphenol A diglycidyl ether (DGEBA) corresponding to the case where n = 0. It is an example of the hardening | curing agent applicable to the adhesion structure which concerns on embodiment, Comprising: The molecular structural example of a dicyandiamide. It is explanatory drawing of the production | generation method of the epoxy resin applicable to the adhesion | attachment structure which concerns on embodiment, Comprising: (a) Molecular structure example of DGEBA, (b) Molecular structure example ((B) structure) of dicyandiamide, (c) ) An example of the molecular structure of the reaction product (epoxy resin) of DGEBA in FIG. 11 (a) and dicyandiamide ((B) structure). It is explanatory drawing of the production | generation method of the epoxy resin applicable to the adhesion structure which concerns on embodiment, Comprising: (a) The reaction product of DGEBA and dicyandiamide ((B) structure) shown by FIG.11 (c), Example of molecular structure of reaction product with DGEBA, (b) Example of molecular structure of reaction product shown in FIG. Schematic explanatory drawing of the state where the adhesive force between the noble metal surface and the molecular skeleton of the adhesive is weak. Schematic explanatory drawing of the state where the adhesive force between the noble metal surface and the molecular skeleton of the adhesive is strong. (A) A method for forming a clean Au surface structure, schematically illustrating the outermost surface structure of an Au plating layer formed using a process using a cyano complex as a raw material, and (b) a clean Au surface structure. A schematic explanatory diagram of the outermost surface structure of an Au plating layer formed by a process using a non-cyano complex as a raw material, and (c) a schematic explanatory diagram of a clean Au surface structure. (A) Schematic explanatory drawing of the outermost surface structure of a cyan noble metal plating layer, (b) Schematic explanatory drawing of the outermost surface structure of a dinitrodiammine noble metal plating layer. (A) Explanatory drawing of (pi) reverse donation in a complex, (b) Explanatory drawing of (pi) reverse donation in adhesion | attachment on a metal surface. It is a chemical formula of a functional group applicable to the adhesive structure according to the embodiment, and includes (a) an example of a cyano group, (b) an example of a thiocyano group, (c) an example of a carbonyl group, and (d) an ester group. Examples (e) Examples of amide groups, (f) Examples of azido groups, (g) Examples of isocyano groups, (h) Examples of sulfo groups, (i) Examples of nitro groups. Relationship between peeling energy E and peeling distance Δr in the presence or absence of a curing agent. Relationship between adhesion stress F with and without curing agent and peel distance Δr. The relationship between the dispersion force, the density functional (DFT), and the adhesive stress F and the peeling distance Δr using the sum of these as parameters (model with added hardener). Dispersion force, density functional (DFT), and relationship between adhesion stress F and peel distance Δr using the sum of these as parameters (model excluding curing agent). The typical section structure figure of the semiconductor module provided with the adhesion structure concerning one embodiment to which this art is applied (example of the semiconductor module mounted in SOP). FIG. 24A is a schematic cross-sectional structure diagram in the vicinity of the region A in FIG. 23, and FIG. The typical section structure figure of the semiconductor module provided with the adhesion structure concerning one embodiment to which this art is applied (example of the semiconductor module mounted in lead frame type MCP).

  Next, the present embodiment will be described with reference to the drawings. In the description of the drawings described below, the same or similar parts are denoted by the same or similar reference numerals. However, it should be noted that the drawings are schematic, and the relationship between the thickness of each component and the planar dimensions is different from the actual one. Therefore, specific thicknesses and dimensions should be determined in consideration of the following description. In addition, it is a matter of course that portions having different dimensional relationships and ratios are included between the drawings.

  Further, the embodiments described below exemplify apparatuses and methods for embodying the technical idea, and do not specify the material, shape, structure, arrangement, and the like of each component. This embodiment can be modified in various ways within the scope of the claims.

(Die bonding of semiconductor devices)
A schematic cross-sectional structure of an adhesive structure 2D according to an embodiment to which the present technology is applied is expressed as shown in FIG. In addition, a schematic cross-sectional structure of a semiconductor module 4D including an adhesive structure 2D according to an embodiment to which the present technology is applied is represented as illustrated in FIG. Further, as a comparative example, a schematic cross-sectional structure of a poorly bonded semiconductor module 4A partially peeled is represented as shown in FIG. 2B, and is completely peeled badly bonded semiconductor module 4A. The schematic cross-sectional structure of is represented as shown in FIG.

  In a semiconductor module 4A in which a gold (Au) plating 10A is formed as a noble metal plating on a die pad, and the semiconductor device 14 is disposed on the Au plating 10A via a conductive resin layer 12A made of Ag paste, If the adhesion with the resin layer 12A is weak, die bonding is peeled off as shown in FIGS. 2B and 2C, and an electrical connection failure occurs. In addition, in the LED chip arranged on the package substrate, the Ag paste may be peeled off on the entire surface as shown in FIG. In a laminated structure composed of the semiconductor device 14 / conductive resin layer 12A / Au plating 10A, there are many modes that peel off at the interface of the conductive resin layer 12A / Au plating 10A.

  In order to strengthen the adhesion interface between the gold surface and the epoxy resin, molecular simulations and experiments were conducted. As a result, an adhesive structure that was stable even at high temperatures was found. Details will be described below.

  As shown in FIG. 1, an adhesive structure 2D according to an embodiment to which the present technology is applied includes a noble metal of the noble metal layer 10 and an adhesive resin 18 bonded by an interaction between the noble metal of the noble metal layer 10. Prepare. Here, the noble metal and the adhesive resin 18 of the noble metal layer 10 are σ donation in which electrons are donated from a part of the functional group constituting the adhesive resin 18 toward the noble metal, and the noble metal of the noble metal layer 10 is converted into the functional group. Bonding is performed by π reverse donation in which electrons are donated.

The functional group constituting the adhesive resin 18 has both a lone electron pair and an empty antibonding π orbit (π ^* orbital), and can form a bond by σ donation and π reverse donation.

  Further, the noble metal of the noble metal layer 10 may include at least one kind or a plurality of kinds selected from the group of Au, Ag, Pt, Pd, Rh, Ru, Ir, Os, and the like.

  In addition, the adhesive resin 18 may include at least one type or a plurality of types selected from the group of, for example, an epoxy resin, an acrylic resin, a phenol resin, and a silicone resin.

  The functional group constituting the adhesive resin 18 is, for example, at least one or more selected from the group of cyano group, thiocyano group, carbonyl group, ester group, amide group, azide group, isocyano group, sulfo group, nitro group and the like. You may have a kind.

  In addition, the adhesive resin 18 may include an epoxy resin formed by a reaction between bisphenol A diglycidyl ether (DGEBA) and dicyandiamide, for example.

  The noble metal layer 10 may include a noble metal plating layer.

  Further, the noble metal and the adhesive resin 18 may further include a hydrogen bond in a partial bond between the noble metal and the adhesive resin 18. This is because, depending on the state of the noble metal surface, there may be a functional group capable of binding to the OH group on a part of the clean surface.

  As shown in FIG. 2A, a semiconductor module 4D including an adhesive structure 2D according to an embodiment to which the present technology is applied includes a noble metal layer 10 and a conductive resin that is bonded to the noble metal layer 10 through interaction. A layer 12 and a semiconductor device 14 disposed on the conductive resin layer 12 are provided. Here, the noble metal layer 10 and the conductive resin layer 12 are supplied with electrons from a part of the functional groups of the first adhesive resin 18 constituting the conductive resin layer 12 toward the noble metal of the noble metal layer 10. And π reverse donation in which electrons are donated from the noble metal of the noble metal layer 10 toward the functional group of the first adhesive resin 18.

  Here, the schematic structure of the conductive resin layer 12 is expressed as shown in FIG.

  As shown in FIG. 3, the conductive resin layer 12 includes a first adhesive resin 18 and a metal filler 16 contained in the first adhesive resin 18. The metal filler 16 consists of metal particles. Here, as a metal material constituting the metal particles, for example, Au, Ag, Pt, Pd, or the like can be applied.

  The noble metal of the noble metal layer 10 may include at least one type or a plurality of types selected from a group such as Au, Ag, Pt, Pd, Rh, Ru, Ir, and Os.

  Moreover, the 1st adhesive resin 18 may be provided with at least 1 type or multiple types chosen, for example from groups, such as an epoxy resin, an acrylic resin, a phenol resin, and a silicone resin.

  In addition, the semiconductor device 14 may include, for example, a light emitting diode (LED), a semiconductor laser, a power semiconductor element, an integrated circuit, or a combination thereof.

  According to the bonded structure according to an embodiment to which the present technology is applied, for example, peeling in die bonding using a conductive resin layer can be prevented.

  According to the adhesive structure according to one embodiment to which the present technology is applied, by performing σ donation from the functional group derived from the curing agent of the first adhesive resin, and simultaneously performing π reverse donation from the metal interface, An adhesive structure that is stable even at high temperatures and a semiconductor module including the adhesive structure can be provided.

(Semiconductor device mold sealing)
A schematic cross-sectional structure of an adhesive structure 2S according to an embodiment to which the present technology is applied is expressed as shown in FIG. In addition, a schematic cross-sectional structure of a semiconductor module 4S including an adhesive structure 2S according to an embodiment to which the present technology is applied is represented as illustrated in FIG.

  As shown in FIG. 4, the bonding structure 2 </ b> S according to the embodiment to which the present technology is applied includes a noble metal of the noble metal layer 10 and a mold resin layer 20 bonded by an interaction between the noble metal of the noble metal layer 10. Prepare. Here, the noble metal of the noble metal layer 10 and the mold resin layer 20 are composed of σ donation in which electrons are donated from a part of functional groups of the second adhesive resin 19 constituting the mold resin layer 20 toward the noble metal, and the noble metal layer. Bonding is performed by π reverse donation in which electrons are donated from ten noble metals toward the functional group of the second adhesive resin 19.

  An adhesive structure 2S according to an embodiment to which the present technology is applied includes a metal frame for external connection of a package as well as a joint between the noble metal layer 10 including the metal frame on which the semiconductor device 14 is mounted and the mold resin layer 20. The present invention can be similarly applied to the joining of the noble metal layer 10 and the mold resin layer 20.

The functional group of the second adhesive resin 19 has both a lone electron pair and an empty antibonding π orbit (π ^* orbital), and can form a bond by σ donation and π reverse donation.

  Further, the noble metal and the mold resin layer 20 may further include hydrogen bonds in a partial bond between the noble metal and the mold resin layer 20. This is because, depending on the state of the noble metal surface, there may be a functional group capable of binding to the OH group on a part of the clean surface.

  Further, the noble metal of the noble metal layer 10 may include at least one kind or a plurality of kinds selected from the group of Au, Ag, Pt, Pd, Rh, Ru, Ir, Os, and the like.

  Moreover, the mold resin layer 20 may include at least one type or a plurality of types selected from the group of, for example, an epoxy resin, an acrylic resin, a phenol resin, and a silicone resin.

  The functional group constituting the mold resin layer 20 is, for example, at least one or more selected from the group of cyano group, thiocyano group, carbonyl group, ester group, amide group, azide group, isocyano group, sulfo group, nitro group and the like. You may have a kind.

  The noble metal layer 10 may include a noble metal plating layer.

  As shown in FIG. 5, a semiconductor module 4 </ b> S including an adhesive structure 2 </ b> S according to the second embodiment includes a noble metal layer 10, a conductive resin layer 12 that is bonded to the noble metal layer 10 through interaction, and a conductive property. A semiconductor device 14 disposed on the resin layer 12 and a mold resin layer 20 bonded to the noble metal layer 10 by interaction are further provided.

  Here, the noble metal layer 10 and the conductive resin layer 12 are supplied with electrons from a part of the functional groups of the first adhesive resin 18 constituting the conductive resin layer 12 toward the noble metal of the noble metal layer 10. And π reverse donation in which electrons are donated from the noble metal of the noble metal layer 10 toward the functional group of the first adhesive resin 18.

  Further, the noble metal layer 10 and the mold resin layer 20 include a σ donation in which electrons are donated from a part of the functional groups of the second adhesive resin 19 constituting the mold resin layer 20 toward the noble metal of the noble metal layer 10, and the noble metal Are bonded by π reverse donation, in which electrons are donated from the functional group toward the functional group.

  A schematic structure of the mold resin layer 20 is expressed as shown in FIG.

  As shown in FIG. 6, the mold resin layer 20 includes an adhesive resin 19 and a filler 22 contained in the adhesive resin 19. The mold resin layer 20 is non-conductive, and the filler 22 is made of ceramic particles. Here, as a ceramic material of the ceramic particles, for example, silica, alumina or the like can be applied. By adding the filler 22 made of ceramic, control of the linear expansion coefficient and reliability are improved.

  The noble metal of the noble metal layer 10 may include at least one type or a plurality of types selected from a group such as Au, Ag, Pt, Pd, Rh, Ru, Ir, and Os.

  Moreover, the 1st adhesive resin 18 and the 2nd adhesive resin 19 are provided with at least 1 type or multiple types chosen from the group, such as an epoxy-type resin, an acrylic resin, a phenol resin, and a silicone resin, for example. Also good.

  The functional groups constituting the first adhesive resin 18 and the second adhesive resin 19 are, for example, a cyano group, a thiocyano group, a carbonyl group, an ester group, an amide group, an azide group, an isocyano group, a sulfo group, and a nitro group. You may provide at least 1 type or multiple types chosen from groups, such as.

  Further, the semiconductor device 14 may include any one of, for example, an LED, a semiconductor laser, a power semiconductor, an integrated circuit, or a combination thereof.

  According to the bonded structure according to the embodiment to which the present technology is applied, not only can the peeling in the die bonding using the conductive resin layer be prevented, but also the strong bond between the mold resin layer and the metal frame. Can also be achieved.

  According to the adhesive structure according to an embodiment to which the present technology is applied, σ donation is performed from the functional group derived from the curing agent of the first adhesive resin and the second adhesive resin, and π reverse donation is simultaneously performed from the metal interface By carrying out the above, it is possible to provide an adhesive structure that is stable even at high temperatures, and a semiconductor module including the adhesive structure.

(Molecular simulation model)
A molecular structure example (molecular simulation model) of a bisphenol A type epoxy resin using dicyandiamide as a curing agent that can be applied to the adhesive structure according to the present embodiment is expressed as shown in FIG. As an example, a molecular structure example of a bisphenol A type epoxy resin excluding a curing agent is represented as shown in FIG.

(General structure of bisphenol A type epoxy resin)
An example of a polymerization structure (n = 0, 1,...) Of a bisphenol A type epoxy resin is represented as shown in FIG. Further, an example of the molecular structure of bisphenol A diglycidyl ether (DGEBA) corresponding to the case of n = 0 in FIG. 8 is represented as shown in FIG.

  In the case of a liquid resin such as an adhesive, the average value of n is said to be about 0.1 to 0.2. In the following reaction formula, the case where n = 0 is described as an example.

(Example of curing agent: dicyandiamide)
FIG. 10 shows an example of the molecular structure of dicyandiamide, which is an example of a curing agent that can be applied to the adhesive structure according to the present embodiment. Since dicyandiamide has tautomerism, there are two structures (A) and (B) shown in FIG. Among these, the (B) structure has a higher existence probability. For this reason, in the following reaction formula, (B) structure is demonstrated as an example.

(Curing reaction between bisphenol A type epoxy resin and dicyandiamide)
A method for producing an epoxy resin applicable to the bonded structure according to the embodiment will be described.

  It is explanatory drawing of the production | generation method of the epoxy resin applicable to the adhesion structure which concerns on embodiment, Comprising: The molecular structural example of DGEBA is represented as shown to Fig.11 (a). An example of the molecular structure of dicyandiamide ((B) structure) is represented as shown in FIG. An example of the molecular structure of a reaction product (epoxy resin) of DGEBA and dicyandiamide ((B) structure) is represented as shown in FIG.

  As the reaction further proceeds, an example of the molecular structure of the reaction product of DGEBA and dicyandiamide (structure (B)) and the reaction product of DGEBA shown in FIG. 11 (c) is shown in FIG. 12 (a). It is expressed in As the reaction further proceeds, due to the elimination of ammonia, an example of the cyclized molecular structure of the reaction product shown in FIG. 12A is expressed as shown in FIG. When the terminal epoxy group further reacts, the curing reaction proceeds.

(Adhesive strength is weak)
A schematic explanatory diagram of a state where the adhesive force due to hydrogen bonding between the noble metal surface and the molecular skeleton of the adhesive is weak is expressed as shown in FIG. An adhesive resin made of an epoxy resin having an Au plating layer 30 and a molecular skeleton 24 will be described as an example of the noble metal layer.

The outermost surface of the noble metal plating is easily terminated with a ligand constituting the raw material complex. For example, in the case of Au plating, when gold (I) potassium cyanide (K [Au (CN) ₂ ]) is applied as a raw material, the surface structure of the Au plating layer 30 is terminated with a CN functional group 26. Was found by analysis.

(Result of outermost surface analysis of Au by XPS)
The outermost surface of the gold land portion of the package substrate was analyzed using X-ray photoelectron spectroscopy (XPS). As a result, about 50% of Au, about 33.8% of C, about 5.4% of O, and about 1.0% of Cu were detected on the outermost surface.

(Au outermost surface analysis result by TOF-SIMS)
Since a large amount of carbon (C) is detected on the outermost surface of the gold land portion of the package substrate, time-of-flight secondary ion mass spectrometry (TOF-SIMS) is used to investigate the existence state of the element. An outermost surface analysis of Au in the gold land portion was performed by mass spectrometry. As a result, AuC ₂ N ₂ , CuAu ₂ , NiAu ₂ , C ₃ N, C ₆ , Au _{4 and the} like were detected. That is, according to the outermost surface analysis result of Au by TOF-SIMS, AuCN system / CN system / C system / Au metal /... Is detected from the outermost surface, and the depth to the AuCN system / CN system / C system is , About 8 cm (about 8 atomic layers). Therefore, it was specified that the outermost surface of Au formed by Au plating of the gold land portion is terminated with an AuCN system.

  That is, the outermost surface of the Au plating layer 30 is easily terminated with a ligand constituting the raw material complex. In this case, adhesion is based on hydrogen bonds, and sufficient adhesive strength cannot be obtained. If hydrogen bonding (OH) is likely to occur, for example, peeling is likely to occur at a high temperature of about 100 ° C. or higher.

  The surface structure of the Au plating layer 30 is terminated with a CN-based functional group 26 as shown in FIG. As a result, the molecular skeleton 24 is bonded to the CN bond on the Au surface terminated with the CN functional group 26 by a hydrogen bond (OH) by the OH group 28. The state where the adhesive force is weak is a weak adhesive state due to hydrogen bonds (OH) by the OH groups 28. Here, the value of the binding energy is, for example, about 5 kJ / mol to 40 kJ / mol. In a state where the adhesive force is weak, the bond energy is low, so that the bond is easily cut at a high temperature.

(Strong adhesion)
We found an adhesion structure that can interact strongly with Au by molecular simulation technology. Compared with the case where it does not interact with Au, an adhesive force of about 1.5 times can be obtained.

  FIG. 14 is a schematic explanatory view showing a state where the adhesive force based on the interaction more stable than the hydrogen bond by the OH group 28 is strong by σ-donation and π-reverse donation simultaneously between the noble metal surface and the molecular skeleton 24 of the adhesive. It is expressed as shown in Hydrogen bonding by the OH groups 28 is difficult for a clean Au surface close to the ideal state, and functional groups other than the OH groups 28 can be bonded. As a functional group other than the OH group 28, for example, as shown in FIG. 14, a CN functional group 34, a CO functional group 32, or the like can be applied.

As a result of molecular simulation, it was found that these bonds are based on σ donation and π reverse donation. A functional group having both a lone electron pair and an empty antibonding π orbital (π ^* orbital) can simultaneously form a bond by σ donation and π reverse donation.

  Here, the value of the bond energy in a state where the adhesive force is strong is, for example, about 100 kJ / mol or more. A lone electron pair is donated to the noble metal surface from a part of the functional group constituting the resin, and at the same time, electrons are donated from the noble metal surface to the functional group by π reverse donation, Adhesive structures based on interactions that are more stable than hydrogen bonds can be formed.

(Method for forming a clean Au surface structure)
A schematic explanatory diagram of the outermost surface structure of the Au plating layer 30 formed by using a process using a cyano complex as a raw material is a method for forming a clean Au surface structure as shown in FIG. Is done.

As for the outermost surface structure of the Au plating layer 30, the Au surface is terminated with a CN system, as shown in FIG. In the case of a process using a cyano complex as a raw material, for example, potassium dicyanogold (I) acid K [Au (CN) ₂ ], tetracyanogold (III) potassium K [Au (CN) ₄ ], or the like is applicable.

Next, due to physical sputtering technology using argon (Ar) plasma and chemical interaction using hydrogen plasma, the CN functional group on the Au surface is changed from CN to C _{x Hy} system + NH ₃ system. Since it can be decomposed, a clean Au surface structure can be formed as shown in FIG.

  FIG. 15B is a schematic explanatory diagram of the outermost surface structure of the Au plating layer 30 formed by using a process using a non-cyano complex as a raw material, which is a method for forming a clean Au surface structure. expressed.

As shown in FIG. 15B, the outermost surface structure of the Au plating layer 30 is terminated with an SO ₃ functional group. In the case of a process using a non-cyano complex as a raw material, for example, disulfite gold (I) sodium Na ₃ [Au (SO ₃ ) ₂ ] and the like can be applied.

  Next, a clean Au surface structure can be formed by a physical sputtering technique using argon (Ar) plasma or a chemical interaction using hydrogen plasma, as shown in 15 (c).

(Comparison of adhesive strength when various treatments are performed)
In the bonded structure subjected to the oxygen (O ₂ ) plasma treatment, the adhesive strength was reduced by about 30% compared to the case where the bonded structure was not performed. On the other hand, in the bonded structure subjected to the argon (Ar) plasma treatment, the adhesive force increased by about 10% or more compared to the case where the bonded structure was not performed. By the oxygen (O ₂ ) plasma treatment, the CN functional group on the Au surface is oxidized to carboxylic acid or ketone, so that adhesion by hydrogen bonding becomes dominant, and the adhesive strength is reduced. On the other hand, in the argon (Ar) plasma treatment, the CN functional group on the Au surface can be removed, so that the adhesive force can be increased.

(Measurement of adhesive strength at high temperature)
The Ag paste layer as the conductive resin layer was subjected to a high-temperature tensile test, and the adhesive strength was evaluated by changing the temperature. As a result, the adhesive strength was reduced by about 15% at 120 ° C. and about 48% at 180 ° C. compared to room temperature. The relationship between the adhesive strength and the amount of displacement was approximately the same at room temperature, 120 ° C., and 180 ° C., and no behavior was observed in which the cured resin was softened.

  From the above results, it is estimated that the decrease in adhesive strength at high temperatures is highly likely due to the breakage of hydrogen bonds at the adhesive interface.

(Type of precious metal plating)
A schematic illustration of the outermost surface structure of the cyan noble metal plating layer is expressed as shown in FIG. For example, Au or Ag can be applied to the noble metal atoms 50 constituting the cyan noble metal plating layer 40. In the case of Au plating, gold (I) potassium cyanide K [Au (CN) ₂ ] can be used as a raw material. In the case of Ag plating, silver (I) potassium cyanide K [Ag (CN) ₂ ] can be used as a raw material.

A schematic illustration of the outermost surface structure of the dinitrodiammine-based noble metal plating layer is expressed as shown in FIG. For example, Pt or Pd can be applied to the noble metal atom 70 constituting the dinitrodiammine-based noble metal plating layer 60. In the case of Pt plating, dinitrodiammine platinum (II) cis- [Pt (NO ₂ ) ₂ (NH ₃ ) ₂ ] can be used as a raw material. In the case of Pd plating, dinitrodiammine platinum (II) cis- [Pd (NO ₂ ) ₂ (NH ₃ ) ₂ ] can be used as a raw material.

  The noble metal applicable to the adhesion structure according to the present embodiment and the semiconductor module including the adhesion structure is selected from the group of, for example, Au, Ag, Pt, Pd, Rh, Ru, Ir, and Os. At least one kind or plural kinds can be mentioned.

(Π reverse donation)
An explanatory view of σ donation and π reverse donation in the complex is expressed as shown in FIG. 17A, and an explanatory view of σ donation and π reverse donation in the adhesion on the metal surface is shown in FIG. 17B. It is expressed in In FIG. 17B, when the full band of metal M is represented by E _V , the conduction band is represented by E _C , and the Fermi level of metal M is represented by E _f , the full band from E _V to Fermi level E _f is filled with electrons. Yes.

  As shown in FIG. 17 (a) and FIG. 17 (b), electrons are usually directed from the ligand (LIGAND) of a specific functional group contained in a polymer chain such as a CO series or CN series toward the metal M. Donated σ donation works. On the other hand, it is π back donation that electrons are donated from the metal M toward the ligand.

For example, an epoxy-based adhesive having an Au plating layer and a CN-based functional group has a σ-donation in which electrons are donated from a part of the CN-based functional group toward Au, and from Au to a CN-based functional group. Are bonded by π reverse donation, in which electrons are donated. Here, π reverse donation works between the Au5d orbital and the CN π ^* orbital.

  In the results obtained using the molecular simulation technique, the C—N distance = 1.30Å and 1.19Å in the σ donation at the HOMO level. On the other hand, in π reverse donation at the LUMO level, C−N = 1.31Å and 1.18Å.

(Example of corresponding functional group)
The applicable functional groups are listed as follows. That is, it is a chemical formula of a functional group applicable to the adhesive structure according to the present embodiment, and an example of a cyano group is represented as shown in FIG. 18A, and an example of a thiocyano group is shown in FIG. An example of a carbonyl group is represented as shown in FIG. 18 (c), an example of an ester group is represented as shown in FIG. 18 (d), and an example of an amide group is shown in FIG. 18 (e). ), Examples of azido groups are represented as shown in FIG. 18 (f), examples of isocyano groups are represented as shown in FIG. 18 (g), and examples of sulfo groups are shown in FIG. 18 (f). h), and examples of nitro groups are represented as shown in FIG. Of these, a cyano group, a carbonyl group, an ester group, an amide group and the like are desirable from the viewpoint of stability.

(Molecular simulation technology)
The theoretically stable molecular structure of the molecular model of bisphenol A type epoxy resin + dicyandiamide system was calculated by molecular simulation technology. As a result, it has been found that it is not an OH group but a CN functional group derived from a curing agent that interacts with the Au surface. Hereinafter, the molecular simulation will be described in detail.

(Explanation on molecular simulation_ 1)
(Implementation procedure)
(1) Create a model structure of Au (111).

In the Au bulk structure optimization, the program is VASP (density functional theory), the functional is GGA-PBE, the cut-off energy is 500 eV, the k-point mesh is 2π × 0.05Å ⁻¹ , the pseudopotential is PAW, and the dispersion Tkatchenko-Scheffler was used for force correction.

  As a result, the (111) plane is cut out from the optimized structure.

  (2) Next, a surface structure of Au is created.

  The cut (111) plane is expanded to produce a 5 × 5 slab model. Here, the number of atoms: 5 × 5 × 3 (75 atoms). The lower two layers were fixed, and a vacuum layer having a thickness of 30 mm was formed on Au.

(Explanation on molecular simulation_2)
(3) Create a model structure of epoxy resin.

―Selection of material system―
The epoxy resin was DGEBA + curing agent (dicyandiamide). The molecular model of the target epoxy resin corresponds to the structure of the chemical formula in FIG.

  Next, molecular modeling was performed. In molecular modeling, the epoxy group of DGEBA and the amino group of dicyandiamide were subjected to an addition reaction, and the glycidyl group on the unreacted side of DGEBA was replaced with a methyl group for the sake of simplicity. As a result, the molecular structure shown in FIG. As a comparative example, the molecular model of the bisphenol A type epoxy resin excluding the curing agent corresponds to the structure of the chemical formula in FIG.

  Next, molecular model placement was performed.

  The molecular model produced by selecting the material system in (3) above was placed in the vacuum layer of the Au slab model produced in (2) above.

(Explanation on molecular simulation_3)
(Implementation procedure)
(4) Calculation of the most stable structure The search for the most stable structure is performed by molecular dynamics calculation.

  The program is Forcite, the time step is 1fs, the force field is COMPASS, the simulation time is 5ps, the temperature is 350K, the quench step is 250, the ensemble is NVE, and the minimize is smart.

Next, the structure optimization of the adhesion model by the density functional method is executed. The initial structure model is the most stable structure found above, the program is VASP, the functional is GGA-PBE, the cut-off energy is 500 eV, the k-point mesh is 2π × 0.05Å ^-1 , the pseudopotential is PAW, Dispersion force correction was performed using Tkatchenko-Scheffler.

  Next, the difference electron density was calculated. As a result, it was found that no electron exchange occurred in the hydroxy group (OH), and that σ donation and π reverse donation occurred in the cyano group.

(Explanation on molecular simulation_4)
(Implementation procedure)
(5) Calculate the adhesive stress.
In the adhesion model optimized by the calculation of the most stable structure in (4) above, the energy E for peeling off the epoxy molecules is calculated by the NEB (Nudged Elastic Band) method. The NEB method is a method for obtaining a minimum energy path (MEP) of a potential energy surface between two local stable structures.

(Adhesive stress calculation method)
The peeling energy E at the time of peeling off the epoxy molecules is approximated by a Morse potential and is expressed by the equation (1).

E = D _e [1-exp (−aΔr)] ² (1)

However, a = ω _e (M / 2D _e ) ^1/2 and Δr = r _e −r. D _e represents dissociation energy, [Delta] r is peeled off distance, respectively. r represents the bond distance of a diatomic molecule. Also, the r _e equilibrium binding interval, M has reduced mass, the omega _e the wave number of the vibration.

By differentiating the Morse potential approximate curve, the adhesion stress F can be estimated. The adhesive stress F is expressed by equation (2).

F = dE / dΔr (2)

(Explanation on molecular simulation_5)
(Implementation procedure)
(6) Calculation was performed with a molecular model for comparison.

  In order to clarify the degree to which the functional group of the curing agent contributed to the adhesive force, the same calculation was performed using a model in which the portion of the curing agent was terminated with H. The molecular model for comparison corresponds to the structure of the chemical formula in FIG.

(Effect of OH group)
In the molecular simulation of the adhesion structure between the Au surface and the epoxy resin, the influence of OH groups was examined. As a result, in the model in which the OH group is far from the Au surface, the distance between Au—N = 2.527 mm, the distance between Au—OH = 5.689 mm, and the binding energy = −583.50 eV. . On the other hand, in the model where the OH group is close to the Au surface, the distance between Au—N = 3.313 Å, the distance between Au—OH = 3.119 Å, and the binding energy = −583.42 eV. The bond energy difference ΔE = 1.8 kcal between the model in which the OH group is far from the Au surface and the model in which the OH group is close to the Au surface.

  From the calculation results of the difference electron density, electron transfer (π reverse donation) was observed in the cyano group in both the model in which the OH group was close to the Au surface and the model in which the OH group was far from the Au surface.

(Effects of CN group of curing agent)
―Evaluation of adhesive stress―
The relationship between the peel energy E and the peel distance Δr with or without the curing agent (comparison of potential energy) is expressed as shown in FIG.

  The tear energy E tends to be higher in the curve with the curing agent than in the curve without the curing agent, compared to the change in potential energy.

  The relationship between the adhesive stress F with and without the curing agent and the peeling distance Δr (comparison of displacement-stress curve) is expressed as shown in FIG.

  The maximum value of the adhesive stress F of the model to which the curing agent is added is about 1150 (MPa). On the other hand, the maximum value of the adhesive stress F of the model excluding the curing agent is about 800 (MPa).

  In the molecular model of gold surface and bisphenol A type epoxy resin + dicyandiamide system, when the peel distance Δr (Å) is 2Å, 3 場合 is compared with 4Å, the case of 4 剥 can be stably peeled off it can.

(DFT and dispersion force)
The relationship in which the contribution of the adhesive force is divided into the component F _disp due to the dispersion force and the other component (component F _DFT that can be calculated by the density functional (DFT)) is expressed as shown in FIG. Moreover, the relationship (model except a hardening | curing agent) which divided _| segmented contribution of adhesive force into the component _Fdisp by dispersion force and the other (component _FDFT which can be calculated by _DFT ) is represented as shown in FIG.

The total value of the adhesive stress F _tot is expressed by equation (3).

F _tot = F _DFT + F _disp (3)

From the results of FIGS. 21 and 22, it can be seen that the influence on the adhesive stress F greatly contributes to the dispersion stress due to the adhesive stress F _disp .

  In summary, the adhesive stress between Au and epoxy resin is largely due to the dispersion force. In a model of an epoxy resin including a curing agent, π reverse donation at a cyano group included in the curing agent contributes to adhesion.

(Semiconductor module mounted on SOP)
In the following description, the description overlapping with the bonding structure according to the embodiment to which the present technology is applied and the semiconductor module including the bonding structure can be similarly applied, and thus the description is omitted.

  A schematic cross-sectional structure of a semiconductor module 6 including an adhesive structure according to an embodiment to which the present technology is applied is expressed as shown in FIG. FIG. 23 shows an example of a semiconductor module mounted on a small outline package (SOP). Further, a schematic cross-sectional structure in the vicinity of the region A in FIG. 23 is expressed as shown in FIG. 24A, and a schematic cross-sectional structure in the vicinity of the region B in FIG. 23 is expressed as shown in FIG. .

  As shown in FIG. 23, the semiconductor module 6 mounted on the SOP includes a lead frame 66, a noble metal layer 10D formed on the lead frame 66, and a conductive resin layer 12 bonded by interaction with the noble metal layer 10D. And a semiconductor device 14 disposed on the conductive resin layer 12. As shown in FIG. 24B, the noble metal layer 10D and the conductive resin layer 12 have electrons from a part of the functional group of the first adhesive resin constituting the conductive resin layer 12 toward the noble metal of the noble metal layer 10D. Is provided by σ donation and π reverse donation in which electrons are donated from the noble metal of the noble metal layer 10D toward the functional group of the first adhesive resin.

  Furthermore, as shown in FIG. 23, the semiconductor module 6 mounted on the SOP includes a mold resin layer 20 bonded to the noble metal layer 10D by interaction. The noble metal layer 10D and the mold resin layer 20 include a σ donation in which electrons are donated from a part of the functional groups of the second adhesive resin constituting the mold resin layer 20 toward the noble metal of the noble metal layer 10D, and the noble metal layer 10D. Bonding is performed by π reverse donation in which electrons are donated from the noble metal toward the functional group of the second adhesive resin.

  Further, as shown in FIG. 23, the semiconductor module 6 mounted on the SOP includes a lead frame 64 and a noble metal layer 10L formed on the lead frame 64 by a plating technique. As shown in FIG. 24 (a), the noble metal layer 10L and the mold resin layer 20 donate electrons from a part of the functional groups of the second adhesive resin constituting the mold resin layer 20 toward the noble metal of the noble metal layer 10L. Σ donation and π reverse donation in which electrons are donated from the noble metal of the noble metal layer 10L toward the functional group of the second adhesive resin.

  The entire semiconductor module 6 mounted on the SOP is resin-sealed with a mold resin layer 20 as shown in FIG. A bonding wire 62 is connected between the noble metal layer 10 </ b> L and the semiconductor device 14.

(Semiconductor module mounted on lead frame type MCP)
A schematic cross-sectional structure of a semiconductor module 6M including an adhesive structure according to an embodiment to which the present technology is applied is expressed as shown in FIG. FIG. 25 shows an example of a semiconductor module mounted on a lead frame type multi-chip package (MCP). Further, the schematic cross-sectional structure in the vicinity of the region A in FIG. 25 is represented in the same manner as FIG. 24A, and the schematic cross-sectional structure in the vicinity of the region B in FIG.

  As shown in FIG. 25, the semiconductor module 6M mounted on the lead frame type MCP includes a lead frame 64L, a noble metal layer 10D formed on the lead frame 64L, and a conductive resin bonded by interaction with the noble metal layer 10D. A semiconductor device 14B disposed on the conductive resin layer 12D; a conductive resin layer 12U disposed on the semiconductor device 14B; and a semiconductor device 14A disposed on the conductive resin layer 12U. . Similarly to FIG. 24 (b), the noble metal layer 10D and the conductive resin layer 12D have electrons from a part of the functional group of the first adhesive resin constituting the conductive resin layer 12D toward the noble metal of the noble metal layer 10D. Bonding is performed by σ donation and π reverse donation in which electrons are donated from the noble metal of the noble metal layer 10D toward the functional group of the first adhesive resin.

  Furthermore, as shown in FIG. 25, the semiconductor module 6M mounted on the lead frame type MCP includes a mold resin layer 20 that is bonded to the noble metal layer 10D by interaction. The noble metal layer 10D and the mold resin layer 20 include a σ donation in which electrons are donated from a part of the functional groups of the second adhesive resin constituting the mold resin layer 20 toward the noble metal of the noble metal layer 10D, and the noble metal layer 10D. Bonding is performed by π reverse donation in which electrons are donated from the noble metal toward the functional group of the second adhesive resin.

  Furthermore, as shown in FIG. 25, the semiconductor module 6M mounted on the lead frame type MCP includes a lead frame 64 and a noble metal layer 10L formed on the lead frame 64 by a plating technique. As shown in FIG. 24 (a), the noble metal layer 10L and the mold resin layer 20 donate electrons from a part of the functional groups of the second adhesive resin constituting the mold resin layer 20 toward the noble metal of the noble metal layer 10L. Σ donation and π reverse donation in which electrons are donated from the noble metal of the noble metal layer 10L toward the functional group of the second adhesive resin.

  The entire semiconductor module 6M mounted on the lead frame type MCP is resin-sealed with a mold resin layer 20, as shown in FIG. A bonding wire 62 is connected between the noble metal layer 10L and the semiconductor devices 14A and 14B.

  The bonding structure according to the present embodiment and the semiconductor device that can be mounted on the semiconductor module including the bonding structure include, for example, an LED, a semiconductor laser, a power semiconductor, an integrated circuit, or a combination thereof. May be.

  As an integrated circuit, for example, for vehicle-mounted electronics, a body control module (BCM: Body Control Module), an advanced driver assistance system (ADAS), a main inverter (Main inverter), an LED lamp module (LED Lamp Module) ), Integrated circuits for in-vehicle electronics such as an engine control unit (ECU) and a car audio can be applied.

  In addition, the bonding structure according to the present embodiment and the semiconductor device that can be mounted on the semiconductor module including the bonding structure include any of Si-based or SiC-based IGBTs, diodes, MOSFETs, and GaN-based FETs. May be.

  Further, the bonding structure according to the present embodiment and the semiconductor device that can be mounted on the semiconductor module including the bonding structure are one-in-one module, two-in-one module, four-in-one module, six-in-one module, seven-in-one module, eight-in-one Any one of a module, a twelve in one module, or a fourteen in one module may be provided.

  According to the present embodiment, it is possible to provide an adhesive structure having an interface structure that is stable even at high temperatures, and a semiconductor module including the adhesive structure. In an adhesive structure in which σ donation and π reverse donation occur at the same time, more electrons are shared, so that adhesion at high temperatures can be improved.

[Other embodiments]
Although several embodiments have been described as described above, it should be understood that the discussion and drawings that form part of the disclosure are illustrative and not limiting. From this disclosure, various alternative embodiments, examples and operational techniques will be apparent to those skilled in the art.

  As described above, the present embodiment includes various embodiments that are not described herein.

  The bonding structure and the semiconductor module of the present embodiment include various semiconductor modules such as LED modules, optical modules, IGBT modules, diode modules, MOS modules (Si, SiC, GaN), integrated circuit technologies, various package technologies, etc. It can be used for a wide range of application fields.

2D, 2S: Adhesive structure, 4D, 4S, 6, 6M ... Semiconductor module, 10, 10D, 10L ... Noble metal layer, 10A ... Gold (Au) plating, 12, 12D, 12U ... Conductive resin layer, 14, 14A , 14B ... Semiconductor device, 16 ... Metal filler, 18, 19 ... Adhesive resin, 20 ... Mold resin layer, 22 ... Filler, 24 ... Molecular skeleton, 26, 34 ... CN functional group, 28 ... OH group, 30 ... Au plating layer, 32 ... CO functional group, 40 ... Cyan noble metal plating layer, 50, 70 ... Noble metal atom, 60 ... Dinitrodiammine noble metal plating layer, 62 ... Bonding wire, 64, 64L, 66 ... Lead frame

Claims (20)

With precious metals,
A resin bonded by interaction with the noble metal,
The noble metal and the resin include a σ donation in which electrons are donated from a part of the functional groups constituting the resin toward the noble metal, and a π reverse donation in which electrons are donated from the noble metal to the functional group. Bonded structure bonded by The adhesion according to claim 1, wherein the functional group has both a lone electron pair and an empty antibonding π orbit (π ^* orbital), and can form a bond by the σ donation and the π reverse donation. Structure.   The bonded structure according to claim 1, wherein the noble metal and the resin further include a hydrogen bond in a partial bond between the noble metal and the resin.   The adhesion structure according to any one of claims 1 to 3, wherein the noble metal includes at least one kind or plural kinds selected from the group consisting of Au, Ag, Pt, Pd, Rh, Ru, Ir, and Os. .   The adhesive structure according to any one of claims 1 to 4, wherein the resin includes at least one kind or a plurality of kinds selected from the group of an epoxy resin, an acrylic resin, a phenol resin, and a silicone resin.   The functional group includes at least one kind or plural kinds selected from the group consisting of a cyano group, a thiocyano group, a carbonyl group, an ester group, an amide group, an azide group, an isocyano group, a sulfo group, and a nitro group. 6. The bonded structure according to any one of 5 above.   The adhesive structure according to claim 1, wherein the resin comprises an adhesive resin and a filler contained in the adhesive resin.   The adhesive structure according to claim 7, wherein the filler includes a metal filler, and the resin includes a conductive resin containing the metal filler.   The adhesive structure according to claim 7, wherein the filler includes a ceramic filler, and the resin includes a nonconductive resin containing the ceramic filler.   A semiconductor module comprising the adhesive structure according to claim 1. A precious metal layer,
A conductive resin layer adhered by interaction with the noble metal layer;
A semiconductor device disposed on the conductive resin layer,
The noble metal layer and the conductive resin layer include a σ donation in which electrons are donated from a part of the functional group of the first adhesive resin constituting the conductive resin layer toward the noble metal of the noble metal layer, and the noble metal A semiconductor module which is bonded by π reverse donation in which electrons are donated toward the functional group. Further comprising a mold resin layer bonded by interaction with the noble metal layer,
The noble metal layer and the mold resin layer are σ donation in which electrons are donated from a part of the functional group of the second adhesive resin constituting the mold resin layer toward the noble metal of the noble metal layer, and the noble metal from the noble metal The semiconductor module according to claim 11, which is adhered by π reverse donation in which electrons are donated toward the functional group.   The semiconductor module according to claim 11 or 12, wherein the noble metal includes at least one kind or a plurality of kinds selected from the group consisting of Au, Ag, Pt, Pd, Rh, Ru, Ir, and Os.   The first adhesive resin and the second adhesive resin include at least one type or a plurality of types selected from the group of epoxy resins, acrylic resins, phenolic resins, and silicone resins. Semiconductor module. A semiconductor device;
A noble metal layer electrically connected to the semiconductor device;
A mold resin layer adhered by interaction with the noble metal layer,
The noble metal layer and the mold resin layer are σ donation in which electrons are donated from a part of the functional group of the second adhesive resin constituting the mold resin layer toward the noble metal of the noble metal layer, and the noble metal from the noble metal A semiconductor module bonded by π reverse donation, in which electrons are donated towards a functional group.   The semiconductor module according to claim 15, wherein the noble metal includes at least one kind or plural kinds selected from the group of Au, Ag, Pt, Pd, Rh, Ru, Ir, and Os.   17. The semiconductor module according to claim 15, wherein the second adhesive resin includes at least one type or a plurality of types selected from the group of epoxy resins, acrylic resins, phenol resins, and silicone resins.   The functional group includes both a lone electron pair and an empty antibonding π orbit (π * orbital), and is capable of forming a bond by the σ donation and the π reverse donation. 2. The semiconductor module according to claim 1.   The functional group includes at least one kind or plural kinds selected from the group consisting of a cyano group, a thiocyano group, a carbonyl group, an ester group, an amide group, an azide group, an isocyano group, a sulfo group, and a nitro group. The semiconductor module according to any one of 18. 20. The semiconductor module according to claim 11, wherein the semiconductor device includes any one of an LED, a semiconductor laser, a power semiconductor, an integrated circuit, or a combination thereof.

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