Encapsulating material composition, semiconductor encapsulating material and semiconductor

Abstract

A sealant composition according to the present invention contains an organometallic complex, wherein the organometallic complex has a structure represented by general formula (1) or general formula (2), the decomposition temperature of the organometallic complex is 150°C or higher, the sealant composition further contains a silicone gel, and the viscosity of the sealant composition at 23°C is no higher than 2000 mPa·s.

Description

[Technical Field]

[0001] The present invention relates to a encapsulating material composition, a semiconductor encapsulating material, and a semiconductor, and more particularly to a encapsulating material composition that prevents sulfidation associated with high temperatures of semiconductor elements and components constituting a semiconductor device, and exhibits a stable encapsulation effect even under high temperatures, and to a semiconductor encapsulating material and a semiconductor using the same. [Background technology]

[0002] Traditionally, in the field of element encapsulation for electronic components such as transistors, ICs (integrated circuits), and LSIs (large-scale integrated circuits), the dominant method has been to use encapsulation materials, such as resins, from the standpoint of productivity and cost.

[0003] Conventionally, electronic components and devices such as diodes, transistors, and integrated circuits have been encapsulated primarily by cured epoxy semiconductor encapsulation compositions. In particular, for integrated circuits, epoxy semiconductor encapsulation compositions containing epoxy resins with reduced chlorine content, phenolic curing agents, and inorganic fillers such as fused silica and crystalline silica have been used to prevent corrosion. Epoxy semiconductor encapsulation compositions are considered to have an excellent balance of various properties, including workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts.

[0004] On the other hand, in the market trends toward miniaturization, weight reduction, and performance improvement of electronic devices, the integration of semiconductor elements is progressing year by year, and surface mounting of semiconductor devices is being promoted. For example, in recent years, power semiconductors, which possess both the properties of an electrical conductor and an electrical insulator, and can handle high voltages and large currents, have attracted attention. In order to provide resistance to high voltages and large currents, it is considered important to reduce the power loss of the semiconductor itself and to efficiently dissipate the heat generated to the outside.

[0005] In recent years, power semiconductors, primarily IGBTs (Insulated Gate Bipolar Transistors), have become widely used in power conversion devices as power modules. The power module casing is filled with a low-modulus silicone gel to insulate and protect the ceramic insulating substrate and the power semiconductor elements on it. Furthermore, SiC (silicon carbide) power semiconductors are being actively studied because, compared to conventional silicon power semiconductors, they exhibit lower energy loss and heat generation during current flow, as well as higher heat resistance, enabling them to handle greater power.

[0006] As described above, in power semiconductors, the amount of heat generated increases with higher integration and higher power output, which accelerates the sulfidation of metals such as electrodes, posing a problem.

[0007] To address the above problem, Patent Document 1 discloses a silicone gel composition and its cured product (silicone gel) that provides excellent heat resistance upon curing by containing a low-viscosity potting-type liquid silicone rubber with high coverage of semiconductor details and high fluidity. However, it has been found that the method disclosed in Patent Document 1 has insufficient gas barrier properties after sealing and curing of electronic devices including power semiconductors, posing a problem for preventing sulfidation.

[0008] Furthermore, Patent Document 2 describes a coating-type translucent gas barrier composition containing inorganic particles, a curable transparent resin, and an organic solvent, wherein the curable transparent resin is a silicone resin or fluororesin soluble in the organic solvent, or an epoxy resin or acrylic resin obtained by modifying silicone or fluorine. A method for applying an anti-sulfidation layer formed from a composition such as urethane resin to an optoelectronic device has been disclosed. The method disclosed in Patent Document 2 is said to provide a high-power optoelectronic device and a method for manufacturing the same that can suppress brightness reduction caused by sulfidation. However, when the silicone resin disclosed in Patent Document 2 was applied to the anti-sulfidation layer of a high-power semiconductor with high heat generation, the fluidity of the silicone resin deteriorated due to the dispersion of high-aspect-ratio inorganic particles, resulting in problems with the coverage of the complex detailed structure of the power semiconductor.

[0009] Furthermore, Patent Document 3 discloses a silver tarnish-preventing resin composition comprising a zinc salt or zinc complex and an addition-reaction type silicone resin as a sealing member, which prevents discoloration of silver or silver-plated components constituting a light-emitting diode. However, while the silver tarnish-preventing resin composition disclosed in Patent Document 3 does not pose a major problem for ultra-small electronic devices such as LED chips, when applied to power semiconductor devices with large package volumes, the volume of the resin composition used also increases, leading to a greater impact from the difference in linear thermal expansion coefficients. As a result, it has been found that there is a problem with the deterioration of sulfidation prevention due to the occurrence of resin cracks caused by heat.

[0010] Therefore, in semiconductors, particularly power semiconductor devices (also called "power semiconductor devices") that generate high power and heat, there is a need for the development of sealing material compositions that suppress sulfidation associated with high temperatures and exhibit a stable sealing effect even under high temperatures. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] Patent No. 6658428 [Patent Document 2] Japanese Patent Publication No. 2017-57339 [Patent Document 3] Patent No. 5948240 [Overview of the project]

Problems to be Solved by the Invention

[0012] The present invention has been made in view of the above problems and situations, and the problem to be solved is to prevent the acceleration of vulcanization accompanying the heat generation of semiconductor elements and components constituting a semiconductor device, and to exhibit a stable sealing effect even under high heat. The present invention provides a sealing material composition, a semiconductor sealing material, and a semiconductor using the same.

Means for Solving the Problems

[0013] In the process of examining the causes of the above problems in order to solve the above problems, the present inventor found that by applying a sealing material composition comprising at least an organometallic complex having a specific structure and decomposition temperature as a vulcanization inhibitor and a silicone gel and having a specific viscosity as a semiconductor sealing material, a vulcanization prevention function accompanying heat generation and stable heat resistance performance can be exhibited, and a semiconductor can be realized, and thus the present invention has been achieved.

[0014] That is, the above problems according to the present invention are solved by the following means.

[0015] 1. A sealing material composition containing an organometallic complex, wherein the organometallic complex is the following Compound 1-4 or Compound 2- 1 exists, the decomposition temperature of the organometallic complex is 150 ° C or higher, furthermore, it contains a silicone gel, and a sealing material composition having a viscosity at 23 ° C of the sealing material composition of 2000 mPa·s or less.

[0016]

Chemical formula

[0017] 2. In the electronic state calculation method based on the density functional theory, the organometallic complex gold the charge of the metal atom is 、1 .4 or less, and before record Molecular bodies of metallochemical complexes The product is 2 00Å 3 The sealing material composition described in paragraph 1 above.

[0020] 3 . A semiconductor encapsulation material using the encapsulation composition described in paragraph 1 or 2, By curing the aforementioned sealing material composition, a material is used to seal a semiconductor including a circuit pattern, elements, and metal wiring provided on an insulating member. ru han Conductor sealing material.

[0021] 4 The material that forms a sulfidation-preventive layer to prevent the sulfidation of copper and silver, which constitute semiconductors. In item 3 The semiconductor encapsulation material described.

[0022] 5 Item 3: The penetration of a 1 / 4 cone, measured in accordance with the consistency test method specified in JIS K2220, is 10 or greater. Or in paragraph 4 The semiconductor encapsulation material described.

[0023] 6 Articles 3 through 3 Section 5 A semiconductor comprising a semiconductor encapsulating material as described in any one of the items up to the above. [Effects of the Invention]

[0024] The above-described means of the present invention make it possible to provide a sealing material composition, a semiconductor sealing material, and a semiconductor using the same that prevent accelerated sulfidation associated with high temperatures of semiconductor elements and components constituting a semiconductor device, and exhibit a stable sealing effect even under high temperatures.

[0025] Although the mechanism of action or mechanism of the present invention is not yet clear, it is speculated as follows.

[0026] In the course of studying the durability of semiconductor devices (hereinafter also referred to as "semiconductor devices"), which have a structure in which semiconductor elements or semiconductor integrated circuits are encapsulated, under various environmental conditions, it has become clear that in semiconductors, especially power semiconductors, the amount of heat generated increases with higher integration and higher output, which accelerates the sulfidation of circuit patterns, elements, metal wiring, etc., and is becoming a problem.

[0027] In conventionally disclosed sulfidation prevention technologies, for example, when using organometallic complex sulfidation inhibitors, it has been found that while a more easily detachable ligand enhances the sulfidation prevention effect when attempting to increase the sulfide adsorption reaction, it is also more susceptible to thermal decomposition in high-temperature environments. Furthermore, in power semiconductors with high volumetric capacity and complex detailed structures, encapsulating material compositions with high viscosity characteristics may not stably fill even the fine details of the structure, potentially resulting in unfilled areas.

[0028] In this invention, we have diligently investigated a sulfidation inhibitor that has excellent sulfidation inhibitory effects, can reliably fill and encapsulate even the detailed structures of power semiconductors, and can obtain high sulfidation inhibitory and heat resistance. As a result, we have found that the above problems can be solved by applying a encapsulating material composition having a specific viscosity, which is composed of an organometallic complex having at least a specific structure and decomposition temperature and a relatively low viscosity silicone gel, as a encapsulating material for semiconductors.

[0029] The inventors conducted further detailed studies on the structure of the compound and concluded that, as an organometallic complex serving as a sulfidation inhibitor, the charge of the metal atoms calculated by an electronic state calculation method based on density functional theory should be 1.4 or less, and the molecular volume constituting the organometallic complex should be 200 Å. 3 By doing so, we found that the above effects were significantly manifested.

[0030] More specifically, for organometallic complexes used as sulfidation inhibitors, the most stable molecular structure was determined using an electronic state calculation method based on density functional theory, and the parameters calculated from this were utilized.

[0031] The inventors diligently investigated the correlation between the above parameters and the sulfidation prevention function and heat resistance, and found that there is a correlation between the charge of the metal atoms constituting the organometallic complex and its molecular volume. The charge of the metal atoms is preferably 1.4 or less, and more preferably 1.35 or less. The molecular volume is preferably 200 Å. 3 The above applies, and more preferably 300 Å. 3 This concludes the explanation. While a lower metal charge and molecular volume makes a ligand more easily detachable and improves molecular adsorption, it has the problem of poor heat resistance. To address this problem, by satisfying the above relationship between the charge and molecular volume of the metal atoms, it is possible to provide a encapsulating material composition, a semiconductor encapsulating material, and a semiconductor using the same that can achieve both sulfidation prevention and heat resistance. [Brief explanation of the drawing]

[0032] [Figure 1] A schematic cross-sectional view showing an example of the configuration of a power semiconductor module to which the encapsulating material composition of the present invention is applied. [Figure 2] A schematic cross-sectional view showing another example of the configuration of a power semiconductor module to which the encapsulating material composition of the present invention is applied. [Figure 3] A schematic cross-sectional view showing the configuration of the evaluation chip used to evaluate the sulfurization resistance of the encapsulating material composition to the Ag substrate in the example. [Figure 4] A schematic diagram showing the configuration of a test patterning substrate having a comb-shaped electrode for evaluating the sulfurization resistance of a sealing material composition to a Cu electrode in the example. [Figure 5] Schematic diagram showing the configuration of an evaluation chip in which the test patterning substrate shown in Figure 4 is sealed with a sealing material composition. [Modes for carrying out the invention]

[0033] The sealing material composition of the present invention is a sealing material composition containing an organometallic complex, wherein the organometallic complex has a structure represented by general formula (1) or general formula (2), the decomposition temperature of the organometallic complex is 150°C or higher, the composition further contains a silicone gel, and the viscosity of the sealing material composition at 23°C is 2000 mPa·s or less. This feature is a technical feature common to or corresponding to each of the embodiments described below.

[0034] In embodiments of the present invention, the organometallic complex is such that, in an electronic state calculation method based on density functional theory, the charge of the metal atom represented by M1 in general formula (1) and the charge of the metal atom represented by M2 in general formula (2) are independently 1.4 or less, and the molecular volume of the organometallic complex having the structure represented by general formula (1) and the molecular volume of the organometallic complex having the structure represented by general formula (2) are independently 200 Å. 3 The above is preferable because it provides a superior sulfidation prevention effect, ensures reliable filling and sealing of the detailed structure of power semiconductors, and provides high sulfidation prevention and heat resistance.

[0035] Furthermore, in the semiconductor encapsulating material of the present invention, it is preferable that M1 in general formula (1) and M2 in general formula (2) are each independently selected metal atoms from Ti, Zr, Sn, Ta, Fe, Zn, Bi, Cu, Mg, Mn, Co, Ni, Ag, and Al, in order to obtain better sulfidation resistance.

[0036] Furthermore, in the semiconductor encapsulation material of the present invention, it is preferable that the organometallic complex contained in the encapsulation material composition is an organometallic complex having the structure represented by the general formula (2), in that this can better express the desired effects of the present invention.

[0037] The semiconductor encapsulating material of the present invention is preferable in that it is a material that encapsulates a semiconductor including a circuit pattern, elements, and metal wiring provided on an insulating member by curing the encapsulating material composition, and furthermore, is a material that forms a sulfidation-preventive layer that prevents the sulfidation of copper and silver constituting the semiconductor, in order to exhibit an excellent sulfidation-preventive effect on the semiconductor.

[0038] Furthermore, it is preferable that the semiconductor encapsulating material of the present invention has a 1 / 4 cone penetration depth of 10 or more, as measured in accordance with the consistency test method specified in JIS K2220, in order to stably fill the fine structure of the power semiconductor and exhibit an excellent sulfidation prevention effect.

[0039] The semiconductor encapsulating material of the present invention, when applied to the encapsulation of a semiconductor, can provide high resistance to sulfidation and heat. In addition, the semiconductor of the present invention, when equipped with the semiconductor encapsulating material of the present invention, can also achieve high resistance to sulfidation and heat.

[0040] The present invention, its components, and embodiments and models for carrying out the present invention will be described in detail below. In this application, "~" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0041] 《Encapsulant composition》 The sealing composition of the present invention is 1) A encapsulating material composition containing an organometallic complex, 2) The organometallic complex has a structure represented by the general formula (1) or general formula (2), 3) The decomposition temperature of the organometallic complex is 150°C or higher. 4) Furthermore, it contains silicone gel, and 5) The viscosity of the sealing material composition at 23°C is 2000 mPa·s or less.

[0042] The following describes in detail each component of the sealing composition of the present invention and its characteristics.

[0043] [Sulfidation inhibitors: Organometallic complexes having a structure represented by general formula (1) or general formula (2)] In the present invention, an organometallic complex having a structure represented by the following general formula (1) or general formula (2) is used as the sulfidation inhibitor.

[0044] [ka] [ka] The following describes the details of organometallic complexes having a structure represented by general formula (1) or general formula (2).

[0045] In general formulas (1) and (2), M1 and M2 each independently represent a metal atom. n and m each independently represent a non-negative integer. p1 to p5 each independently represent a non-negative integer. R1 and R2 each independently represent an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group, or heterocyclic group having 1 or more carbon atoms. Furthermore, R1 and R2 may also contain a fluorine atom. X1 to X5 each independently represent N, O, or S. L1 and L2 each independently represent a monovalent substituent that forms a substructure of the ligand of the metal complex.

[0046] (Organometallic complexes having a structure represented by general formula (1)) In the general formula (1) above, M1 represents a metal atom. p1 and p2 each independently represent an integer of 0 or more. R1 and R2 each independently represent an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group, or heterocyclic group having 1 or more carbon atoms. Furthermore, R1 and R2 may also contain a fluorine atom. X1 and X2 each independently represent N, O, or S.

[0047] In the above general formula (1), the alkyl groups in R1 and R2 may be substituted or unsubstituted. Specific examples include methyl group, ethyl group, propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, These include pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, and docosyl groups. There are no particular restrictions on the number of carbon atoms, but it is generally preferable that it is in the range of 6 to 18.

[0048] The alkenyl group may be substituted or unsubstituted, and specific examples include vinyl, allyl, butenyl, pentenyl, and hexycenyl groups. There are no particular restrictions on the number of carbon atoms, but it is generally preferred to be in the range of 6 to 18.

[0049] The aryl group may be substituted or unsubstituted. Specific examples include phenyl, tolyl, 4-cyanophenyl, biphenyl, o,m,p-terphenyl, naphthyl, anthranyl, phenantrenyl, fluorenyl, 9-phenylanthranyl, 9,10-diphenylanthranyl, and pyrenyl groups. There are no particular restrictions on the number of carbon atoms, but it is generally preferable that it be within the range of 6 to 18.

[0050] Specific examples of substituted or unsubstituted alkoxy groups include methoxy, n-butoxy, tert-butoxy, trichloromethoxy, and trifluoromethoxy groups. There are no particular restrictions on the number of carbon atoms, but it is generally preferred to be in the range of 6 to 18.

[0051] Specific examples of substituted or unsubstituted cycloalkyl groups include cyclopentyl group, cyclohexyl group, norbonane group, adamantane group, 4-methylcyclohexyl group, 4-cyanocyclohexyl group, and preferably those having 8 or more carbon atoms.

[0052] Specific examples of substituted or unsubstituted heterocyclic groups include pyrrole group, pyrroline group, pyrazole group, pyrazoline group, imidazole group, triazole group, pyridine group, pyridazine group, pyrimidine group, pyrazine group, triazine group, indole group, benzimidazole group, purine group, quinoline group, isoquinoline group, cinolin group, quinoxaline group, benzoquinoline group, fluorenone group, dicyanofluorenone group, carbazole group, oxazole group, oxadiazole group, thiazole group, thiadiazole group, benzoxazole group, benzothiazole group, benzotriazole group, bisbenzoxazole group, bisbenzothiazole group, and bisbenzimidazole group.

[0053] Specific examples of substituted or unsubstituted acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, lauroyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, succinyl, glutaryl, adipoyl, pimeloyl, suberoyl, azerayl, sebacoyl, acryloyl, propioloyl, methacryloyl, crotonoyl, isocrotonoyl, oleoyl, elidoyl, maleoyl, fumaroyl, citraconoyl, mesaconoyl, canholoyl, benzoyl, phthaloyl, isophthaloyl, terephthaloyl The acyl groups of the following groups may be substituted with fluorine, chlorine, bromine, or iodine: yl group, naphthoyl group, toluyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, froyl group, tenoyl group, nicotinoyl group, isonicotinoyl group, glycoyl group, lactolyl group, glyceroyl group, tartronoyl group, maloyl group, tartaroyl group, tropoyl group, benzyloyl group, salicyloyl group, anisoyl group, vanilloyl group, veratroyl group, piperoniloyl group, protocatecoyl group, galloyl group, glyoxyloyl group, pyruvoyl group, acetoacetyl group, mesooxalyl group, mesooxalo group, oxalacetyl group, oxalaceto group, levulinoyl group.

[0054] Examples of metal atoms represented by M1 in general formula (1) include Ti, Zr, Sn, Si, Ta, Yb, Y, Al, Zn, Co, In, Fe, Mo, Ni, Pd, Ag, Sr, Bi, Cu, Mg, Mn, etc., and at least one or two of these are selected. It may consist of more than one species. Among them, it is preferable that it be at least one selected from Ti, Zr, Sn, Ta, Fe, Zn, Bi, Cu, Mg, Mn, Co, Ni, Ag, and Al.

[0055] (Organometallic complexes having a structure represented by general formula (2)) In general formula (2), M2 represents a metal atom. n and m each represent an independent integer of 0 or more. p3 to p5 each represent an independent integer of 0 or more. X3 to X5 each represent an independent N, O, or S.

[0056] In general formula (2), L1 and L2 each independently represent a monovalent substituent that forms a substructure of the ligand of the metal complex. Examples of monovalent substituents include aromatic hydrocarbon ring groups, heterocyclic groups (such as piperidine rings), and aromatic heterocyclic groups. Preferably, these include aromatic hydrocarbon ring groups (such as benzene rings and naphthalene rings) and aromatic heterocyclic groups (such as pyridine rings, quinoline rings, and benzothiazole rings).

[0057] Examples of metal atoms represented by M2 in general formula (2) include Ti, Zr, Sn, Si, Ta, Yb, Y, Al, Zn, Co, In, Fe, Mo, Ni, Pd, Ag, Sr, Bi, Cu, Mg, Mn, etc., and may consist of at least one or two or more selected from these. Among these, it is preferable that it be at least one selected from Ti, Zr, Sn, Ta, Fe, Zn, Bi, Cu, Mg, Mn, Co, Ni, Ag, and Al.

[0058] Next, examples of organometallic complexes having the structure represented by general formula (1) and organometallic complexes having the structure represented by general formula (2) are shown below, but the present invention is not limited to these exemplary compounds.

[0059] Examples of organometallic complexes having the structure represented by general formula (1) are shown below. [ka] Next, the following are examples of organometallic complex compounds having the structure represented by general formula (2). [ka] Of the organometallic complexes having the structure represented by general formula (1) and the organometallic complex having the structure represented by general formula (2) described above, the organometallic complex having the structure represented by general formula (2) is more preferable from the viewpoint of being able to better express the desired effects of the present invention.

[0060] [Characteristic values ​​of organometallic complexes according to the present invention] (decomposition temperature) In the organometallic complex according to the present invention, the decomposition temperature is 150°C or higher.

[0061] In this invention, the decomposition temperature is defined as the temperature at which the mass equivalent decreases by 10%, as measured by the following measurement method.

[0062] <Measurement of decomposition temperature> The decomposition temperature of organometallic complexes can be measured by thermogravimetric analysis (hereinafter abbreviated as TG).

[0063] TG (Thermal Grading) is a method of measuring the mass of a sample as a function of temperature or time while changing or maintaining the sample's temperature according to a set program, and is performed in accordance with the general principles of thermal analysis specified in JIS K 0129. More specifically, it is a method of measuring the physical changes of an object as a function of temperature while changing its temperature according to a controlled program.

[0064] Furthermore, the measurement conditions for TG are carried out in accordance with the thermogravimetric analysis method for plastics specified in JIS K 7120. The decomposition temperature in this invention is measured in accordance with JIS K 7120, and the mass change onset temperature (T1), i.e., the line representing the mass m0 before the start of measurement, and the maximum slope of the TG curve are used. It was determined by finding the intersection point of the tangent lines.

[0065] The following is an example of decomposition temperature measurement.

[0066] Measurement device: Hitachi High-Tech Science Corporation Differential Thermogravimetric Simultaneous Thermomeasuring Device TG / DTA6200 Sample quantity: 10 mg, using Alpane Atmosphere gas: Nitrogen 200 mL / min Heating rate: Heats up to 500°C at a rate of 10°C / min. The decomposition temperature of the organometallic complex according to the present invention is 150°C or higher, but considering the balance between ease of handling, heat resistance, and sulfurization resistance in the semiconductor device to which it is applied, it is preferably in the range of 150 to 500°C, and more preferably in the range of 250 to 400°C.

[0067] (Measurement of the charge and molecular volume of metal atoms) In the organometallic complex according to the present invention, in an electronic state calculation method based on density functional theory, the charge of the metal atom represented by M1 in general formula (1) and the charge of the metal atom represented by M2 in general formula (2) are independently 1.4 or less, and the molecular volume of the organometallic complex having the structure represented by general formula (1) and the molecular volume of the organometallic complex having the structure represented by general formula (2) are independently 200 Å. 3 The above is a preferred embodiment.

[0068] In this invention, the charge and molecular volume of the metal atoms in the organometallic complex were calculated based on density functional theory (DFT: Discrete Fourier Transform). The calculation was performed using Gaussian16 software from Gaussian, Inc., and the density functional method could be used as the calculation technique.

[0069] Density functional theory (DFT) is a theory that posits that it is possible to calculate physical properties such as energy of an electron system from its electron density. Furthermore, density functional theory is a method for calculating electronic states based on density functional theory.

[0070] In the process of designing molecules that achieve both heat resistance and sulfurization prevention for the encapsulating material composition or semiconductor encapsulating material of the present invention, parameters derived from computational chemistry were also considered. For calculations, Gaussian16 (Revision B.01,MJFrisch,GWTrucks,HBSchlegel,GEScuseria,MARobb,JRCeeseman,G.Scalmani,V.Barone,GAPetersson,H.Nakatsuji,X.Li,M.Caricato,AVMarenich,J.Bloino,BGJanesko,R.Gomperts,B.Mennucci,HPHratchi an,JVOrtiz,AFIzmaylov,JLSonnenberg,D.Williams-Young,F.Ding,F.Lipparini,F.Egidi,J.Goings,B.Peng,A.Petrone,T.Henderson,D.Ranasinghe,VGZakrzewski,J.Gao,N.Rega,G.Toyota,R.Fukuda,J.Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. hrossell, JAMontgomery, Jr., JEPeralta, F. Ogliaro, MJBear park,JJHeyd,ENBrothers,KNKudin,VNStaroverov,TAKeith,R.Kobayashi,J.Normand,K.Raghavachari,APRendell,JCBurant, The software can be used, and density functional theory can be used as the computational method. (SSIyengar, J. Tomasi, M. Cossi, J. Millam, M. Klene, C. Adamo, R. Cammi, JW Ochterski, R. Martin, K. Morokuma, O. Farkas, J. Foresman, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2016.)

[0071] In this invention, the most stable molecular structure of the organometallic complex acting as a sulfidation inhibitor was determined by the above calculation, and the parameters derived therefrom were utilized. In this case, for example, M06 was used as the functional, LanL2DZ was used for metal atoms (zinc, copper, silver, nickel, etc.), and 6-31G was used for other elements (carbon, nitrogen, oxygen, hydrogen, sulfur, halogen, etc.) as the basis functions. ** It can be used. There are no particular restrictions on the software or calculation method; the same value can be obtained using any of them. Charge is defined as Natural Population. It is calculated using a method based on Analyze (NPA).

[0072] Parameters derived from the structure (such as molecular volume) are calculated using the functions of Winmostar (Version 10.2.4) based on the stable structure obtained by the above calculation.

[0073] (Charge, molecular volume, and decomposition temperature of the metal atoms in the example compounds) Table I shows an example of the measured values ​​of the metal atom charge, molecular volume, and decomposition temperature for the aforementioned representative example compounds of organometallic complexes, as measured by the method described above.

[0074] [Table 1]

[0075] [Silicone gel] In the sealing material composition of the present invention, a silicone gel is used together with an organometallic complex having a structure represented by general formula (1) or general formula (2) as described above.

[0076] Silicone is a hybrid polymer material that combines inorganic and organic components, with an inorganic siloxane bond (Si-O-Si) in its main chain and organic groups in its side chains.

[0077] The main chain forming silicone consists of siloxane bonds with high and stable bond energy. Compared to organic polymer materials whose main chain consists of a carbon skeleton (CC: bond energy 85 kcal / mol), silicone bonds have a much higher and more stable bond energy of 106 kcal / mol, resulting in superior properties such as heat resistance.

[0078] Furthermore, a characteristic of siloxane bonds is that, compared to carbon bonds (bond distance 1.54 Å, bond angle 110°), the bond distance is longer and larger, and the rotational energy is smaller. As a result, siloxane bonds are more mobile, have weaker intermolecular forces, and exhibit less change in hardness (elastic modulus) and viscosity with respect to temperature.

[0079] In silicones, hardness can be controlled to desired conditions, for example, by designing the three-dimensional structure using siloxane bonds or molecular structures as described above.

[0080] Generally, examples of silicone gels include polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, and silicone compounds in which at least one of the terminal or side chains is modified with an organic functional group, such as alkyl-modified silicone, halogenated alkyl-modified silicone, vinyl-modified silicone, polyether-modified silicone, alcohol-modified silicone, amino-modified silicone, epoxy-modified silicone, epoxy-polyether-modified silicone, phenol-modified silicone, carboxyl-group-modified silicone, and mercapto-modified silicone. These are used individually or in combination of two or more. For the above-mentioned silicone oils and silicone gels, a higher molecular weight is preferable to suppress seepage during molding. Furthermore, polymethylhydrogensiloxane, vinyl-modified silicone, amino-modified silicone, epoxy-modified silicone, epoxy-polyether-modified silicone, and phenol-modified silicone react with epoxy resins and silicones, respectively, so even with a low molecular weight, seepage during molding can be suppressed, making them preferable.

[0081] Typical silicone gels include: (A) Organopolysiloxanes having at least one alkenyl group bonded to a silicon atom in one molecule, (B) Organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule, (C) platinum-based curing catalyst, (D) Isocyanuric acid derivatives The materials that make up this can be listed.

[0082] Furthermore, as silicone gels, for example, compounds described in Japanese Patent Publication No. 2014-216558, Japanese Patent Publication No. 2015-115442, Japanese Patent Publication No. 2016-169331, Japanese Patent Publication No. 2018-053015, Japanese Patent Publication No. 2019-14779, Japanese Patent Publication No. 2019-130960, Japanese Patent Publication No. 2021-011510, etc., can be appropriately selected and used as silicone gels that satisfy the conditions specified in the present invention.

[0083] In particular, the silicone gel according to the present invention is preferably used as a potting material when manufacturing power semiconductors (IGBTs).

[0084] The silicone gels applicable to this invention can be obtained as commercially available products, and while representative silicone gels are shown below, the invention is not limited to those listed below.

[0085] The commercially available products listed below are silicone gels for potting applications and are all manufactured by Shin-Etsu Chemical Co., Ltd. The viscosity values ​​shown below were all measured at 23°C. Penetration values ​​were measured using a 1 / 4 cone.

[0086] (One-component addition-type silicone gel) 1) Product name: KE-1056 (Viscosity before curing: 800mPa·s, Penetration after curing: 90, Curing conditions: 130℃, 30 minutes) 2) Product name: KE-1057 (Viscosity before curing: 800mPa·s, Penetration after curing: 65, Curing conditions: 150℃, 30 minutes) 3) Product name: KE-1061 (Viscosity before curing: 600mPa·s, Penetration after curing: 90, Curing conditions: 120℃, 30 minutes) 4) Product name: KE-1062 (Viscosity before curing: 700mPa·s, Penetration after curing: 40, Curing conditions: 130℃, 30 minutes) <Viscosity measurement> In the present invention, viscosity can be measured using a rotational viscometer (e.g., BL type, BH type, BS type, E type, cone plate type, rheometer, etc.). In particular, the viscosity (23°C) of the silicone gel and encapsulant composition can be measured and determined using an E-type rotational viscometer (cone plate type) according to the viscosity measurement method specified in JIS K7117-1.

[0087] In the present invention, the viscosity of the sealing material composition at 23°C is 2000 mPa·s or less, preferably in the range of 500 to 2000 mPa·s, and more preferably in the range of 750 to 1800 mPa·s.

[0088] Furthermore, the viscosity of the silicone gel to be applied at 23°C is not particularly limited as long as it satisfies the conditions specified above as a sealing material composition, but it is preferably in the range of 500 to 1000 mPa·s, and more preferably in the range of 600 to 1000 mPa·s.

[0089] In the case of silicone gels, high-viscosity silicone gels with a viscosity of 1000 mPa·s or higher are used in potting-type viscosity classifications. Furthermore, in LED semiconductor applications, except for special applications, high-viscosity silicone gels with a viscosity of approximately 3000 mPa·s or higher are generally applied. When such high-viscosity silicone gels are applied, it becomes impossible to impart the ductility necessary to adequately fill the fine structural parts that constitute the semiconductor with encapsulant.

[0090] In silicone gels with such viscosity characteristics, it is preferable to avoid excessively high viscosity silicone gels in power semiconductors (IGBT modules) having a structure as shown in Figure 1, and it is preferable that the viscosity be 1000 mPa·s or less. In the present invention, by setting the viscosity of the encapsulating material composition to 2000 mPa·s or less, it is possible to prevent accelerated sulfidation associated with the high temperature of the power semiconductor and to obtain an encapsulating material composition that exhibits a stable encapsulating effect even under high temperatures.

[0091] <Measurement of Penetration> In the semiconductor encapsulating material using the silicone gel of the present invention, the penetration of a 1 / 4 cone measured in accordance with the consistency test method specified in JIS K2220 is preferably 10 or more, more preferably in the range of 10 to 150, and even more preferably in the range of 30 to 100.

[0092] Generally, since the elastic modulus of silicone gel is 10 5 N / m 2 or less, the commonly used rubber hardness tester cannot be applied. Therefore, in the present invention, in accordance with the consistency test method defined in JIS K2220, it was measured as the penetration of a 1 / 4 cone.

[0093] 〔Other Additives for the Sealing Material Composition〕 In the sealing material composition of the present invention, in addition to the above-described organometallic complex and silicone gel, optional components can be blended as long as the object and effect of the present invention are not impaired. Examples of such optional components include reaction inhibitors, inorganic fillers, organopolysiloxanes that do not contain silicon atom-bonded hydrogen atoms and silicon atom-bonded alkenyl groups, adhesion-imparting agents such as alkoxyorganosilanes that contribute to the improvement of adhesiveness or tackiness, heat-resistant additives, flame retardant-imparting agents, thixotropic agents, pigments, dyes, and the like.

[0094] (Filler (Inorganic Filler)) Examples of the filler (hereinafter also referred to as inorganic filler) applicable to the sealing layer of the present invention include those used in general compositions for forming a sealing layer. For example, large-spherical silica, small-spherical silica, crystalline silica, talc, alumina, titanium white, silicon nitride, and the like can be mentioned. Among them, large-spherical silica and small-spherical silica are particularly preferable. However, it is not limited thereto.

[0095] As the filler, it is preferable to use large-spherical silica and small-spherical silica. Large-spherical silica can be used for the purpose of high filling, and small-spherical silica can be used for the purpose of narrow-gap injectability. Examples of large-spherical silica and small-spherical silica include fused silica manufactured by Denka Co., Ltd., spherical silica "HS series" manufactured by Nippon Steel Chemical & Material Co., Ltd., silica fine particles manufactured by Tosoh Corporation, crystalline silica manufactured by Hosokawa Micron Corporation, and the like.

[0096] These fillers may be used individually or in combination of two or more. Furthermore, in order to suppress the increase in the melt viscosity of the sealing material composition and to further increase the filler content, the fillers are preferably as spherical as possible and have a broad particle size distribution. The fillers may also be surface-treated with a coupling agent.

[0097] (Neutralizing agent) In the encapsulating material composition of the present invention, a neutralizing agent may be included to neutralize corrosive gases generated by heating the cured semiconductor encapsulating material, in order to suppress corrosion (oxidative degradation) at the joint between the copper wire (bonding wire) and the electrode pad (land) of the semiconductor element. Specifically, it is preferable to include at least one neutralizing agent selected from the group consisting of basic metal salts, particularly compounds containing calcium, compounds containing aluminum, and compounds containing magnesium.

[0098] (Other additives) In addition to the components described above, the sealing material composition of the present invention may optionally contain one or more additives selected from coupling agents, leveling agents, colorants, modifiers, release agents, stress reducers, photosensitive agents, defoamers, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, and ion scavengers. Examples of coupling agents include silane coupling agents such as epoxy silane coupling agents, cationic silane coupling agents, amino silane coupling agents, γ-glycidoxypropyltrimethoxysilane coupling agents, phenylaminopropyltrimethoxysilane coupling agents, mercaptosilane coupling agents, and 3-mercaptopropyltrimethoxysilane coupling agents, as well as titanate-based coupling agents and silicone oil-type coupling agents. Examples of leveling agents include acrylic copolymers. Examples of colorants include carbon black. Examples of release agents include natural waxes, synthetic waxes such as montanic acid esters, higher fatty acids or their metal salts, paraffin, and oxidized polyethylene. Examples of stress reducers include silicone oil and silicone rubber. Examples of ion scavenging agents include hydrotalcite. Examples of flame retardants include aluminum hydroxide.

[0099] "semiconductor" In this invention, "semiconductor" refers to a substance or material such as silicon that has properties intermediate between "conductors" such as metals that conduct electricity well and "insulators" such as rubber that conduct electricity almost nothing ("semiconductor in the narrow sense"). However, individual elements such as transistors and diodes (discrete semiconductor components; also called "semiconductor elements") and integrated circuits (ICs) that integrate circuits composed of transistors, etc., will also conventionally be called "semiconductors" ("semiconductors in the broad sense").

[0100] The present invention can be particularly suitably applied to "power semiconductors." Here, "power semiconductors" refer to semiconductors used for controlling and supplying electrical energy, such as converting alternating current to direct current or reducing voltage. Generally, they refer to semiconductors that control motors, lighting, etc., or change power, and are characterized by handling large voltages and currents.

[0101] Examples of power semiconductors include diodes, transistors (for example, IGBTs (Insulated Gate Bipolar Transistors), MOSFETs (metal-oxide-semiconductor field-effect transistors), ICs (integrated circuits), etc.), and the present invention is applicable to these semiconductors.

[0102] The present invention is applicable to hybrid vehicles, electric vehicles, and the like, and is effective for encapsulating power devices using highly efficient power semiconductors, such as Si, SiC, and GaN materials, which are expected to improve fuel efficiency and reduce size, but is not limited to these.

[0103] Furthermore, in the present invention, the semiconductor components such as applicable semiconductors and power semiconductors can be made from any semiconductor material suitable for the manufacture of semiconductor devices. For example, such materials include elemental semiconductor materials, such as silicon (Si), group IV compound semiconductor materials, such as silicon carbide (SiC) or silicon germanium (SiGe), and binary, ternary, or quaternary group III-V semiconductor materials, such as gallium arsenide (GaAs) and gallium phosphide. Examples include, but are not limited to, gallium (GaP), indium phosphide (InP), gallium nitride (GaN), aluminum gallium nitride (AlGaN), indium gallium phosphide (InGaPa), or indium gallium arsenide phosphide (InGaAsP), binary or ternary II-VI group semiconductor materials such as cadmium telluride (CdTe) and mercury cadmium telluride (HgCdTe).

[0104] Semiconductor equipment A broad semiconductor or semiconductor device to which the semiconductor encapsulation material of the present invention is applied is a semiconductor device composed of at least semiconductor elements and components, wherein the member or semiconductor element is encapsulated with the semiconductor encapsulation material of the present invention containing an organometallic complex and a silicone gel, for example, in the form illustrated in Figures 1 and 2 described later, specifically a semiconductor including a circuit pattern, elements and metal wiring provided on an insulating member of a power semiconductor.

[0105] Examples of semiconductor devices include integrated circuits, large-scale integrated circuits, active devices, passive devices, solid-state image sensors, discrete devices, semiconductor devices using SiC, power semiconductors such as power transistors, and automotive electronic components.

[0106] The semiconductor (semiconductor in a broad sense) of the present invention comprises at least a semiconductor element, a circuit pattern provided on an insulating member constituting the semiconductor, and a semiconductor encapsulating material of the present invention for encapsulating the element and metal wiring.

[0107] In the semiconductor of the present invention, for example, the encapsulating material composition of the present invention can be used to encapsulate electronic components such as semiconductor elements using molding methods such as transfer molding, compression molding, and injection molding. For example, transfer molding is a molding method (encapsulation method) that has generally been used for resin encapsulation of electronic components such as semiconductors, in which the encapsulating material composition is filled into a cavity in a plunger and cured to form an encapsulation layer. Compression molding, on the other hand, involves directly placing liquid semiconductor encapsulating material into a cavity and then immersing a lead frame, silicon interposer, organic interposer, flip-chip substrate, etc., on which the semiconductor element is fixed, after which... This method involves curing a semiconductor encapsulation material to form an encapsulation layer.

[0108] Furthermore, the encapsulating material composition of the present invention can be dissolved in various organic solvents to prepare a liquid coating solution for forming a semiconductor encapsulating layer, and then coated onto a semiconductor device using a coating method. Applicable coating methods include, for example, the transfer method and compression method described above, as well as wet coating methods such as the dispenser method, spin coating method, cast method, screen printing method, die coating method, blade coating method, roll coating method, spray coating method, curtain coating method, LB method (Langmuir-Bludget method), and inkjet printing method to form the encapsulating layer. Among these, the dispenser method, spin coating method, die coating method, transfer method, compression method, or inkjet printing method are preferred.

[0109] After forming a sealing layer with the sealing material composition of the present invention by the method described above, the material is cured by heat treatment. The curing conditions can be appropriately selected from conventionally known conditions, but for example, from the viewpoint of reaction rate, the temperature (curing temperature) is preferably in the range of 25 to 180°C, more preferably in the range of 60 to 150°C, and the time (curing time) is preferably in the range of 5 to 720 minutes. The curing can be carried out in one step or in multiple steps.

[0110] Specifically, semiconductor devices to which the present invention can be applied include semiconductor devices in which active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils are mounted on a copper lead frame support member, and the necessary parts are sealed with the semiconductor encapsulation material of the present invention. Such a semiconductor device may be constructed, for example, by fixing semiconductor elements on a copper lead frame, connecting the terminal parts of the elements, such as bonding pads, to the lead parts with wire bonding or bumps, and then sealing them using the semiconductor encapsulation material of the present invention.

[0111] Basic Configuration of Semiconductor Devices Next, as a representative example among the semiconductors of the present invention described above, the basic configuration of a power semiconductor module will be explained with the help of diagrams.

[0112] Figure 1 is a schematic cross-sectional view showing an example of the configuration of a power semiconductor module to which the encapsulating material composition of the present invention is applied.

[0113] The semiconductor module M shown in Figure 1 is a heat sink integrated power semiconductor module M, and mainly consists of a semiconductor device 1, which includes a semiconductor element 9 that is a power semiconductor (IGBT), and a heat sink 2. The semiconductor device 1 is joined to one main surface of the heat sink 2 by molten solder 7A using a heat sink 6 as a heat source via grease 5. The component including the semiconductor element 9 includes a heat sink 6, a ceramic substrate 8 as an insulating substrate joined to one main surface of the heat sink 6 by solder 7A, and a semiconductor element 9 fixed to one main surface of the ceramic substrate 8 by solder 7B.

[0114] Furthermore, the power semiconductor module M includes wires 10 electrically connected to the semiconductor element 9 and metal plate 13, external lead terminals 12, and a resin case 11 fixed to the periphery in a manner that surrounds the semiconductor element 9, etc. In the present invention, the inside of this resin case 11 is filled with a semiconductor encapsulation material SA containing the organometallic complex of the present invention and silicone. In the configuration shown in Figure 1, a single layer of the semiconductor encapsulation material SA is filled to form an encapsulation layer.

[0115] Here, the semiconductor element 9 is, for example, an IGBT (Insulated Gate Bipolar Transistor), which is a power semiconductor element capable of high-power, high-speed switching. Examples include bipolar transistor chips and FWD (Free Wheeling Diode) chips that recirculate the induced current generated when IGBT chips are off.

[0116] The ceramic substrate 8 is constructed by bonding metal plates to both sides of a ceramic insulating board. For example, it is a DCB (Direct Copper Bonding) substrate. A circuit pattern is formed on the metal plate formed on one main surface of the insulating board. The thickness of the ceramic substrate 8 is 0.6 mm or more and 2.0 mm or less. The material of the insulating board is various ceramics, preferably alumina, alumina with zirconia added, silicon nitride, or aluminum nitride. Its thickness is 0.2 mm or more and 1.0 mm or less, preferably 0.2 mm or more and 0.6 mm or less. The metal plate is copper, copper alloy, aluminum, or aluminum alloy.

[0117] The heat sink 6 is made of copper, copper alloy, pure aluminum, aluminum alloy, copper-molybdenum, pure iron, or iron alloy, and is preferably nickel-plated, gold-plated, or tin-plated on its surface.

[0118] The heat sink 2 is made of, for example, copper, copper alloy, aluminum, aluminum alloy, copper-molybdenum, or aluminum-silicon carbide, and its surface is further plated with nickel, gold, or tin. The heat sink 22 consists of a heat sink base 3 and fins 4. The fins 4 may be plate-shaped, corrugated, or calgate-shaped.

[0119] Solders 7A and 7B primarily consist of one of the following alloys: tin (Sn)-lead (Pb), tin (Sn)-silver (Ag), tin (Sn)-bismuth (Bi), tin (Sn)-antimony (Sb), tin (Sn)-copper (Cu), or tin (Sn)-indium (ln), and also contain additives and unavoidable impurities.

[0120] Figure 2 is a schematic cross-sectional view showing another example of the configuration of a power semiconductor module to which the encapsulating material composition of the present invention is applied.

[0121] Figure 2 shows a model in which a power semiconductor module M has the same configuration as in Figure 1, but a lower layer of silicone gel alone SG is formed as the encapsulation layer, and an upper encapsulation layer composed of a semiconductor encapsulation material SA2 containing the organometallic complex and silicone of the present invention is formed on its surface.

[0122] The semiconductor encapsulation material SA of the present invention is a material that encapsulates a semiconductor module including a circuit pattern, semiconductor elements, and metal wiring provided on an insulating member by curing the encapsulation material composition of the present invention.

[0123] For details of semiconductor modules applicable to the present invention, refer to, for example, the contents described in Japanese Patent Publication No. 2013-16525, Japanese Patent Publication No. 2016-313336, Japanese Patent Publication No. 2018-133598, Japanese Patent Publication No. 2019-93450, Japanese Patent Publication No. 2019-150879, Japanese Patent Publication No. 2020-13920, Japanese Patent Publication No. 2020-47763, Japanese Patent Publication No. 2020-115568, etc. [Examples]

[0124] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these. In the examples, the notation "parts" or "%" is used, but unless otherwise specified, it refers to "parts by mass" or "mass%". In the examples, the component is indicated in parentheses at the end. The numbers listed represent the symbols indicated in each figure.

[0125] Example 1 The sulfurization resistance of semiconductor encapsulating materials to Ag substrates was evaluated according to the method described below.

[0126] 《Preparation of evaluation chips》 (Fabrication of evaluation chip 1: This invention) An evaluation chip equipped with an Ag substrate having the configuration shown in Figure 3 was fabricated.

[0127] As shown in Figure 3, a silver substrate for evaluation was formed by depositing silver to a thickness of 100 nm onto a 30 × 30 × 0.7 mmt glass substrate G. Next, a frame was formed on the surface of the Ag substrate using a circular silicon ring SR with an inner diameter of 24 mm and a thickness of 3 mm, and an evaluation chip was fabricated having an Ag substrate with voids for filling with a sealing material composition.

[0128] (Filling and curing of sealing material composition 1) Next, as the silicone gel, we used Shin-Etsu Chemical's silicone gel KE-1062 (a one-component addition type potting material with a curing method, viscosity: 700 mPa·s at 23℃, penetration (1 / 4 cone): 40), and as the organometallic complex, we used example compound (1-3) (zinc stearate, metal atom charge: 1.29, molecular volume: 587 Å). 3 A encapsulant composition 1 was prepared by adding a substance (decomposition temperature: 340°C) to the silicone gel at a ratio of 1.0% by mass and performing ultrasonic dispersion. The viscosity of encapsulant composition 1 at 23°C is 800 mPa·s.

[0129] Next, the prepared sealing material composition 1 was filled into the circular silicone ring SR of the evaluation chip shown in Figure 3, under conditions that the thickness after curing would be 2.5 mm, and then cured at 120°C for 30 minutes to produce the evaluation chip 1.

[0130] (Fabrication of evaluation chip 2: This invention) Evaluation chip 2 was prepared in the same manner as the preparation of evaluation chip 1, except that the amount of example compound (1-3), which is an organometallic complex, added to the silicone gel was changed to 5.0% by mass, while evaluation chip 2 was prepared in the same manner as the preparation of evaluation chip 1. The viscosity of evaluation chip 2 at 23°C is 1200 mPa·s.

[0131] (Fabrication of evaluation chip 3: This invention) Evaluation chip 3 was prepared in the same manner as the preparation of the sealing material composition 1 used for the production of the evaluation chip 1, except that the amount of exemplary compounds (1-3), which are organometallic complexes, added to the silicone gel was changed to 10.0% by mass. The viscosity of sealing material composition 3 at 23°C is 1800 mPa·s.

[0132] (Fabrication of evaluation chip 4: This invention) Evaluation chip 4 was prepared in the same manner as the evaluation chip 2 described above, except that in the preparation of the sealing material composition 2 used for the production of the evaluation chip 2, the silicone gel KE-1057 (a one-component addition-type potting material with a curing method, viscosity: 800 mPa·s at 23℃, penetration (1 / 4 cone): 65) manufactured by Shin-Etsu Chemical Co., Ltd. was used instead of KE-1062 for the silicone gel. The viscosity of sealing material composition 4 at 23℃ is 1300 mPa·s.

[0133] (Fabrication of evaluation chip 5: This invention) In preparing the sealing material composition 2 used to manufacture the above evaluation chip 2, the silicone gel was replaced with Shin-Etsu Chemical's silicone gel KE-1061 (curing method is An evaluation chip 5 was prepared in the same manner as above, except that a one-component addition-type potting material (viscosity: 600 mPa·s at 23℃, penetration (1 / 4 cone): 90) was used as the sealing material composition 5. The viscosity of the sealing material composition 5 at 23℃ is 1100 mPa·s.

[0134] (Fabrication of evaluation chip 6: The present invention) In the preparation of the sealing material composition 2 used to fabricate the evaluation chip 2 described above, example compound (1-2) (zinc laurate, metal atom charge: 1.29, molecular volume: 486 Å) was used as the organometallic complex instead of example compound (1-3). 3 An evaluation chip 6 was prepared in the same manner except that an encapsulating material composition 6 prepared in the same manner was used, except that a decomposition temperature of 320°C was used. The viscosity of the encapsulating material composition 6 at 23°C is 1000 mPa·s.

[0135] (Fabrication of evaluation chip 7: This invention) In the preparation of the sealing material composition 2 used to fabricate the evaluation chip 2 described above, the organometallic complex was replaced with example compound (2-1) (1-hydroxypyridine-2-thione zinc salt, metal atom charge: 1.37, molecular volume: 388 Å). 3 An evaluation chip 7 was prepared in the same manner except that an encapsulating material composition 7 prepared in the same manner was used, except that a decomposition temperature of 300°C was used. The viscosity of the encapsulating material composition 7 at 23°C is 1200 mPa·s.

[0136] (Fabrication of evaluation chip 8: This invention) In preparing the sealing material composition 2 used to fabricate the evaluation chip 2 described above, the organometallic complex was replaced with example compound (2-2) (8-hydroxyquinoline zinc, metal atom charge: 1.34, molecular volume: 264 Å). 3 An evaluation chip 8 was prepared in the same manner except that an encapsulating material composition 8 prepared in the same manner was used, except that a decomposition temperature of 390°C was used. The viscosity of the encapsulating material composition 8 at 23°C is 1200 mPa·s.

[0137] (Fabrication of evaluation chip 9: This invention) In the preparation of the sealing material composition 2 used to fabricate the evaluation chip 2 described above, example compound (1-4) (bis(2,2,6,6-tetramethylpiperidinyl)zinc, metal atom charge: 1.18, molecular volume: 332 Å) was used instead of example compound (1-3) as the organometallic complex. 3 An evaluation chip 9 was prepared in the same manner as above, except that a sealing material composition 6 prepared in the same manner as above was used, except that a decomposition temperature of 390°C was used. The viscosity of the sealing material composition 9 at 23°C is 1100 mPa·s.

[0138] (Fabrication of evaluation chip 10: Comparative example) In preparing the sealing material composition 2 used to fabricate the evaluation chip 2 described above, zinc acetate (metal atom charge: 1.37, molecular volume: 116 Å) was used instead of the example compounds (1-3) as the organometallic complex. 3 An evaluation chip 10 was prepared in the same manner except that an encapsulating material composition 10 prepared in the same manner was used, except that a decomposition temperature of 110°C was used. The viscosity of the encapsulating material composition 10 at 23°C is 800 mPa·s.

[0139] (Fabrication of evaluation chip 11: Comparative example) In preparing the sealing material composition 2 used to fabricate the evaluation chip 2 described above, zinc sulfate (metal atom charge: 1.49, molecular volume: 70 Å) was used instead of the example compounds (1-3) as the organometallic complex. 3 An evaluation chip 11 was prepared in the same manner except that an encapsulating material composition 11 prepared in the same manner was used, except that a decomposition temperature of 105°C was used. The viscosity of the encapsulating material composition 11 at 23°C is 800 mPa·s.

[0140] (Fabrication of evaluation chip 12: Comparative example) The evaluation chip 12 was prepared in the same manner as the evaluation chip 2 described above, except that the sealing material composition 2 used in the preparation of the evaluation chip 2 was prepared in the same manner as the sealing material composition 12 used in the preparation of the sealing material composition 2, except that KER-2500-A / B (methyl rubber, viscosity: 4300 mPa·s at 23℃, penetration (1 / 4 cone): less than 10) manufactured by Shin-Etsu Chemical Co., Ltd. was used instead of KE-1062 for the silicone gel. The viscosity of the sealing material composition 12 at 23℃ is 5000 mPa·s.

[0141] (Fabrication of evaluation chip 13: Comparative example) The evaluation chip 13 was prepared in the same manner as the evaluation chip 2 described above, except that the sealing material composition 2 used for the preparation of the evaluation chip 2 was prepared in the same manner as the sealing material composition 13 used for the preparation of the sealing material composition 2 evaluation chip 2 was ASP-2010-A / B (two-component addition type phenyl resin, viscosity: 2300 mPa·s at 23℃, penetration (1 / 4 cone): less than 10) manufactured by Shin-Etsu Chemical Co., Ltd., instead of KE-1062 for the silicone gel.

[0142] [Measurement of each characteristic value] <Viscosity measurement> The viscosity (at 23°C) of the silicone gel and encapsulant composition was measured using an E-type rotational viscometer (cone plate type) according to the viscosity measurement method specified in JIS K7117-1.

[0143] <Measurement of decomposition temperature> The decomposition temperatures of organometallic complexes were measured under the following conditions, in accordance with the methods described in JIS K 0129 and JIS K 7120.

[0144] Measurement device: Hitachi High-Tech Science Corporation Differential Thermogravimetric Simultaneous Thermomeasuring Device TG / DTA6200 Sample quantity: 10 mg, using Alpane Atmosphere gas: Nitrogen 200 mL / min Heating rate: Heats up to 500°C at a rate of 10°C / min. <Measurement of Penetration> The consistency test was performed in accordance with the consistency test method specified in JIS K2220, using a 1 / 4 cone.

[0145] <Calculation of metal atom charge and molecular volume of organometallic complexes> The results were obtained computationally based on the aforementioned density functional theory (DFT: Discrete Fourier Transform). The calculations were performed using Gaussian16 software from Gaussian, Inc., and the density functional method was employed as the computational technique.

[0146] Specifically, the charge of the metal atoms was calculated using a method based on Natural Population Analysis (NPA).

[0147] Furthermore, the structure-derived parameter (molecular volume) was calculated using the functions of Winmostar (Version 10.2.4) based on the stable structure obtained in the above calculation.

[0148] Evaluation of sulfurization resistance of evaluation chips Each of the evaluation chips prepared as described above was subjected to a forced degradation treatment for 100 hours in an environment with a hydrogen sulfide concentration of 5 ppm, a temperature of 85°C, and a humidity of 85% RH.

[0149] Next, the reflectance of the Ag substrate surface before and after forced degradation treatment was measured at a wavelength of 700 nm using a Hitachi High-Technologies U-4100 spectrophotometer.

[0150] Next, the decrease in reflectance after forced degradation treatment relative to the reflectance before forced degradation treatment (ΔT%) was determined, and the sulfidation resistance of the encapsulating material composition to the Ag substrate was evaluated according to the following criteria.

[0151] 5: ΔT is less than 20% 4: ΔT is 20% or more and less than 40% 3: ΔT is 40% or more and less than 60% 2: ΔT is 60% or greater, but less than 80%. 1: ΔT is 80% or greater. The results obtained from the above are shown in Table II. In Table II, the term "the present invention" in the remarks column for evaluation chip number 8 shall be read as "reference example".

[0152] [Table 2] As is clear from the results shown in Table II, the evaluation chip of the present invention using a encapsulating material composition that satisfies the conditions defined in the present invention exhibits superior sulfidation prevention effect on the Ag substrate compared to the comparative example.

[0153] Example 2 《Preparation of evaluation chips》 Each evaluation chip was fabricated according to the following method.

[0154] [Preparation of evaluation chip 21] (Fabrication of test patterned substrates) A test patterning substrate 53 for evaluating sulfur resistance using a Cu electrode, configured as shown in Figure 4, was fabricated according to the method described below.

[0155] A 5 cm thick Corning EagleXG non-alkali glass test element substrate 54 was used and cleaned by wet cleaning. Next, an adhesion layer was formed on the test element substrate 54 by sputtering to a thickness of 10 nm using SiO2. Then, a 1 μm thick Cu film was deposited at a predetermined location, also by sputtering.

[0156] Next, to form a 75 μm thick L / S comb-type electrode 57 by photoprocessing, a 1 μm thick photoresist from Tokyo Ohka Chemical was applied, followed by exposure and development, and then patterning with a Cu etching solution from Kanto Chemical. After stripping and pure rinsing, a test patterning substrate 53 with the configuration shown in Figure 4 was fabricated.

[0157] In Figure 4, the test patterning substrate 53 has a comb-like electrode 57 formed on the test element substrate 54, connected to a negative electrode 55 and a positive electrode 56.

[0158] (Preparation of evaluation chips) Next, as shown in Figure 5, the sealing material composition 1 prepared in Example 1 was applied to the upper and lower layers of the test patterning substrate 53 to cover the entire comb-shaped electrode, under conditions that the cured film thickness would be 3 mm. By drying at 120°C for 30 minutes, a sealing layer 60 was formed with the sealing material composition 1, and an evaluation chip 21 was fabricated.

[0159] [Preparation of evaluation chips 22-33] Evaluation chips 22 to 33 were prepared in the same manner as the evaluation chip 21, except that sealing material compositions 2 to 13 prepared in Example 1 were used instead of sealing material composition 1.

[0160] Evaluation of sulfurization resistance of evaluation chips The sulfurization resistance of the evaluation chip having the Cu electrode prepared as described above was evaluated by the following method.

[0161] Two of each evaluation chip (240 comb electrodes) consisting of the configuration shown in Figure 5 were prepared, and their sulfurization resistance was evaluated according to the following method.

[0162] The sulfidation resistance of the copper comb-tooth electrodes was evaluated by measuring the time it took for the leakage current to reach 0.5 mA when a voltage of 100V from power supply 58 was applied to the comb-tooth electrode of each of the evaluation chips prepared above, under conditions of a hydrogen sulfide concentration of 5 ppm, a temperature of 85°C, and a humidity of 85% RH, according to the following conditions.

[0163] 5. The time it takes for the leakage current to reach 0.5mA is 100 hours or more. 4. The time during which the leakage current is 0.5 mA is 75 hours or more and less than 100 hours. 3. The time during which the leakage current is 0.5 mA is 50 hours or more and less than 75 hours. 2: The time during which the leakage current is 0.5 mA is 25 hours or more and less than 50 hours. 1: The time during which the leakage current is 0.5 mA is less than 25 hours. The results obtained from the above are shown in Table III. In Table III, the term "the present invention" in the remarks column for evaluation chip number 28 shall be read as "reference example".

[0164] [Table 3] As is clear from the results shown in Table III, the sealing material composition that satisfies the conditions specified in the present invention The evaluation chip of the present invention using this method exhibits superior sulfidation prevention effect on the Cu electrode compared to the comparative example.

[0165] Example 3 The encapsulation effect in power semiconductors (IGBT modules) was evaluated according to the following method.

[0166] As Model 1, a configuration was created in which a sulfidation prevention layer was formed by a single layer containing the silicone gel prepared in Example 1 and the organometallic complex encapsulating composition SA, as shown in Figure 1. As Model 2, two types of power semiconductors (IGBT modules) were fabricated in which the lower layer, as shown in Figure 2, was composed of a single layer of silicone gel, and the upper layer was formed with a sulfidation prevention layer containing the silicone gel prepared in Example 1 and the organometallic complex encapsulating composition SA.

[0167] Specifically, a semiconductor device was fabricated using the components described in Figure 13 of Japanese Patent Publication No. 6440794.

[0168] The energization test was conducted under the same energization conditions as described in paragraph (0062) of Japanese Patent Publication No. 6440794. Specifically, a gate voltage of 15V was applied to the fabricated IGBT module, and a current of 200A was passed through it. The temperature of the IGBT module reached a steady state at 150°C. In this state, the module was energized for 300 hours under conditions of a hydrogen sulfide concentration of 5 ppm, a temperature of 85°C, and a humidity of 85%RH. The presence or absence of leakage current due to sulfidation corrosion of the electrodes was checked, and all IGBT modules to which the sealing material composition of the present invention was applied showed no leakage current and demonstrated good sealing stability under high temperatures. [Industrial applicability]

[0169] The present invention provides a sealing material composition that prevents sulfidation associated with high temperatures of semiconductor elements and components constituting a semiconductor device, and exhibits a stable sealing effect even under high temperatures, as well as a semiconductor sealing material and semiconductors that can be used with the same. [Explanation of Symbols]

[0170] 1 Semiconductor device 2 Heatsinks 3 Heatsink Base 4 fins 5. Grease 6 Heat sink 7A, 7B solder 8. Ceramic substrate 9. Semiconductor devices (IGBTs) 10 wires 11. Resin case 12 External output terminals 13 Metal plate 53 Test Patterning Boards 54-element substrate 55 Negative electrode 56 Positive electrode 57 Comb-shaped electrode 58 Power supply 59 Evaluation Chips 60 Sealing layer Ag Silver Plate G Glass Substrate M Semiconductor Module SA, SA2 encapsulant composition SG Silicone Gel SR Silicone Ring TP Test Plate

Claims

1. A sealing material composition containing an organometallic complex, The organometallic complex is one of the following compounds 1-4 or 2-1. The decomposition temperature of the organometallic complex is 150°C or higher. Furthermore, it contains silicone gel, and A sealing material composition having a viscosity of 2000 mPa·s or less at 23°C. 【Chemistry 1】

2. In the electronic state calculation method based on density functional theory, the organometallic complex The charge of the metal atom is 1.4 or less, and The molecular volume of the organometallic complex is 200 Å. ３ The sealing material composition according to claim 1, as described above.

3. A semiconductor encapsulation material using the encapsulation composition described in claim 1 or claim 2, A semiconductor encapsulation material is a material that encapsulates a semiconductor including a circuit pattern, elements, and metal wiring provided on an insulating member by curing the aforementioned encapsulation composition.

4. The semiconductor encapsulating material according to claim 3, which is a material that forms a sulfidation-preventive layer for preventing the sulfidation of copper and silver constituting a semiconductor.

5. The semiconductor encapsulating material according to claim 3 or claim 4, wherein the penetration of a 1 / 4 cone measured in accordance with the consistency test method specified in JIS K2220 is 10 or more.

6. A semiconductor comprising the semiconductor encapsulation material described in any one of claims 3 to 5.

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