TW202031859A - Sealing method, sealing layer, mixed liquid for sealing layer formation, method for producing sealing layer, and semiconductor device - Google Patents

Sealing method, sealing layer, mixed liquid for sealing layer formation, method for producing sealing layer, and semiconductor device Download PDF

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TW202031859A
TW202031859A TW108140215A TW108140215A TW202031859A TW 202031859 A TW202031859 A TW 202031859A TW 108140215 A TW108140215 A TW 108140215A TW 108140215 A TW108140215 A TW 108140215A TW 202031859 A TW202031859 A TW 202031859A
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sealing layer
group
sealing
semiconductor device
oxide
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TWI741405B (en
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志田有章
井宏元
牧島幸宏
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日商柯尼卡美能達股份有限公司
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
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    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48135—Connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
    • H01L2224/48145—Connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
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    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

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Abstract

The present invention addresses the problem of providing: a sealing method which prevents a semiconductor element and a component that constitute a semiconductor device from corrosion caused by harmful substances; a sealing layer which is used for the sealing method; a mixed liquid which is used for the formation of the sealing layer; a method for producing a sealing layer; and a semiconductor device which uses the sealing method. A sealing method of the present invention for sealing a semiconductor element and a component that constitute a semiconductor device is characterized by forming a sealing layer by any one of (1) a method 1 which uses a composition that contains an epoxy resin and an organic metal oxide, (2) a method 2 which uses a composition that contains an epoxy resin and a filler that is coated with an organic metal oxide, and (3) a method 3 wherein the component is sealed by means of an organic metal oxide, and is subsequently coated with an epoxy resin.

Description

封止方法、封止層、封止層形成用之混合液、封止層之製造方法及半導體裝置Sealing method, sealing layer, mixed solution for forming sealing layer, manufacturing method of sealing layer, and semiconductor device

本發明係有關於一種封止方法、封止層、封止層形成用之混合液、封止層之製造方法及半導體裝置，更詳而言之，係有關於一種防止構成半導體裝置之半導體元件或零件被有害物質腐蝕之封止方法、用於該封止方法之封止層、用於該封止層的形成之混合液、封止層之製造方法及使用該製造方法之半導體裝置。The present invention relates to a sealing method, a sealing layer, a mixed solution for forming the sealing layer, a manufacturing method of the sealing layer, and a semiconductor device. More specifically, it relates to a semiconductor device that prevents the formation of a semiconductor device Or a sealing method in which parts are corroded by harmful substances, a sealing layer used in the sealing method, a mixed solution used in the formation of the sealing layer, a manufacturing method of the sealing layer, and a semiconductor device using the manufacturing method.

傳統上，作為封止電晶體、IC(積體電路， Integrated Circuit)、LSI(大規模積體電路，Large Scale Integration)等電子零件裝置的元件之方法，基於生產性或成本等觀點，係以使用樹脂為代表之封止用材料來進行封止的方法為主流。Traditionally, as a sealed transistor, IC (integrated circuit, Integrated Circuit), LSI (Large Scale Integration) and other electronic component devices. Based on the viewpoint of productivity and cost, it is a method of sealing using sealing materials represented by resin As the mainstream.

向來，二極體、電晶體、積體電路等電子零件主要係藉由環氧半導體封止用組成物的硬化物來進行封止。尤其是積體電路向來係使用含有為防止腐蝕而降低氯含量之環氧樹脂、酚系硬化劑及熔融二氧化矽、結晶二氧化矽等無機填充材的環氧半導體封止用組成物。環氧半導體封止用組成物，咸認係具備作業性、成形性、電特性、耐濕性、耐熱性、機械特性、與嵌件之接著性等各種特性之極佳的平衡。Traditionally, electronic parts such as diodes, transistors, and integrated circuits are mainly sealed by hardened materials of epoxy semiconductor sealing compositions. In particular, integrated circuits have always used epoxy semiconductor sealing compositions containing epoxy resins to prevent corrosion and reduce chlorine content, phenolic hardeners, and inorganic fillers such as fused silica and crystalline silica. Epoxy semiconductor sealing composition is believed to have an excellent balance of various properties such as workability, formability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts.

再者，作為半導體之封止用材料使用的封止樹脂，由密接性等觀點而言係使用環氧樹脂等，而由安全性觀點而言則要求高難燃性；對於此要求，一般係藉由使環氧半導體封止用組成物含有鹵素系化合物來實現難燃化。Furthermore, the sealing resin used as a sealing material for semiconductors uses epoxy resin from the standpoint of adhesion, etc., but requires high flame retardancy from the standpoint of safety; for this requirement, generally Flame retardancy is achieved by containing a halogen-based compound in the epoxy semiconductor sealing composition.

然而，近年來隨著電子設備的小型化、輕量化、高性能化之市場動向，半導體元件亦逐年持續高積體化，而且在促進半導體裝置的表面安裝化的情況下，對於半導體元件之封止所用的封止用環氧半導體封止用組成物的要求亦日趨嚴格。However, in recent years, with the market trends of miniaturization, lighter weight, and higher performance of electronic equipment, semiconductor components have also continued to increase year by year, and in the case of promoting the surface mounting of semiconductor devices, the packaging of semiconductor components The requirements for sealing epoxy semiconductor sealing compositions used for sealing are also becoming stricter.

例如，專利文獻1中，近年來作為替代金線之廉價接合線，提出一種半導體裝置用接合線，其具有：芯材，係以銅為主成分；及外皮層，係於該芯材上含有與芯材不同之組成的導電性金屬及銅。就該半導體裝置用接合線，藉由控制外皮層的厚度，可因應材料費低廉，球接合性、線接合性等優異且迴圈形成性亦良好的窄間距用細線化或電力系統IC用途的粗徑化。For example, in Patent Document 1, in recent years, as an inexpensive bonding wire to replace gold wire, a bonding wire for semiconductor devices is proposed, which has: a core material containing copper as the main component; and an outer skin layer containing on the core material Conductive metal and copper with a different composition from the core material. With regard to the bonding wire for semiconductor devices, by controlling the thickness of the outer skin layer, it is possible to respond to low material costs, excellent ball bonding, wire bonding, etc., and good loop forming properties for narrow pitch wire thinning or power system IC applications. Coarse diameter.

然而，持續進行詳細的研究，在構成電子零件裝置的封止構件中若含有微量的鹵素物質的話，若線狀的接合端子部等採用使用此等銅線來連接於含鋁金屬銲點之構成時，因銅與鋁的功函數差所引發之電池效應或作動時與電場發生離子化之鹵素物質而發生腐蝕，而有導致連接不良或可靠性降低的問題。 [先前技術文獻] [專利文獻]However, detailed research continues. If a small amount of halogen is contained in the sealing member that constitutes the electronic component device, if the wire-shaped bonding terminal portion is used to use such a copper wire to connect to the aluminum-containing metal solder joint. At this time, due to the battery effect caused by the difference in work function between copper and aluminum or the halogen substance ionized with the electric field during operation, corrosion occurs, resulting in poor connection or reduced reliability. [Prior Technical Literature] [Patent Literature]

[專利文獻1] 日本特開2007-12776號公報[Patent Document 1] JP 2007-12776 A

[發明所欲解決之課題][The problem to be solved by the invention]

本發明係有鑑於上述問題･狀況而完成者，其解決課題在於提供一種防止存在於封止構造中，或者由外部侵入之水分、鹵素成分、硫化氫氣體等引起構成半導體裝置之半導體元件或零件的腐蝕之封止方法，與用於該封止方法之封止層、用於該封止層的形成之混合液、封止層之製造方法及使用該製造方法之半導體裝置。 [解決課題之手段]The present invention was completed in view of the above-mentioned problems and conditions, and the problem to be solved is to provide a semiconductor element or part that prevents it from being present in a sealed structure or caused by moisture, halogen components, hydrogen sulfide gas, etc. entering from the outside. The sealing method of etching, the sealing layer used in the sealing method, the mixed solution used in the formation of the sealing layer, the manufacturing method of the sealing layer, and the semiconductor device using the manufacturing method. [Means to solve the problem]

本案發明人在為解決上述課題而針對上述問題的原因等進行探討的過程中發現，藉由使具有特定結構的有機金屬氧化物存在於封止層內，而由該有機金屬氧化物捕獲(捕集、吸附等)存在於封止層內或者侵入而至之對半導體元件或零件會造成腐蝕的物質，例如水分、鹵素成分、硫化氫氣體等，可實現防止腐蝕之封止方法、用於該封止方法之封止層、用於該封止層的形成之混合液、封止層之製造方法及使用該製造方法之半導體裝置，而臻至完成本發明。The inventors of the present invention, in the process of investigating the causes of the above-mentioned problems in order to solve the above-mentioned problems, discovered that by allowing the organometallic oxide with a specific structure to exist in the sealing layer, the organometallic oxide is trapped (trapped). (Collection, adsorption, etc.) existing in the sealing layer or intruding into the semiconductor components or parts that will cause corrosion, such as moisture, halogen components, hydrogen sulfide gas, etc., can achieve a sealing method to prevent corrosion. The sealing layer of the sealing method, the mixed solution used for the formation of the sealing layer, the manufacturing method of the sealing layer, and the semiconductor device using the manufacturing method have completed the present invention.

亦即，本發明之上述課題可藉由以下手段來解決。That is, the above-mentioned problems of the present invention can be solved by the following means.

1. 一種封止方法，其係構成半導體裝置之半導體元件及零件的封止方法，其特徵為藉由以下任一種方法來形成封止層： (1)使用含有環氧樹脂與有機金屬氧化物的組成物之方法1； (2)使用含有環氧樹脂與由有機金屬氧化物被覆之填料的組成物之方法2；或 (3)將前述零件以有機金屬氧化物封止後，以環氧樹脂予以被覆之方法3。1. A sealing method, which is a method of sealing semiconductor elements and parts constituting a semiconductor device, characterized by forming a sealing layer by any of the following methods: (1) Method 1 of using a composition containing epoxy resin and organic metal oxide; (2) Method 2 of using a composition containing an epoxy resin and a filler coated with an organic metal oxide; or (3) Method 3 where the aforementioned parts are sealed with organometallic oxide and then coated with epoxy resin.

2. 如第1項之封止方法，其中前述有機金屬氧化物為具有下述通式(1)所示之結構的有機金屬氧化物。2. The sealing method according to item 1, wherein the aforementioned organometallic oxide is an organometallic oxide having a structure represented by the following general formula (1).

Figure 02_image001
[式中，R表示氫原子、碳數1個以上之烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基；惟，R亦可包含氟原子作為取代基；M表示金屬原子；OR1 表示氟化烷氧基；x表示金屬原子的價數，y表示1與x之間的任意之整數；n表示聚縮合度]。 3. 如第1項或第2項之封止方法，其係具有以塗佈法形成前述封止層之步驟。
Figure 02_image001
[In the formula, R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group with more than 1 carbon; however, R may also contain a fluorine atom as a substituent ; M represents a metal atom; OR 1 represents a fluorinated alkoxy group; x represents the valence of the metal atom, y represents an integer between 1 and x; n represents the degree of polycondensation]. 3. The sealing method as described in item 1 or 2, which has the step of forming the aforementioned sealing layer by a coating method.

4. 一種封止層，其特徵為至少由環氧樹脂及具有下述通式(1)所示之結構的有機金屬氧化物所構成。4. A sealing layer characterized by being composed of at least epoxy resin and organometallic oxide having the structure represented by the following general formula (1).

Figure 02_image003
[式中，R表示氫原子、碳數1個以上之烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基；惟，R亦可包含氟原子作為取代基；M表示金屬原子；OR1 表示氟化烷氧基；x表示金屬原子的價數，y表示1與x之間的任意之整數；n表示聚縮合度]。 5. 一種封止層，其特徵為由具有下述通式(1)所示之結構的有機金屬氧化物所構成。
Figure 02_image003
[In the formula, R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group with more than 1 carbon; however, R may also contain a fluorine atom as a substituent ; M represents a metal atom; OR 1 represents a fluorinated alkoxy group; x represents the valence of the metal atom, y represents an integer between 1 and x; n represents the degree of polycondensation]. 5. A sealing layer characterized by being composed of an organometallic oxide having a structure represented by the following general formula (1).

Figure 02_image005
[式中，R表示氫原子、碳數1個以上之烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基；惟，R亦可包含氟原子作為取代基；M表示金屬原子；OR1 表示氟化烷氧基；x表示金屬原子的價數，y表示1與x之間的任意之整數；n表示聚縮合度]。 6. 如第4項或第5項之封止層，其中前述有機金屬氧化物中氟原子數相對於碳原子數與氟原子數之總數的比值F/(C+F)係滿足下式(a)所規定之條件。
Figure 02_image005
[In the formula, R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group with more than 1 carbon; however, R may also contain a fluorine atom as a substituent ; M represents a metal atom; OR 1 represents a fluorinated alkoxy group; x represents the valence of the metal atom, y represents an integer between 1 and x; n represents the degree of polycondensation]. 6. The sealing layer of item 4 or item 5, wherein the ratio F/(C+F) of the number of fluorine atoms in the aforementioned organometallic oxide to the total number of carbon atoms and the total number of fluorine atoms satisfies the following formula ( a) The prescribed conditions.

Figure 02_image007
7. 如第4項至第6項中任一項之封止層，其中前述通式(1)中以M表示之金屬原子係由Ti、Zr、Sn、Ta、Fe、Zn、Bi、Cu、Mg、Mn、Co、Ni、Ag及Al選出的至少一種。
Figure 02_image007
7. The sealing layer of any one of items 4 to 6, wherein the metal atom represented by M in the general formula (1) is composed of Ti, Zr, Sn, Ta, Fe, Zn, Bi, Cu At least one selected from, Mg, Mn, Co, Ni, Ag and Al.

8. 如第4項至第7項中任一項之封止層，其係含有由前述有機金屬氧化物被覆之填料。8. The sealing layer of any one of items 4 to 7, which contains a filler coated with the aforementioned organometallic oxide.

9. 一種封止層形成用之混合液，其特徵為含有下述通式(A)所示之化合物或具有下述通式(1)所示之結構的有機金屬氧化物與醇類。9. A mixed solution for forming a sealing layer, characterized by containing a compound represented by the following general formula (A) or an organometallic oxide having a structure represented by the following general formula (1) and alcohols.

Figure 02_image009
[式中，R表示氫原子、碳數1個以上之烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基；惟，R亦可包含氟原子作為取代基；M表示金屬原子；OR1 表示氟化烷氧基；x表示金屬原子的價數，y表示1與x之間的任意之整數；n表示聚縮合度]。 10. 一種封止層之製造方法，其係製造如第4項至第8項中任一項之封止層的封止層之製造方法，其特徵為： 使用如第9項之封止層形成用之混合液來製造。
Figure 02_image009
[In the formula, R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group with more than 1 carbon; however, R may also contain a fluorine atom as a substituent ; M represents a metal atom; OR 1 represents a fluorinated alkoxy group; x represents the valence of the metal atom, y represents an integer between 1 and x; n represents the degree of polycondensation]. 10. A method for manufacturing a sealing layer, which is a method for manufacturing a sealing layer such as the sealing layer of any one of items 4 to 8, characterized by: using the sealing layer as described in item 9 The mixture is made for forming.

11. 一種半導體裝置，其係至少由半導體元件及零件所構成的半導體裝置，其特徵為： 前述半導體元件或零件係由如第4項至第7項中任一項之封止層所被覆。11. A semiconductor device, which is a semiconductor device composed of at least semiconductor elements and parts, characterized by: The aforementioned semiconductor element or component is covered by the sealing layer as in any one of items 4 to 7.

12. 如第11項之半導體裝置，其中由前述封止層所被覆之前述零件為接合線或金屬銲點(land)。 [發明之效果]12. The semiconductor device according to item 11, wherein the aforementioned parts covered by the aforementioned sealing layer are bonding wires or metal lands. [Effects of Invention]

根據本發明之上述手段，可提供一種防止存在於封止構造中，或者由外部侵入之水分、鹵素成分、硫化氫氣體等引起構成半導體元件之零件(例如金屬端子部等)的腐蝕之封止方法，與用於該封止方法之封止層、用於該封止層的形成之混合液、封止層之製造方法及使用該製造方法之半導體裝置。According to the above-mentioned means of the present invention, it is possible to provide a seal that prevents corrosion of the parts (such as metal terminals, etc.) constituting the semiconductor element caused by moisture, halogen components, hydrogen sulfide gas, etc. in the sealing structure or caused by external intrusion. A method, a sealing layer used in the sealing method, a mixed solution used in the formation of the sealing layer, a manufacturing method of the sealing layer, and a semiconductor device using the manufacturing method.

就本發明效果之展現機構或作用機構尚不明確，但可如下推察。The display mechanism or action mechanism of the effect of the present invention is not clear, but it can be inferred as follows.

對於具有半導體元件或半導體積體電路經封止之構造的半導體裝置進行在各種環境下之耐久性的研究判明，半導體封止層內的鹵素成分會引起構成半導體裝置之接合線端子的腐蝕。Studies on the durability of semiconductor devices with sealed semiconductor elements or semiconductor integrated circuits under various environments have revealed that halogen components in the semiconductor sealing layer cause corrosion of the bonding wire terminals constituting the semiconductor device.

這是因為，由於接合線的端子部係由不同金屬相連接而成，所以會產生由氧化還原電位差所引起的電池效應，甚而，於作動時電場會發生作用。經判明水分與鹵素，尤為鹵素存在於該處，會引起腐蝕。然而，由於封止構件為了增加難燃性而含有些微的鹵素，甚而鹵素會從外部侵入而引起腐蝕，而處於腐蝕更為惡化的環境。This is because, since the terminals of the bonding wire are connected by different metals, a battery effect caused by a difference in oxidation-reduction potential will occur, and even an electric field will act when it is activated. It has been found that moisture and halogens, especially halogens, are present there, which can cause corrosion. However, since the sealing member contains a slight amount of halogen in order to increase the flame retardancy, even halogen invades from the outside to cause corrosion, and the corrosion is more deteriorated.

本案發明人在持續進行上述問題之解決手段的研究當中發現，藉由以使作為吸附材料之可有效捕集水分、硫化氫、鹵素分子、鹵素離子等的有機金屬氧化物，特佳為具有前述通式(1)所示之結構的有機金屬氧化物含於環氧樹脂(模封劑)中而構成之封止層進行封止的方法、以由封止層中含有將填料(亦稱無機填充材)表面以該有機金屬氧化物塗覆之粒子的環氧樹脂所構成之封止層進行封止的方法，或將零件以該有機金屬氧化物被覆後，以環氧樹脂予以封止的方法，而以前述有機金屬氧化物將半導體裝置的零件，例如以Cu或Ag,Au連接之線接合或該金屬線經焊接而成的端子部表面被覆，由此可藉由防止腐蝕之封止方法來防止半導體裝置的腐蝕。The inventors of the present case have continued to conduct research on solutions to the above-mentioned problems and found that it is particularly preferable to use organic metal oxides as adsorbents that can effectively trap moisture, hydrogen sulfide, halogen molecules, halogen ions, etc. The organic metal oxide of the structure represented by the general formula (1) is contained in the epoxy resin (molding agent) to form a sealing layer. The sealing layer contains the filler (also known as inorganic Filling material) The method of sealing the surface with a sealing layer composed of epoxy resin of the organometallic oxide coated particles, or the part is covered with the organometallic oxide and then sealed with epoxy resin Method, and the aforementioned organometallic oxide is used to bond the parts of the semiconductor device, such as the wire bonding of Cu or Ag, Au, or the surface of the terminal portion formed by welding the metal wire, which can be sealed by preventing corrosion Methods to prevent corrosion of semiconductor devices.

亦即，本發明係藉由形成包含具捕集鹵素機能之有機金屬氧化物的封止層，而能夠獲得防止水分、鹵素成分、硫化氫氣體等引起構成半導體元件之金屬端子部的腐蝕之具高可靠性的封止層。That is, in the present invention, by forming a sealing layer containing an organometallic oxide with a halogen trapping function, it is possible to obtain a device to prevent corrosion of the metal terminal portion constituting the semiconductor element caused by moisture, halogen components, hydrogen sulfide gas, etc. Highly reliable sealing layer.

具體而言，存在於封止層內的鹵素，例如氯等會與該樹脂內外的水分或氫反應而形成HCl，而且水分會與存在於添加劑或組成物內的硫化合物同樣地發生反應而產生SO2 或H2 S。又，水會與鹵素反應而產生HCl，甚而H2 S易與Cu反應而引起Cu配線的直接腐蝕或遷移。Specifically, the halogen present in the sealing layer, such as chlorine, will react with the moisture or hydrogen inside and outside the resin to form HCl, and the moisture will react with the sulfur compounds present in the additive or composition to form HCl. SO 2 or H 2 S. In addition, water reacts with halogen to generate HCl, and even H 2 S easily reacts with Cu to cause direct corrosion or migration of Cu wiring.

於本發明中，藉由吸附此等腐蝕之源由的鹵素，並進一步吸附導致SO2 產生的H2 O，可阻斷鹵化氫化(例如HCl化)而遏止腐蝕循環。再者，由於亦可防止H2 S氣體所造成之Cu的直接腐蝕，而能夠提供具有高可靠性的封止層。In the present invention, by adsorbing the halogen that is the source of corrosion, and further adsorbing the H 2 O that causes SO 2 to be generated, hydrogen halide (for example, HCl conversion) can be blocked and the corrosion cycle can be prevented. Furthermore, since the direct corrosion of Cu caused by H 2 S gas can also be prevented, a sealing layer with high reliability can be provided.

[實施發明之形態][The form of implementing the invention]

本發明之封止方法係構成半導體裝置之半導體元件及零件的封止方法，其特徵為藉由以下任一種方法來形成封止層：(1)使用含有環氧樹脂與有機金屬氧化物的組成物之方法1；(2)使用含有環氧樹脂與由有機金屬氧化物被覆之填料的組成物之方法2；或(3)將前述零件以有機金屬氧化物封止後，以環氧樹脂予以被覆之方法3。此特徵係共通或對應於下述各實施形態之技術特徵。The sealing method of the present invention is a method for sealing semiconductor elements and parts constituting a semiconductor device, and is characterized by forming a sealing layer by any of the following methods: (1) Using a composition containing epoxy resin and organic metal oxide Method 1 of the object; (2) Method 2 of using a composition containing epoxy resin and filler coated with organic metal oxide; or (3) After sealing the aforementioned parts with organic metal oxide, use epoxy resin Method of covering 3. This feature is common or corresponds to the technical features of the following embodiments.

就本發明之實施形態，有機金屬氧化物為具有前述通式(1)所示之結構的有機金屬氧化物，由可進一步防止構成半導體元件之各零件的腐蝕而言係特佳。According to the embodiment of the present invention, the organometallic oxide is an organometallic oxide having the structure represented by the aforementioned general formula (1), which is particularly preferable in terms of further preventing corrosion of the parts constituting the semiconductor element.

又，就本發明之封止方法，以塗佈法形成封止層，由裝置簡易且能以高精確度封止而言係較佳。Furthermore, in the sealing method of the present invention, it is preferable that the sealing layer is formed by a coating method, and the device is simple and can be sealed with high accuracy.

本發明之封止層，其特徵為至少含有環氧樹脂與具有前述通式(1)所示之結構的有機金屬氧化物。The sealing layer of the present invention is characterized by containing at least an epoxy resin and an organometallic oxide having the structure represented by the aforementioned general formula (1).

又，本發明之封止層，其特徵為由具有前述通式(1)所示之結構的有機金屬氧化物所構成。Furthermore, the sealing layer of the present invention is characterized by being composed of an organometallic oxide having a structure represented by the aforementioned general formula (1).

又，就本發明之實施形態，具有前述通式(1)所示之結構的有機金屬氧化物中氟原子數相對於碳原子數與氟原子數之總數的比值F/(C+F)為0.05≦F/(C+F)≦1.00的範圍內，由可進一步展現本發明之目的效果而言係較佳。Furthermore, in the embodiment of the present invention, the ratio of the number of fluorine atoms to the total number of carbon atoms and the total number of fluorine atoms in the organometallic oxide having the structure represented by the aforementioned general formula (1) is F/(C+F) The range of 0.05≦F/(C+F)≦1.00 is preferable in terms of further exhibiting the objective effect of the present invention.

又，通式(1)中以M表示之金屬原子係由Ti、Zr、Sn、Ta、Fe、Zn、Bi、Cu、Mg、Mn、Co、Ni、Ag及Al選出的至少一種，以可進一步提高封止結構內之水分、鹵素等的捕集性而言係較佳。In addition, the metal atom represented by M in the general formula (1) is at least one selected from Ti, Zr, Sn, Ta, Fe, Zn, Bi, Cu, Mg, Mn, Co, Ni, Ag, and Al, which can be It is preferable to further improve the trapping properties of moisture, halogen, etc. in the sealing structure.

又，含有由有機金屬氧化物被覆之填料，由可展現更優良的腐蝕性防止效果而言係較佳。In addition, it is preferable to include a filler coated with an organometallic oxide because it can exhibit a better corrosion prevention effect.

本發明之封止層形成用之混合液，其特徵為含有前述通式(A)所示之化合物、或具有前述通式(1)所示之結構的有機金屬氧化物與醇類。The mixed solution for forming a sealing layer of the present invention is characterized by containing a compound represented by the aforementioned general formula (A) or an organometallic oxide having a structure represented by the aforementioned general formula (1) and alcohols.

本發明之封止層之製造方法，其特徵為使用本發明之封止層形成用之混合液來製造。The manufacturing method of the sealing layer of the present invention is characterized by using the mixed solution for forming the sealing layer of the present invention.

又，本發明之半導體裝置其特徵為至少由半導體元件及零件所構成，且前述半導體元件或零件係由：由具有環氧樹脂及前述通式(1)所示之結構的有機金屬氧化物所構成的封止層、或藉由利用具有前述通式(1)所示之結構的有機金屬氧化物所構成的封止層所被覆。In addition, the semiconductor device of the present invention is characterized in that it is composed of at least semiconductor elements and parts, and the aforementioned semiconductor elements or parts are composed of epoxy resin and an organometallic oxide having the structure represented by the general formula (1). The formed sealing layer may be covered by a sealing layer formed of an organometallic oxide having the structure represented by the aforementioned general formula (1).

又，於本發明之半導體裝置中，由本發明之封止層所被覆之零件較佳為接合線或金屬銲點。In addition, in the semiconductor device of the present invention, the parts covered by the sealing layer of the present invention are preferably bonding wires or metal solder joints.

以下，就本發明與其構成要素及供實施本發明的形態･樣態進行詳細的說明。此外，本案中，「～」係以包含其前後所記載之數值作為下限值及上限值的意義使用。Hereinafter, the present invention, its constituent elements, and modes and aspects for implementing the present invention will be described in detail. In addition, in this case, "~" is used to include the numerical value described before and after it as the lower limit and upper limit.

《半導體元件及零件的封止方法》 於本發明之封止方法中，其特徵為藉由選自以下之方法來形成供封止半導體元件或零件的封止層： (1)使用含有環氧樹脂與有機金屬氧化物的組成物之方法1； (2)使用含有環氧樹脂與由有機金屬氧化物被覆之填料的組成物之方法2； (3)將零件以有機金屬氧化物封止後，以環氧樹脂予以被覆之方法3。"Semiconductor components and parts sealing method" In the sealing method of the present invention, it is characterized in that the sealing layer for sealing semiconductor elements or parts is formed by a method selected from the following: (1) Method 1 of using a composition containing epoxy resin and organic metal oxide; (2) Method 2 of using a composition containing an epoxy resin and a filler coated with an organic metal oxide; (3) Method 3 where the parts are sealed with organometallic oxide and then coated with epoxy resin.

本發明中所稱「零件」，係指構成半導體裝置之如後述圖2及圖3所示之金屬線(下稱「接合線」)、金屬端子(下稱「金屬銲點」)、構成基板等半導體裝置之半導體元件以外的構成零件。The term "parts" in the present invention refers to the metal wires (hereinafter referred to as "bonding wires"), metal terminals (hereinafter referred to as "metal solder joints"), and constituting substrates as shown in FIGS. 2 and 3 which will be described later. Components other than semiconductor devices such as semiconductor devices.

此處所稱「接合線」，係指圖2及圖3中以符號8表示者，係為了進行半導體元件3與外部的訊號交換，而用來連接構成半導體元件之電極與外部電極的零件。The "bonding wire" referred to here refers to the symbol 8 in FIGS. 2 and 3, and is a part used to connect the electrode constituting the semiconductor element and the external electrode in order to exchange signals between the semiconductor element 3 and the outside.

又，「金屬銲點」係圖2及圖3中以符號7表示者，係指用於各零件的安裝及零件間的連接的導電圖型。作為金屬銲點，有包含表面安裝用之焊墊、零件之安裝孔、通孔的導電圖型等。In addition, the "metal solder joint" is indicated by the symbol 7 in FIGS. 2 and 3, and refers to a conductive pattern used for the installation of each part and the connection between the parts. As metal solder joints, there are conductive patterns including solder pads for surface mounting, mounting holes for parts, and through holes.

圖1A～圖1C為表示本發明之封止方法之環氧樹脂與有機金屬氧化物、或單獨由有機金屬氧化物所形成之封止層之構成的一例的示意剖面圖。1A to 1C are schematic cross-sectional views showing an example of the structure of an epoxy resin and an organometallic oxide or a sealing layer formed of an organometallic oxide alone in the sealing method of the present invention.

圖1A所示類型A係表示本發明所規定之方法1之封止層4的構成者，係構成封止層4的方法，該封止層4係以有機金屬氧化物5，較佳為具有通式(1)所示之結構的有機金屬氧化物以粒子狀分散於環氧樹脂6中的狀態存在。Type A shown in FIG. 1A represents the composition of the sealing layer 4 of the method 1 specified in the present invention, and is a method of forming the sealing layer 4. The sealing layer 4 is made of organometallic oxide 5, preferably having The organometallic oxide of the structure represented by the general formula (1) exists in the state of being dispersed in the epoxy resin 6 in the form of particles.

又，圖1B所示類型B係表示本發明所規定之方法2之封止層4的構成，係構成封止層4的方法，該封止層4係以使藉由有機金屬氧化物5被覆表面之填料F分散於環氧樹脂6中的狀態存在。In addition, the type B shown in FIG. 1B represents the structure of the sealing layer 4 of the method 2 specified in the present invention, and is a method of forming the sealing layer 4, which is coated with an organic metal oxide 5 The filler F on the surface is dispersed in the epoxy resin 6 and exists.

再者，圖1C所示類型C係表示本發明所規定之方法3之封止層4的構成者，係首先將零件P，例如接合線或金屬銲點的表面藉由有機金屬氧化物5選擇性地封止，再形成單獨由有機金屬氧化物5所構成的封止層4後，藉由環氧樹脂6被覆全體的方法。Furthermore, the type C shown in FIG. 1C represents the composition of the sealing layer 4 of the method 3 specified in the present invention. First, the surface of the part P, such as the bonding wire or the metal solder joint, is selected by the organic metal oxide 5 It is a method in which a sealing layer 4 composed of an organometallic oxide 5 alone is formed, and then the whole is covered with an epoxy resin 6.

就形成本發明之封止層的方法，可適用濕式塗佈法；亦可使用例如採轉移方式或壓縮方式之填充法、或分配器法、旋轉塗佈法、澆鑄法、網版印刷法、模頭塗佈法、刮刀塗佈法、輥塗法、噴塗法、幕塗法、LB法(Langmuir-Blodgett法)、噴墨印刷法等濕式塗佈方式來形成封止層。As for the method of forming the sealing layer of the present invention, a wet coating method can be used; for example, a filling method using a transfer method or a compression method, or a dispenser method, a spin coating method, a casting method, or a screen printing method can also be used , Die coating method, knife coating method, roll coating method, spray method, curtain coating method, LB method (Langmuir-Blodgett method), inkjet printing method and other wet coating methods to form the sealing layer.

《半導體裝置的基本構成》 其次，就具有藉由上述說明之本發明之封止方法所形成的封止層之半導體裝置的構成，變更圖式加以說明。"Basic Structure of Semiconductor Devices" Next, the structure of a semiconductor device having a sealing layer formed by the sealing method of the present invention described above will be described with a modified drawing.

圖2為表示具有藉由本發明之封止方法之方法1所形成的封止層之半導體裝置的構造的一例的示意結構圖。2 is a schematic structural view showing an example of the structure of a semiconductor device having a sealing layer formed by the method 1 of the sealing method of the present invention.

圖2所示半導體裝置1係主要由以下所構成：電路基板11；封裝基板2；由與該封裝基板2電性接合之多個半導體元件3所構成的半導體層合體9；及供封止該半導體層合體9之上表面部區域的封止層4等。The semiconductor device 1 shown in FIG. 2 is mainly composed of: a circuit substrate 11; a packaging substrate 2; a semiconductor laminate 9 composed of a plurality of semiconductor elements 3 electrically bonded to the packaging substrate 2; The sealing layer 4 and the like in the upper surface area of the semiconductor laminate 9.

茲就半導體裝置1的詳細構成進一步加以說明。The detailed structure of the semiconductor device 1 will be further described.

圖2所示半導體裝置1，其中電路基板11與和半導體元件3電性接合之封裝基板2的間隙係藉由底部填充材10填滿。此底部填充材內配置有多個球形焊料凸塊12，經由該焊料凸塊，使電路基板11與封裝基板2電性連接。前述底部填充材10與構成本發明之封止層4的材料可由彼此不同的材料構成；而基於防止底部填充材10所保持之焊料凸塊12被腐蝕成分G，例如鹵素離子(Cl- )、水分、硫化氫氣體等所造成的腐蝕之觀點，則較佳包含本發明之有機金屬氧化物。In the semiconductor device 1 shown in FIG. 2, the gap between the circuit substrate 11 and the package substrate 2 electrically connected to the semiconductor element 3 is filled with an underfill material 10. A plurality of spherical solder bumps 12 are arranged in the underfill material, and the circuit substrate 11 and the package substrate 2 are electrically connected through the solder bumps. The bottom of the filler 10 and the material constituting the closure of the present invention, the stopper layer 4 may be mutually different materials; and of preventing the holding of the underfill material 10 solder bump 12 is G corrosive components, for example, a halogen ion (Cl -), From the viewpoint of corrosion caused by moisture, hydrogen sulfide gas, etc., it is preferable to include the organometallic oxide of the present invention.

半導體裝置1係藉由在封裝基板2上配置一個以上之半導體元件3或予以並列配置而構成，於圖2所示構成中，藉由如記憶體般層合多個半導體元件3，並將彼等以線接合電性進行與半導體元件間或封裝基板的連接，而構成半導體元件層合體9。The semiconductor device 1 is constructed by arranging more than one semiconductor element 3 on the package substrate 2 or by arranging them side by side. In the structure shown in FIG. 2, a plurality of semiconductor elements 3 are laminated like a memory, and each The electrical connection with the semiconductor elements or the package substrate is performed by wire bonding, and the semiconductor element laminate 9 is formed.

此時，第1層之半導體元件3係經由薄膜接著劑、熱硬化性接著劑等接著於封裝基板2。第2層以後之半導體元件3亦是經由絕緣性薄膜或熱硬化接著劑(未圖示)依序層合而成。At this time, the semiconductor element 3 of the first layer is bonded to the package substrate 2 via a thin film adhesive, a thermosetting adhesive, or the like. The semiconductor elements 3 after the second layer are also sequentially laminated through an insulating film or a thermosetting adhesive (not shown).

於此封裝基板2及各半導體元件3的端部設有金屬銲點7，各金屬銲點7間係藉由接合線8電性連接而成。金屬銲點7主要係以鋁為主成分；接合線8則可舉出例如金、銀、銅、鋁等構成材料，而於本發明中，接合線8其主成分較佳由銅所構成；甚而，更佳之樣態為在銅線的表面具有由含鈀之金屬材料所構成之被覆層的構造。The end portions of the package substrate 2 and each semiconductor element 3 are provided with metal solder joints 7, and the metal solder joints 7 are electrically connected by bonding wires 8. The metal solder joint 7 is mainly composed of aluminum; the bonding wire 8 can be composed of materials such as gold, silver, copper, aluminum, etc., and in the present invention, the main component of the bonding wire 8 is preferably composed of copper; Furthermore, a more preferable aspect is a structure having a coating layer made of a metal material containing palladium on the surface of the copper wire.

於此封裝基板2及多個半導體元件3的上表面部設有由本發明所規定之構造所構成的封止層4。圖2所示封止層4為藉由方法1之形成方法所形成的封止層，係由環氧樹脂所成之樹脂黏結劑6、本發明之具有通式(1)所示之結構的有機金屬氧化物5、填料F(無機填充材)所構成。The upper surface of the package substrate 2 and the plurality of semiconductor elements 3 is provided with a sealing layer 4 composed of a structure prescribed by the present invention. The sealing layer 4 shown in FIG. 2 is a sealing layer formed by the forming method of method 1, which is a resin adhesive 6 made of epoxy resin, and the structure of the present invention having the structure represented by general formula (1) It is composed of organometal oxide 5 and filler F (inorganic filler).

藉由將封裝基板2及多個半導體元件3以包含本發明之有機金屬氧化物5的封止層4封止，可防止由外部侵入而至之腐蝕成分G(例如鹵素離子、水分、硫化氫氣體等)，或者存在於封止層內之鹵素離子等一所產生之對接合線8或金屬銲點7的腐蝕。By sealing the packaging substrate 2 and the plurality of semiconductor elements 3 with the sealing layer 4 containing the organometallic oxide 5 of the present invention, it is possible to prevent the corrosive components G (such as halogen ions, moisture, hydrogen sulfide) from entering from the outside. Gas, etc.), or the corrosion of the bonding wire 8 or the metal solder joint 7 caused by halogen ions in the sealing layer.

圖2中，作為半導體元件3係示出層合3層之實例，惟亦較佳採用3層以上之構成；圖3係表示具備以更多層構成半導體元件3(例如64層)之半導體元件層合體的半導體裝置之構造的一例。基本的其他構成係與上述圖2相同。In FIG. 2, as the semiconductor element 3 is shown as an example in which three layers are laminated, it is also preferable to use a structure of more than three layers; FIG. 3 shows a semiconductor element with more layers constituting the semiconductor element 3 (for example, 64 layers) An example of the structure of a laminated semiconductor device. The other basic structure is the same as that of FIG. 2 described above.

《封止層》 其次，就本發明之封止層加以說明。"Sealing Layer" Next, the sealing layer of the present invention will be described.

本發明之封止層其特徵為，其係至少由環氧樹脂與具有前述通式(1)所示之結構的有機金屬氧化物所構成的封止層、或單獨構成具有前述通式(1)所示之結構的有機金屬氧化物的封止層。The sealing layer of the present invention is characterized in that it is a sealing layer composed of at least an epoxy resin and an organometallic oxide having a structure represented by the foregoing general formula (1), or a single structure having the foregoing general formula (1) ) Sealing layer of organometallic oxide of the structure shown.

[具有通式(1)所示之結構的有機金屬氧化物] 本發明之有機金屬氧化物較佳含有由下述通式(A)所示之化合物所製造之具有下述通式(1)所示之結構的有機金屬氧化物。[Organic metal oxide with the structure represented by the general formula (1)] The organometallic oxide of the present invention preferably contains an organometallic oxide having a structure represented by the following general formula (1) produced from a compound represented by the following general formula (A).

Figure 02_image011
通式(A)中，R表示氫原子、碳數1個以上之烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基。惟，R亦可包含氟原子作為取代基。M表示金屬原子。OR1 表示氟化烷氧基。x表示金屬原子的價數，y表示1與x之間的任意之整數。
Figure 02_image011
In the general formula (A), R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group having 1 or more carbon atoms. However, R may also contain a fluorine atom as a substituent. M represents a metal atom. OR 1 represents a fluorinated alkoxy group. x represents the valence of the metal atom, and y represents any integer between 1 and x.

Figure 02_image013
上述通式(1)中，R表示氫原子、碳數1個以上之烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基。惟，R亦可包含氟原子作為取代基。M表示金屬原子。OR1 表示氟化烷氧基。x表示金屬原子的價數，y表示1與x之間的任意之整數。n表示聚縮合度。
Figure 02_image013
In the above general formula (1), R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group having 1 or more carbon atoms. However, R may also contain a fluorine atom as a substituent. M represents a metal atom. OR 1 represents a fluorinated alkoxy group. x represents the valence of the metal atom, and y represents any integer between 1 and x. n represents the degree of polycondensation.

上述通式(1)中，OR1 表示氟化烷氧基。R1 表示經至少一個氟原子取代之烷基、芳基、環烷基、醯基、烷氧基或雜環基。各取代基的具體例係於後述。In the above general formula (1), OR 1 represents a fluorinated alkoxy group. R 1 represents an alkyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group or a heterocyclic group substituted with at least one fluorine atom. The specific example of each substituent is mentioned later.

R表示氫原子、碳數1個以上之烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基。或者，亦可為各個基團之至少一部分的氫經鹵素取代者。又，亦可為聚合物。R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group having 1 or more carbon atoms. Alternatively, at least a part of hydrogen in each group may be substituted with halogen. Moreover, it may be a polymer.

烷基係經取代或未取代者，具體例有甲基、乙基、丙基、丁基、二級丁基、三級丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基、二十一烷基、二十二烷基等，較佳為碳數為8以上者。又，亦可為此等之寡聚物、聚合物。Alkyl is substituted or unsubstituted, specific examples are methyl, ethyl, propyl, butyl, secondary butyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl Alkyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosan Group, docosyl group, behenyl group, etc., preferably having 8 or more carbon atoms. In addition, oligomers and polymers of this type may also be used.

烯基係經取代或未取代者，具體例有乙烯基、烯丙基、丁烯基、戊烯基、己烯基等，較佳為碳數為8以上者。又，亦可為此等之寡聚物或聚合物。The alkenyl group is substituted or unsubstituted, and specific examples include vinyl, allyl, butenyl, pentenyl, hexenyl, etc., preferably having 8 or more carbon atoms. In addition, such oligomers or polymers may also be used.

芳基係經取代或未取代者，具體例有苯基、甲苯基、4-氰基苯基、聯苯基、鄰,間,對三聯苯基、萘基、蒽基、菲基、芴基、9-苯基蒽基、9,10-二苯基蒽基、芘基等，較佳為碳數為8以上者。又，亦可為此等之寡聚物或聚合物。The aryl group is substituted or unsubstituted. Specific examples are phenyl, tolyl, 4-cyanophenyl, biphenyl, ortho, meta, p-terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl , 9-phenylanthryl, 9,10-diphenylanthryl, pyrenyl, etc., preferably having 8 or more carbon atoms. In addition, such oligomers or polymers may also be used.

經取代或未取代之烷氧基的具體例為甲氧基、正丁氧基、三級丁氧基、三氯甲氧基、三氟甲氧基等，較佳為碳數為8以上者。又，亦可為此等之寡聚物、聚合物。Specific examples of the substituted or unsubstituted alkoxy group include methoxy, n-butoxy, tertiary butoxy, trichloromethoxy, trifluoromethoxy, etc., preferably those with 8 or more carbon atoms . In addition, oligomers and polymers of this type may also be used.

經取代或未取代之環烷基的具體例為環戊基、環己基、降莰烷基、金剛烷基、4-甲基環己基、4-氰基環己基等，較佳為碳數為8以上者。又，亦可為此等之寡聚物或聚合物。Specific examples of substituted or unsubstituted cycloalkyl groups are cyclopentyl, cyclohexyl, norbornanyl, adamantyl, 4-methylcyclohexyl, 4-cyanocyclohexyl, etc., preferably the number of carbons is 8 or more. In addition, such oligomers or polymers may also be used.

經取代或未取代之雜環基的具體例，有吡咯基、吡咯啉基、吡唑基、吡唑啉基、咪唑基、三唑基、吡啶基、噠嗪基、嘧啶基、吡嗪基、三嗪基、吲哚基、苯并咪唑基、嘌呤基、喹啉基、異喹啉基、噌啉基、喹喔啉基、苯并喹啉基、茀酮基、二氰基茀酮基、咔唑基、噁唑基、噁二唑基、噻唑基、噻二唑基、苯并噁唑基、苯并噻唑基、苯并三唑基、雙苯并噁唑基、雙苯并噻唑基、雙苯并咪唑基等。又，亦可為此等之寡聚物或聚合物。Specific examples of substituted or unsubstituted heterocyclic groups include pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, imidazolyl, triazolyl, pyridyl, pyridazinyl, pyrimidinyl, and pyrazinyl , Triazinyl, indolyl, benzimidazolyl, purinyl, quinolinyl, isoquinolinyl, cinolinyl, quinoxalinyl, benzoquinolinyl, quinolinone, dicyanoquinolinone Group, carbazolyl, oxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl, benzoxazolyl, benzothiazolyl, benzotriazolyl, bisbenzoxazolyl, bisbenzo Thiazolyl, bisbenzimidazolyl, etc. In addition, such oligomers or polymers may also be used.

經取代或未取代之醯基的具體例，有甲醯基、乙醯基、丙醯基、丁醯基、異丁醯基、戊醯基、異戊醯基、新戊醯基、月桂醯基、肉荳蔻醯基、棕櫚醯基、硬脂醯基、草醯基、丙二醯基、琥珀醯基、戊二醯基、己二醯基、庚二醯基、辛二醯基、壬二醯基、癸二醯基、丙烯醯基、丙醯基、甲基丙烯醯基、巴豆醯基、異巴豆醯基、油醯基、芥子醯基、馬來醯基、富馬醯基、檸康醯基、中康醯基、樟腦醯基、苯甲醯基、鄰苯二甲醯基、間苯二甲醯基、對苯二甲醯基、萘甲醯基、甲苯甲醯基、氫脫水甲醯基、阿托甲醯基、肉桂醯基、呋喃醯基、噻吩甲醯基、煙醯基、異煙醯基、乙醇醯基、乳醯基、甘油醯基、羥丙二醯基、蘋果醯基、酒石醯基、對苯二甲醯基、芐醯基、水楊醯基、茴香醯基、香草醯基、藜蘆醯基、向日葵醯基、原兒茶醯基、沒食子醯基、乙醛醯基、丙酮醯基、乙醯乙醯基、中草醯基、中草醯氧基、草醯乙醯基、草醯乙醯基、乙醯丙醯基。此等醯基亦可經氟、氯、溴或碘等取代。較佳的是醯基的碳為8個以上。又，亦可為此等之寡聚物或聚合物。Specific examples of substituted or unsubstituted acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, pentamyl, isopentyl, neopentyl, lauryl, and myristyl Acetyl, palmitoyl, stearyl, succinyl, malonyl, succinyl, glutaryl, hexadiyl, pimelic acid, octanedicyl, azelaic, Sebacic acid, acrylic acid, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, oleic acid, mustard acid, maleic acid, fumaric acid, citraconic acid, methacrylic acid, Camphoryl, benzyl, phthalate, m-phthalate, terephthalate, naphthyl, tolyl, hydrodehydroformyl, atormethal Base, cinnamyl, furanyl, thienyl, nicotinyl, isonicotinyl, ethanolyl, lactoyl, glyceryl, hydroxypropyl diacetate, apple saccharin, tartrate, to Phthalyl, benzyl, salicyl, fennel, vanillyl, veratrum, sunflower, protocatechu, gallate, acetaldehyde, acetaldehyde , Acetyl acetyl, acetamide, acetoxy, acetamide, acetamide, acetamide. These acyl groups may also be substituted by fluorine, chlorine, bromine or iodine. Preferably, the acyl group has 8 or more carbons. In addition, such oligomers or polymers may also be used.

通式(1)中以M表示之金屬原子可舉出例如Ti、Zr、Sn、Si、Ta、Yb,Y、Al、Zn、Co、In、Fe、Mo、Ni、Pd、Ag、Sr、Bi、Cu、Mg、Mn等，亦能以由此等選出的至少一種、或二種以上所構成。其中，較佳為由Ti、Zr、Sn、Ta、Fe、Zn、Bi、Cu、Mg、Mn、Co、Ni、Ag及Al選出的至少一種。The metal atom represented by M in the general formula (1) can include, for example, Ti, Zr, Sn, Si, Ta, Yb, Y, Al, Zn, Co, In, Fe, Mo, Ni, Pd, Ag, Sr, Bi, Cu, Mg, Mn, etc. can also be composed of at least one or two or more selected from these. Among them, it is preferably at least one selected from Ti, Zr, Sn, Ta, Fe, Zn, Bi, Cu, Mg, Mn, Co, Ni, Ag, and Al.

以下例示供形成本發明之具有通式(1)所示之結構的有機金屬氧化物的金屬烷氧化物、金屬羧酸鹽及氟醇之具體組合。惟，本發明非限定於此。The following exemplifies specific combinations of metal alkoxides, metal carboxylates and fluoroalcohols for forming the organometallic oxide having the structure represented by the general formula (1) of the present invention. However, the present invention is not limited to this.

前述金屬烷氧化物、金屬羧酸鹽與氟醇 (R'-OH)係根據以下反應路徑圖I形成本發明之有機金屬氧化物。於此，(R'-OH)可例示以下F-1～F-16之結構。The aforementioned metal alkoxides, metal carboxylates and fluoroalcohols (R'-OH) forms the organometallic oxide of the present invention according to the following reaction scheme I. Here, (R'-OH) can exemplify the following structures of F-1 to F-16.

Figure 02_image015
Figure 02_image015

Figure 02_image017
Figure 02_image017

本發明之金屬烷氧化物或金屬羧酸鹽可例示以下M(OR)n 或M(OCOR)n 所示之化合物，本發明之有機金屬氧化物係根據與前述(R'-OH：F-1～F-16)之組合，而形成具有下述例示化合物編號1～145之結構的化合物(茲參照下述例示化合物I、II、III、IV及V)。本發明之有機金屬氧化物非限定於此。The metal alkoxide or metal carboxylate of the present invention can be exemplified by the following compounds represented by M(OR) n or M(OCOR) n . The organometal oxide of the present invention is based on the aforementioned (R'-OH:F- 1 to F-16) to form a compound having the structure of the following exemplary compound numbers 1 to 145 (refer to the following exemplary compounds I, II, III, IV, and V). The organometallic oxide of the present invention is not limited to this.

Figure 02_image019
Figure 02_image019

Figure 02_image021
Figure 02_image021

Figure 02_image023
Figure 02_image023

Figure 02_image025
Figure 02_image025

Figure 02_image027
Figure 02_image027

就本發明之封止層，其特徵為使用至少1種上述所說明之本發明之有機金屬氧化物，較佳使用金屬物種不同的2種以上之有機金屬氧化物。The sealing layer of the present invention is characterized by using at least one of the organometallic oxides of the present invention described above, and preferably using two or more organometallic oxides of different metal species.

(有機金屬氧化物的反應性) 本發明之有機金屬氧化物係顯示如以下反應路徑圖II及反應路徑圖III所示之反應性者。此外，在燒結後之有機金屬氧化物之聚縮合物的結構式中，「O-M」部的「M」係進一步具有取代基，但予以省略。(Reactivity of organometallic oxide) The organometallic oxide of the present invention shows reactivity as shown in the following reaction pathway diagram II and reaction pathway diagram III. In addition, in the structural formula of the polycondensate of the organic metal oxide after sintering, the "M" of the "O-M" part further has a substituent, but is omitted.

Figure 02_image029
Figure 02_image029

例如當金屬物種不同的2種金屬氧化物共存時，係具有如下述反應路徑圖III所示之反應性。For example, when two metal oxides with different metal species coexist, they have reactivity as shown in the following reaction pathway diagram III.

Figure 02_image031
Figure 02_image031

上述有機金屬氧化物藉由燒結或紫外線照射等進行聚縮合而形成的有機薄膜係具有如以下反應路徑圖IV所示之反應性。The organic thin film formed by polycondensation of the above-mentioned organometal oxide by sintering or ultraviolet irradiation has reactivity as shown in the following reaction pathway diagram IV.

若為反應路徑圖IV時，係藉由來自系統外的水分(H2 O)而水解，而釋放出屬撥水性或疏水性物質的氟醇(R'-OH)。藉此氟醇，可進一步防止水分穿透電子裝置內部。In the case of reaction scheme IV, it is hydrolyzed by moisture (H 2 O) from outside the system to release fluoroalcohol (R'-OH) which is a water-repellent or hydrophobic substance. This fluoroalcohol can further prevent moisture from penetrating the inside of the electronic device.

亦即，本發明之有機金屬氧化物係具此特徵：由於藉由水解而生成的氟醇為撥水性或疏水性，除了原本的乾燥性(除濕性)，再藉由與水分的反應而附加撥水機能，而使封止性發揮相乘效果(協同效應)。That is, the organometallic oxide of the present invention has this characteristic: Since the fluoroalcohol produced by hydrolysis is water-repellent or hydrophobic, in addition to the original dryness (dehumidification), it is added by the reaction with moisture. Water-repellent function, and the sealing performance has a synergistic effect (synergistic effect).

此外，下述結構式中，「O-M」部的「M」係進一步具有取代基，但予以省略。In addition, in the following structural formula, the "M" of the "O-M" part further has a substituent, but it is omitted.

Figure 02_image033
Figure 02_image033

(有機金屬氧化物之製造方法) 本發明之封止層之製造方法中，其特徵為該封止層所含有之有機金屬氧化物係使用金屬烷氧化物或金屬羧酸鹽與氟醇之混合液來製造。(Manufacturing method of organic metal oxide) In the method for producing a sealing layer of the present invention, the organometal oxide contained in the sealing layer is produced using a mixture of metal alkoxide or metal carboxylate and fluoroalcohol.

本發明之有機金屬氧化物之製造方法可舉出對金屬烷氧化物或金屬羧酸鹽添加氟醇而調成混合液再予以攪拌混合後，視需求添加水與觸媒並於既定溫度使其反應的方法。The production method of the organometallic oxide of the present invention can include adding a fluoroalcohol to a metal alkoxide or a metal carboxylate to prepare a mixed solution and then stir and mix, then add water and a catalyst as required and make it at a predetermined temperature. The method of reaction.

進行溶膠-凝膠反應時，以促進水解・聚縮合反應為目的亦可添加如下述所示之可作為水解･聚合反應的觸媒者。作為溶膠-凝膠反應之水解･聚合反應的觸媒使用者係「藉由最新溶膠-凝膠法來製作機能性薄膜之技術」(平島碩著，綜合技術中心股份有限公司，P29)或「溶膠-凝膠法的科學」(作花濟夫著，AGNE承風公司，P154)等所記載在一般的溶膠-凝膠反應中所使用的觸媒。例如，就酸觸媒可舉出鹽酸、硝酸、硫酸、磷酸、乙酸、草酸、酒石酸、甲苯磺酸等無機及有機酸類等。When performing a sol-gel reaction, for the purpose of promoting the hydrolysis and polycondensation reaction, it is also possible to add a catalyst that can be used as a hydrolysis and polymerization reaction as shown below. As a catalyst for the hydrolysis and polymerization of the sol-gel reaction, the user is "Technology for the production of functional thin films by the latest sol-gel method" (Hiroshima Hirashima, General Technology Center Co., Ltd., P29) or " The "Science of Sol-Gel Process" (by Hana Chio, AGNE Chengfeng Co., Ltd., P154) describes the catalysts used in general sol-gel reactions. For example, the acid catalyst includes inorganic and organic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, tartaric acid, and toluenesulfonic acid.

較佳之觸媒用量，相對於作為有機金屬氧化物的原料之金屬烷氧化物或金屬羧酸鹽1莫耳為2莫耳當量以下，再更佳為1莫耳當量以下。The preferred amount of the catalyst is 2 mole equivalents or less, and more preferably 1 mole equivalent or less, relative to 1 mole of the metal alkoxide or metal carboxylate as the raw material of the organometallic oxide.

進行溶膠-凝膠反應時，較佳的水添加量，相對於作為有機金屬氧化物的原料之金屬烷氧化物或金屬羧酸鹽1莫耳為40莫耳當量以下，更佳為10莫耳當量以下，再更佳為5莫耳當量以下。When carrying out a sol-gel reaction, the preferred amount of water added is 40 mol equivalent or less, more preferably 10 mol relative to 1 mol of the metal alkoxide or metal carboxylate as the raw material of the organic metal oxide It is less than equivalent, and more preferably less than 5 molar equivalent.

本發明中，較佳之溶膠-凝膠反應的反應濃度、溫度、時間由於係與所用金屬烷氧化物或金屬羧酸鹽的種類或分子量等各條件彼此相關，而無法一概而論。亦即，當烷氧化物或金屬羧酸鹽的分子量較高時、或反應濃度較高時，若將反應溫度設得較高，或將反應時間設得過長，則反應生成物的分子量會隨著水解、聚縮合反應而上升，而有可能成高黏度化或凝膠化。從而，一般的較佳反應濃度，以溶液中之固體成分的質量%濃度計約為1～50%的範圍內，更佳為5～30%的範圍內。又，反應溫度係隨反應時間而異，一般為0～150℃的範圍內，較佳為1～100℃的範圍內，更佳為20～60℃的範圍內、反應時間為1～50小時的範圍內。In the present invention, the preferred reaction concentration, temperature and time of the sol-gel reaction are related to each other, such as the type or molecular weight of the metal alkoxide or metal carboxylate used, and cannot be generalized. That is, when the molecular weight of the alkoxide or metal carboxylate is high, or the reaction concentration is high, if the reaction temperature is set high, or the reaction time is set too long, the molecular weight of the reaction product will be With the increase of hydrolysis and polycondensation reaction, it may become high viscosity or gelation. Therefore, the generally preferred reaction concentration is in the range of about 1-50%, more preferably in the range of 5-30%, based on the mass% concentration of the solid content in the solution. In addition, the reaction temperature varies with the reaction time, and is generally in the range of 0 to 150°C, preferably in the range of 1 to 100°C, more preferably in the range of 20 to 60°C, and the reaction time is 1 to 50 hours. In the range.

於本發明中，封止層所含有之前述有機金屬氧化物中氟原子數相對於碳原子數與氟原子數之總數的比值F/(C+F)為0.05～1.00的範圍內，由撥水性或疏水性觀點而現較佳。亦即，本發明之有機金屬錯氧化物中的氟比率(F/(C+F))較佳滿足下述式(a)所規定之條件。In the present invention, the ratio F/(C+F) of the number of fluorine atoms to the total number of carbon atoms and the total number of fluorine atoms in the aforementioned organometallic oxide contained in the sealing layer is in the range of 0.05 to 1.00, It is currently preferred from the viewpoint of water or hydrophobicity. That is, the fluorine ratio (F/(C+F)) in the organometallic complex oxide of the present invention preferably satisfies the condition specified by the following formula (a).

Figure 02_image035
式(a)的測定意義係將藉由溶膠-凝膠法所製作之有機薄膜需要一定量以上的氟原子此要件數值化者。上述式(a)中的F及C係分別表示氟原子及碳原子的濃度。
Figure 02_image035
The measurement meaning of the formula (a) is to quantify the requirement that the organic film produced by the sol-gel method requires a certain amount of fluorine atoms. F and C in the above formula (a) respectively represent the concentration of fluorine atoms and carbon atoms.

更佳之範圍係0.20≦F/(C+F)≦0.60的範圍內。A more preferable range is within the range of 0.20≦F/(C+F)≦0.60.

上述氟原子的比率可將使用於有機薄膜層形成的溶膠-凝膠液塗佈於矽晶圓上而製作薄膜後，對該薄膜藉由採SEM･EDS(Energy Dispersive X-ray Spectoroscopy ：能量分散型X光分析裝置)之元素分析，分別求出氟原子及碳原子的濃度。作為SEM･EDS裝置的一例，可舉出JSM-IT100(日本電子公司製)。The above-mentioned ratio of fluorine atoms can be used to form a sol-gel liquid used in the formation of an organic thin film layer on a silicon wafer to form a thin film, and then use SEM･EDS (Energy Dispersive X-ray Spectoroscopy ：Energy dispersive X-ray analyzer) elemental analysis to obtain the concentration of fluorine atoms and carbon atoms. As an example of the SEM and EDS device, JSM-IT100 (manufactured by JEOL Ltd.) can be cited.

SEM･EDS分析係具有能以高速、高靈敏度精確度良好地檢測出元素之特徵。The SEM･EDS analysis system has the characteristics of detecting elements with high speed, high sensitivity and accuracy.

本發明之有機金屬氧化物，只要是可使用溶膠-凝膠法而製作者則特不予限制，可舉出如「溶膠-凝膠法的科學」P13、P20所介紹的金屬，例如Ti、Zr、Sn、Si、Ta、Yb、Y、Al、Zn、Co、In、Fe、Mo、Ni、Pd、Ag、Sr、Bi、Cu、Mg、Mn等，亦能以由此等選出的至少一種、或二種以上所構成。其中，為由Ti、Zr、Sn、Ta、Fe、Zn、Bi、Cu、Mg、Mn、Co、Ni、Ag及Al選出的至少一種，由可獲得本發明之效果的觀點而言係較佳。The organometallic oxide of the present invention is not limited as long as it can be produced by the sol-gel method. Examples include metals such as those described in "Science of the Sol-gel Method" P13 and P20, such as Ti, Zr, Sn, Si, Ta, Yb, Y, Al, Zn, Co, In, Fe, Mo, Ni, Pd, Ag, Sr, Bi, Cu, Mg, Mn, etc. can also be selected from at least One, or two or more types. Among them, at least one selected from Ti, Zr, Sn, Ta, Fe, Zn, Bi, Cu, Mg, Mn, Co, Ni, Ag, and Al is preferable from the viewpoint of obtaining the effects of the present invention .

又，要起始此等溶膠-凝膠液的聚合反應，較佳照射可於低溫下進行聚合反應的電漿、臭氧或紫外光，使用紫外光當中的真空紫外線(亦稱VUV)，由於可提升薄膜表面的平滑性而較佳。In addition, to initiate the polymerization reaction of these sol-gel solutions, it is preferable to irradiate plasma, ozone or ultraviolet light, which can carry out the polymerization reaction at a low temperature, and use vacuum ultraviolet light (also known as VUV) among the ultraviolet light. It is better to improve the smoothness of the film surface.

真空紫外線處理中之紫外線的產生手段，可舉出例如金屬鹵化物燈、高壓水銀燈、低壓水銀燈、氙弧燈、碳弧燈、準分子燈、UV光雷射等，但不特別限定，較佳使用準分子燈。The means for generating ultraviolet rays in vacuum ultraviolet treatment include, for example, metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, UV light lasers, etc., but are not particularly limited, preferably Use excimer lights.

紫外線照射可應用分批處理或連續處理，可根據所用基材的形狀來適宜選定。當形成封止層之基材為長型薄膜狀時，可藉由邊予以運送邊於具備如上述之紫外線產生源的乾燥區連續地照射紫外線來進行。紫外線照射所需時間係隨所用基材或含有有機金屬氧化物等之塗佈液的組成、濃度而異，一般為0.1秒～10分鐘，較佳為0.5秒～3分鐘。The ultraviolet irradiation can be applied in batch or continuous processing, and can be appropriately selected according to the shape of the substrate used. When the base material forming the sealing layer is in the form of a long film, it can be carried out by continuously irradiating ultraviolet rays in a drying zone equipped with an ultraviolet generating source as described above while being transported. The time required for ultraviolet irradiation varies with the composition and concentration of the substrate used or the coating liquid containing organometallic oxide, etc., and is generally 0.1 second to 10 minutes, preferably 0.5 second to 3 minutes.

就塗膜面所受能量，基於形成均勻且堅固的薄膜之觀點，較佳為1.0J/cm2 以上，更佳為1.5J/cm2 以上。又，同樣地基於避免過度照射紫外線之觀點，較佳為14.0J/cm2 以下，更佳為12.0J/cm2 以下，特佳為10.0J/cm2 以下。Suffered on the coating film surface energy, based on a uniform and strong film of view, preferably 1.0J / cm 2 or more, more preferably 1.5J / cm 2 or more. Also, from the viewpoint of avoiding excessive ultraviolet irradiation, it is preferably 14.0 J/cm 2 or less, more preferably 12.0 J/cm 2 or less, and particularly preferably 10.0 J/cm 2 or less.

又，照射真空紫外線(VUV)時的氧氣濃度較佳採300～10000體積ppm(1體積%)，更佳為500～5000體積ppm。藉由調整於此種氧氣濃度的範圍，可防止封止層氧氣過多，而能夠防止吸收水分所致之劣化。In addition, the oxygen concentration when irradiating vacuum ultraviolet (VUV) is preferably 300 to 10,000 volume ppm (1 volume %), more preferably 500 to 5000 volume ppm. By adjusting the oxygen concentration in this range, it is possible to prevent the sealing layer from being over-oxygenated and to prevent deterioration due to moisture absorption.

(VUV：真空紫外線照射處理) M.D.COM(股)製準分子照射裝置MODEL：MECL-M-1-200 波長：172nm 燈封入氣體：Xe 準分子光強度：6J/cm2 (172nm) 試料與光源的距離：2mm 載臺加熱溫度：80℃ 照射裝置內的氧氣濃度：0.3體積% 照射真空紫外線(VUV)時，此等氧氣以外的氣體較佳使用乾燥惰性氣體，尤其是由成本觀點而言，較佳採用乾燥氮氣。(VUV: vacuum ultraviolet radiation treatment) MDCOM (stock) excimer irradiation device MODEL: MECL-M-1-200 Wavelength: 172nm Lamp enclosed gas: Xe Excimer light intensity: 6J/cm 2 (172nm) of sample and light source Distance: 2mm Carrier heating temperature: 80℃ Oxygen concentration in the irradiation device: 0.3% by volume When irradiating vacuum ultraviolet (VUV), it is better to use dry inert gas for gases other than oxygen, especially from a cost point of view. Preferably use dry nitrogen.

就此等真空紫外線照射處理的細節，可參照例如日本特開2012-086394號公報之段落(0055)～(0091)、日本特開2012-006154號公報之段落(0049)～(0085)、日本特開2011-251460號公報之段落(0046)～(0074)等所記載的內容。For details of the vacuum ultraviolet irradiation treatment, refer to, for example, paragraphs (0055) to (0091) of JP 2012-086394, paragraphs (0049) to (0085) of JP 2012-006154, and Japanese Patent Open the contents described in paragraphs (0046) to (0074) of the 2011-251460 bulletin.

此外，同樣地為了進行聚合反應，而藉由110℃、30分鐘以上的加熱處理來促進反應。因此，對封止層添加本發明之有機金屬氧化物時，較佳藉由加熱處理來促進反應；又，對本發明之有機金屬氧化物進行藉由塗敷之單獨製程處理時，能以加熱處理或準分子光照射來進行聚合反應。In addition, in order to proceed the polymerization reaction similarly, the reaction is promoted by heat treatment at 110°C for 30 minutes or more. Therefore, when the organometallic oxide of the present invention is added to the sealing layer, it is preferable to promote the reaction by heat treatment. Moreover, when the organometallic oxide of the present invention is subjected to a separate process by coating, it can be treated by heat Or excimer light irradiation to carry out the polymerization reaction.

[環氧樹脂] 供形成本發明之封止層的封止層形成用組成物中，除上述所說明之有機金屬氧化物外，作為黏結劑成分，係至少含有環氧樹脂。[Epoxy resin] The composition for forming the sealing layer for forming the sealing layer of the present invention contains at least epoxy resin as a binder component in addition to the organometallic oxide described above.

可適用於本發明之封止層的環氧樹脂可舉出例如聯苯型環氧樹脂；雙酚A型環氧樹脂、雙酚F型環氧樹脂、四甲基雙酚F型環氧樹脂等雙酚型環氧樹脂；二苯乙烯型環氧樹脂；酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等酚醛清漆型環氧樹脂；三苯基甲烷型環氧樹脂、烷基改性三苯基甲烷型環氧樹脂等多官能環氧樹脂；具有伸苯基骨架之酚芳烷基型環氧樹脂、具有伸聯苯基骨架之酚芳烷基型環氧樹脂等聯苯芳烷基型環氧樹脂；二羥基萘型環氧樹脂、將二羥基萘之二聚物進行環氧丙基醚化而得之環氧樹脂等萘酚型環氧樹脂；異氰脲酸三縮水甘油酯、異氰脲酸單烯丙基二縮水甘油酯等含三嗪核環氧樹脂；二環戊二烯改性酚型環氧樹脂等橋聯環狀烴化合物改性酚型環氧樹脂等。此等可單獨使用或組合2種以上使用。Examples of epoxy resins applicable to the sealing layer of the present invention include biphenyl type epoxy resins; bisphenol A type epoxy resins, bisphenol F type epoxy resins, and tetramethyl bisphenol F type epoxy resins. Bisphenol type epoxy resin; stilbene type epoxy resin; novolac type epoxy resin such as phenol novolac type epoxy resin, cresol novolak type epoxy resin; triphenylmethane type epoxy resin, alkyl Multifunctional epoxy resins such as modified triphenylmethane type epoxy resin; phenol aralkyl type epoxy resin with phenylene skeleton, phenol aralkyl type epoxy resin with phenylene skeleton, etc. Phenyl aralkyl epoxy resin; dihydroxy naphthalene epoxy resin, epoxy resin obtained by glycidyl etherification of dihydroxy naphthalene dimer; naphthol epoxy resin; isocyanuric acid Triglycidyl ester, monoallyl diglycidyl isocyanurate, etc. containing triazine core epoxy resin; dicyclopentadiene modified phenol epoxy resin and other bridged cyclic hydrocarbon compounds modified phenolic ring Oxygen resin, etc. These can be used alone or in combination of two or more kinds.

又，環氧樹脂可使用市售品。可舉出例如作為雙酚A型環氧樹脂的AER-X8501(旭化成股份有限公司製造，商品名)、R-301(三菱化學股份有限公司製造，商品名)、YL-980(三菱化學股份有限公司製造，商品名)；作為雙酚F型環氧樹脂的YDF-170(東都化成股份有限公司製造，商品名)、YL-983(三菱化學股份有限公司製造，商品名)；作為雙酚AD型環氧樹脂的R-1710(三井化學股份有限公司製造，商品名)；作為苯酚酚醛清漆型環氧樹脂的N-730S(迪愛生(DIC)股份有限公司製造，商品名)、庫阿萊克斯(Quatrex)-2010(陶氏化學(Dow Chemical)股份有限公司製造，商品名)；作為甲酚酚醛清漆型環氧樹脂的YDCN-702S(東都化成股份有限公司製造，商品名)、EOCN-100 (日本化藥股份有限公司製造，商品名)；作為多官能環氧樹脂的EPPN-501(日本化藥公司製造，商品名)、TACTIX-742(陶氏化學(Dow Chemical)股份有限公司製造，商品名)、VG-3010(三井化學股份有限公司製造，商品名)、1032S(三菱化學股份有限公司製造，商品名)；作為具有萘骨架的環氧樹脂的HP-4032(迪愛生(DIC)股份有限公司製造，商品名)；作為脂環式環氧樹脂的EHPE-3150、CEL-3000(均為大賽璐(Daicel)股份有限公司製造，商品名)、DME-100(新日本理化股份有限公司製造，商品名)、EX-216L(長瀨(Nagase)化成工業股份有限公司製造，商品名)；作為脂肪族環氧樹脂的W-100(新日本理化股份有限公司製造，商品名)；作為胺型環氧樹脂的ELM-100(住友化學股份有限公司製造，商品名)、YH-434L(東都化成股份有限公司製造，商品名)、泰拉德(TETRAD)-X、泰拉德(TETRAD)-C(均為三菱瓦斯化學股份有限公司製造，商品名)、630、630LSD(均為三菱化學股份有限公司製造，商品名)；作為間苯二酚型環氧樹脂的丹納考爾(Denacol)EX-201(長瀨(Nagase)化成工業股份有限公司製造，商品名)；作為新戊二醇型環氧樹脂的丹納考爾(Denacol)EX-211(長瀨(Nagase)化成工業股份有限公司製造，商品名)；作為己二醇型環氧樹脂的丹納考爾(Denacol)EX-212(長瀨(Nagase)化成工業股份有限公司製造，商品名)；作為乙二醇/丙二醇型環氧樹脂的丹納考爾(Denacol)EX系列(EX-810、811、850、851、821、830、832、841、861(均為長瀨(Nagase)化成工業股份有限公司製造，商品名))、環氧樹脂E-XL-24、E-XL-3L(均為三井化學股份有限公司製造，商品名)等。此等環氧樹脂當中，基於離子性雜質較少且反應性優良之觀點，較佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AD型環氧樹脂及胺型環氧樹脂。此等環氧樹脂可單獨使用1種或組合2種以上使用。In addition, a commercially available product can be used for the epoxy resin. Examples include AER-X8501 (manufactured by Asahi Kasei Co., Ltd., trade name), R-301 (manufactured by Mitsubishi Chemical Co., Ltd., trade name), and YL-980 (Mitsubishi Chemical Co., Ltd. Company manufacture, trade name); YDF-170 (manufactured by Dongdu Chemical Co., Ltd., trade name), YL-983 (manufactured by Mitsubishi Chemical Co., Ltd., trade name) as bisphenol F type epoxy resin; as bisphenol AD Type epoxy resin R-1710 (manufactured by Mitsui Chemicals Co., Ltd., trade name); N-730S (manufactured by DIC Co., Ltd., trade name) as phenol novolac type epoxy resin, Kualek Quatrex-2010 (manufactured by Dow Chemical Co., Ltd., trade name); YDCN-702S (manufactured by Dongdu Chemical Co., Ltd., trade name) as cresol novolac epoxy resin, EOCN- 100 (manufactured by Nippon Kayaku Co., Ltd., trade name); EPPN-501 (manufactured by Nippon Kayaku Co., Ltd., trade name) as a multifunctional epoxy resin, TACTIX-742 (manufactured by Dow Chemical Co., Ltd.) , Trade name), VG-3010 (manufactured by Mitsui Chemicals Co., Ltd., trade name), 1032S (manufactured by Mitsubishi Chemical Co., Ltd., trade name); HP-4032 (DIC) as an epoxy resin having a naphthalene skeleton ) Co., Ltd., trade name); EHPE-3150, CEL-3000 (both are manufactured by Daicel Co., Ltd., trade name) as alicyclic epoxy resins, DME-100 (New Japan Physical Chemical Co., Ltd. Co., Ltd., trade name), EX-216L (Nagase Chemical Industry Co., Ltd., trade name); as aliphatic epoxy resin W-100 (New Japan Rika Co., Ltd., trade name) ; ELM-100 (manufactured by Sumitomo Chemical Co., Ltd., trade name), YH-434L (manufactured by Dongdu Chemical Co., Ltd., trade name), TETRAD-X, and Tyrad (TETRAD)-C (all made by Mitsubishi Gas Chemical Co., Ltd., trade name), 630, 630LSD (all made by Mitsubishi Chemical Co., Ltd., trade name); Tanakao as resorcinol type epoxy resin Denacol EX-201 (manufactured by Nagase Chemical Industry Co., Ltd., trade name); Denacol EX-211 (Nagase) as a neopentyl glycol type epoxy resin Manufactured by Chemical Industry Co., Ltd., trade name); Denacol EX-212 (manufactured by Nagase Chemical Industry Co., Ltd., trade name) as a hexylene glycol epoxy resin; As an ethylene glycol/propylene glycol type epoxy resin, Denacol EX series (EX-810, 811, 850, 851, 821, 830, 832, 841, 861 are all Nagase Chemical Industries Co., Ltd., trade name)), epoxy resin E-XL-24, E-XL-3L (all manufactured by Mitsui Chemicals Co., Ltd., trade name), etc. Among these epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, and amine type epoxy resins are preferred from the viewpoint of less ionic impurities and excellent reactivity. Oxy resin. These epoxy resins can be used individually by 1 type or in combination of 2 or more types.

又，就本發明之封止層，除上述所說明之環氧樹脂外，在不損及本發明目的效果的範圍內，亦可併用向來周知之各種樹脂成分。In addition, in addition to the epoxy resin described above, for the sealing layer of the present invention, various conventionally known resin components may be used in combination within a range that does not impair the objective effects of the present invention.

[添加劑] 就本發明之封止層，除上述所說明之有機金屬氧化物及環氧樹脂外，在不損及本發明目的效果的範圍內，亦可添加各種添加劑。[additive] With regard to the sealing layer of the present invention, in addition to the organometallic oxide and epoxy resin described above, various additives may be added within a range that does not impair the objective effects of the present invention.

(硬化劑) 可適用於本發明之封止層的硬化劑，可使用例如加成聚合型硬化劑、觸媒型硬化劑、縮合型硬化劑此3種類型。(hardener) As the hardener applicable to the sealing layer of the present invention, three types can be used, for example, an addition polymerization hardener, a catalyst hardener, and a condensation hardener.

加成聚合型硬化劑，除例如二伸乙三胺(DETA)、三伸乙四胺(TETA)或間二甲苯二胺(MXDA)等脂肪族多胺、二胺基二苯甲烷(DDM)、間苯二胺(MPDA)或二胺基二苯碸(DDS)等芳香族多胺外，尚可舉出包含雙氰胺(DICY)或有機酸二醯肼等的多胺化合物；六氫鄰苯二甲酸酐(HHPA)或甲基四氫鄰苯二甲酸酐(MTHPA)等脂環族酸酐；包含偏苯三酸酐(TMA)、均苯四酸酐(PMDA)或二苯甲酮四羧酸(BTDA)等芳香族酸酐等的酸酐、使酚類(苯酚、萘酚等)與醛類縮合而合成之酚醛清漆型酚樹脂等酚樹脂、聚乙烯基酚為代表之酚聚合物等聚酚化合物、異氰酸酯預聚物或嵌段化異氰酸酯等異氰酸酯化合物、含羧酸之聚酯樹脂等有機酸類等。惟，非限定於此等。Addition polymerization hardeners, except for aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA) or m-xylene diamine (MXDA), diaminodiphenylmethane (DDM) In addition to aromatic polyamines such as, m-phenylenediamine (MPDA) or diaminodiphenyl sulfide (DDS), polyamine compounds including dicyandiamide (DICY) or organic acid dihydrazine; hexahydro Phthalic anhydride (HHPA) or methyltetrahydrophthalic anhydride (MTHPA) and other alicyclic anhydrides; including trimellitic anhydride (TMA), pyromellitic anhydride (PMDA) or benzophenone tetracarboxylic acid (BTDA) ) And other aromatic acid anhydrides, phenolic resins such as novolac type phenol resin synthesized by condensation of phenols (phenol, naphthol, etc.) with aldehydes, polyphenol compounds such as phenol polymers represented by polyvinyl phenol, Isocyanate compounds such as isocyanate prepolymers or blocked isocyanates, organic acids such as carboxylic acid-containing polyester resins, etc. However, it is not limited to this.

觸媒型硬化劑可舉出例如苯甲基二甲胺(BDMA)、2,4,6-參二甲胺基甲基酚(DMP-30)等三級胺化合物、2-甲基咪唑、2-乙基-4-甲基咪唑(EMI24)等咪唑化合物、BF3 錯合物等路易士酸等。惟，非限定於此等。Catalytic hardeners include, for example, tertiary amine compounds such as benzyldimethylamine (BDMA), 2,4,6-dimethylaminomethylphenol (DMP-30), 2-methylimidazole, Imidazole compounds such as 2-ethyl-4-methylimidazole (EMI24), Lewis acid such as BF 3 complexes, etc. However, it is not limited to this.

縮合型硬化劑可舉出例如甲階酚醛型酚樹脂等酚系硬化劑、如含羥甲基之尿素樹脂之尿素樹脂、如含羥甲基之三聚氰胺樹脂之三聚氰胺樹脂等。惟，非限定於此等。Examples of the condensation type hardener include phenolic hardeners such as resol-type phenol resins, urea resins such as methylol-containing urea resins, and melamine resins such as methylol-containing melamine resins. However, it is not limited to this.

此等當中，由耐燃性、耐濕性、電特性、硬化性、保存穩定性等的平衡而言較佳為加成聚合型酚系硬化劑。Among these, an addition polymerization type phenol-based curing agent is preferable in terms of the balance of flame resistance, moisture resistance, electrical properties, curability, storage stability, and the like.

加成聚合型酚系硬化劑係一分子內具有2個以上酚性羥基之單體、寡聚物、聚合物全體，其分子量、分子結構不特別限定。可舉出例如酚醛清漆型樹脂(苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、雙酚酚醛清漆等)、多官能型酚樹脂(三酚甲烷型酚樹脂等)、改性酚樹脂(萜烯改性酚樹脂、二環戊二烯改性酚樹脂等)、芳烷基型樹脂(具有伸苯基骨架及/或伸聯苯基骨架之酚芳烷基樹脂、具有伸苯基骨架及/或伸聯苯基骨架之萘酚芳烷基樹脂等)、雙酚化合物(雙酚A、雙酚F等)等。此等硬化劑可單獨使用1種或併用2種以上。The addition polymerization type phenolic curing agent is a total of monomers, oligomers, and polymers having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. Examples include novolak type resins (phenol novolak resin, cresol novolak resin, bisphenol novolak, etc.), multifunctional phenol resins (triphenol methane type phenol resin, etc.), modified phenol resins (terpene modified Phenol resin, dicyclopentadiene modified phenol resin, etc.), aralkyl resin (phenol aralkyl resin with phenylene skeleton and/or biphenylene skeleton, phenylene skeleton and/or Biphenyl skeleton naphthol aralkyl resin, etc.), bisphenol compounds (bisphenol A, bisphenol F, etc.), etc. These hardeners can be used alone or in combination of two or more.

(填料(無機填充材)) 可適用於本發明之封止層的填料(以下亦稱無機填充材)可舉出一般使用於封止層形成用組成物者。可列舉例如大顆粒二氧化矽、小顆粒二氧化矽、結晶二氧化矽、滑石、氧化鋁、鈦白、氮化矽等，其中特佳為大顆粒二氧化矽及小顆粒二氧化矽。惟，非限定於此等。(Filler (inorganic filler)) The filler (hereinafter also referred to as an inorganic filler) applicable to the sealing layer of the present invention may be generally used in the composition for forming a sealing layer. Examples include large particles of silica, small particles of silica, crystalline silica, talc, alumina, titanium dioxide, silicon nitride, etc., among which large particles of silica and small particles of silica are particularly preferred. However, it is not limited to this.

填料較佳使用大顆粒二氧化矽及小顆粒二氧化矽；大顆粒二氧化矽能以高填充為目的，小顆粒二氧化矽則能以窄間距注入性為目的而使用。大顆粒二氧化矽或小顆粒二氧化矽，可舉出例如Denka公司製熔融二氧化矽、NIPPON STEEL Chemical & Material公司製球狀二氧化矽「HS系列」、TOSOH公司製二氧化矽微粒子、 Hosokawa Micron公司製結晶二氧化矽等。The filler preferably uses large particles of silica and small particles of silica; large particles of silica can be used for the purpose of high filling, and small particles of silica can be used for the purpose of narrow pitch implantation. Examples of large particles of silica or small particles of silica include fused silica manufactured by Denka, spherical silica "HS series" manufactured by NIPPON STEEL Chemical & Material, and fine particles of silica manufactured by TOSOH. Hosokawa Micron Company's crystalline silica, etc.

此等填料可單獨使用1種或併用2種以上。又，就填料的形狀，為了抑制封止層形成用組成物的熔融黏度上升，且進一步提高填料的含量，係以近似真球狀且粒度分佈較廣為佳。又，填料亦可藉由偶合劑進行表面處理。再者，亦可視需求對填料以環氧樹脂預先進行處理而使用。此外，於本發明中，可適用對填料，尤為二氧化矽的表面塗覆而賦予本發明之金屬氧化物的本發明之方法2。These fillers can be used individually by 1 type or in combination of 2 or more types. In addition, with regard to the shape of the filler, in order to suppress the increase in the melt viscosity of the composition for forming the sealing layer and to further increase the content of the filler, it is preferable to have an approximately true spherical shape and a wide particle size distribution. In addition, the filler may be surface-treated with a coupling agent. Furthermore, the filler can be pre-treated with epoxy resin for use as required. In addition, in the present invention, the method 2 of the present invention for coating the surface of fillers, especially silicon dioxide, to give the metal oxide of the present invention can be applied.

(中和劑) 本發明之封止層中，為了抑制銅線(接合線)與半導體元件之電極焊墊(金屬銲點)的接合部的腐蝕(氧化劣化)，亦可包含供中和藉由對半導層形成用組成物之硬化物加熱而產生的酸性腐蝕性氣體之中和劑。具體而言，較佳含有由鹼性金屬鹽，尤為含鈣元素之化合物、含鋁元素之化合物及含鎂元素之化合物所成群組選出的至少1種中和劑。(Neutralizer) In the sealing layer of the present invention, in order to suppress the corrosion (oxidation degradation) of the joint between the copper wire (bonding wire) and the electrode pad (metal solder joint) of the semiconductor element, it may also include a neutralization by the semiconductor layer The acidic corrosive gas neutralizer generated by heating the hardened material of the forming composition. Specifically, it is preferable to contain at least one neutralizing agent selected from the group consisting of alkaline metal salts, especially calcium-containing compounds, aluminum-containing compounds, and magnesium-containing compounds.

(硬化促進劑) 本發明之封止層可使用硬化促進劑。此硬化促進劑，只要是可促進環氧基與硬化劑之硬化反應者即可。具體而言，上述硬化促進劑可舉出1,8-二氮雜雙環[5.4.0]十一烯-7等二氮雜雙環烯及其衍生物；三丁胺、苯甲基二甲胺等胺系化合物；2-甲基咪唑等咪唑化合物；三苯基膦、甲基二苯基膦等有機膦類；四苯基鏻･四苯基硼酸鹽、四苯基鏻･四苯甲酸硼酸鹽、四苯基鏻･四萘甲酸硼酸鹽、四苯基鏻･四萘甲醯氧基硼酸鹽、四苯基鏻･四萘氧基硼酸鹽等四取代鏻･四取代硼酸鹽；苯醌經加合之三苯基膦等。此等可單獨使用1種或組合2種以上使用。(Hardening accelerator) The sealing layer of the present invention can use a hardening accelerator. The hardening accelerator may be any one that can promote the hardening reaction between the epoxy group and the hardening agent. Specifically, the above-mentioned hardening accelerators include diazabicycloalkenes such as 1,8-diazabicyclo[5.4.0]undecene-7 and their derivatives; tributylamine, benzyldimethylamine Other amine compounds; 2-methylimidazole and other imidazole compounds; Triphenylphosphine, methyldiphenylphosphine and other organic phosphines; Tetraphenylphosphonium･tetraphenylborate, tetraphenylphosphonium･tetrabenzoic acid boric acid Salt, tetraphenylphosphonium tetranaphthoic acid borate, tetraphenylphosphonium tetranaphthoyloxy borate, tetraphenylphosphonium tetranaphthyloxy borate and other tetrasubstituted phosphonium tetrasubstituted borate; benzoquinone Addition of triphenylphosphine and so on. These can be used individually by 1 type or in combination of 2 or more types.

(其他添加劑) 本發明之封止層中，除上述各成分以外，亦可視需求添加由偶合劑、調平劑、著色劑、改性劑、脫模劑、低應力劑、感光劑、消泡劑、紫外線吸收劑、發泡劑、抗氧化劑、阻燃劑及離子捕捉劑等選出的一種或二種以上之添加物。偶合劑可舉出例如環氧矽烷偶合劑、陽離子矽烷偶合劑、胺基矽烷偶合劑、γ-環氧丙氧基丙基三甲氧基矽烷偶合劑、苯基胺基丙基三甲氧基矽烷偶合劑、巰基矽烷偶合劑、3-巰基丙基三甲氧基矽烷偶合劑等矽烷偶合劑、鈦酸酯系偶合劑及聚矽氧油型偶合劑等。調平劑可舉出丙烯酸系共聚物等。著色劑可舉出碳黑等。脫模劑可舉出天然蠟、褐煤酸酯等合成蠟、高級脂肪酸或其金屬鹽類、石蠟、氧化聚乙烯等。低應力劑可舉出聚矽氧油、聚矽氧橡膠等。離子捕捉劑可舉出水滑石等。阻燃劑可舉出氫氧化鋁等。(Other additives) In the sealing layer of the present invention, in addition to the above-mentioned components, coupling agents, leveling agents, coloring agents, modifiers, release agents, low stress agents, photosensitizers, defoamers, and ultraviolet absorbers can also be added as required. One or two or more additives selected from additives, foaming agents, antioxidants, flame retardants, and ion scavengers. Coupling agents can include, for example, siloxane oxide coupling agents, cationic silane coupling agents, aminosilane coupling agents, γ-glycidoxypropyltrimethoxysilane coupling agents, phenylaminopropyltrimethoxysilane coupling agents Mixing agent, mercaptosilane coupling agent, 3-mercaptopropyl trimethoxysilane coupling agent and other silane coupling agents, titanate coupling agents and silicone oil coupling agents, etc. The leveling agent includes acrylic copolymers and the like. Examples of the coloring agent include carbon black. Examples of mold release agents include natural waxes, synthetic waxes such as montanic acid esters, higher fatty acids or metal salts thereof, paraffin wax, and oxidized polyethylene. Examples of low-stress agents include silicone oil and silicone rubber. Examples of the ion scavenger include hydrotalcite. Examples of the flame retardant include aluminum hydroxide.

[封止層之製造方法] 本發明之封止層之製造方法，其特徵為使用含有前述通式(A)所示之化合物或前述具有通式(1)所示之結構的有機金屬氧化物與醇類的封止層形成用之混合液來製造。[Method of manufacturing sealing layer] The method for producing a sealing layer of the present invention is characterized by using a sealing layer containing the compound represented by the general formula (A) or the organometallic oxide having the structure represented by the general formula (1) and alcohols. Use the mixed liquid to manufacture.

本發明之封止層形成用之混合液係呈單體成分之前述通式(A)所示之化合物與作為前述通式(A)所示之化合物之聚縮合成分的具有通式(1)所示之結構的有機金屬氧化物與醇類共存之狀態，於本發明中，係以相對於具有通式(1)所示之結構的有機金屬氧化物，通式(A)所示之化合物的成分比率較高之構成為佳。The mixed solution for forming the sealing layer of the present invention is a monomer component of the compound represented by the aforementioned general formula (A) and the polycondensation component of the compound represented by the aforementioned general formula (A) has the general formula (1) The state in which the organometallic oxide of the structure shown and the alcohol coexist, in the present invention, is relative to the organometallic oxide having the structure represented by the general formula (1), the compound represented by the general formula (A) The composition with higher component ratio is better.

再者，本發明之封止層之製造方法中，封止層所含有機金屬氧化物係以使用金屬烷氧化物或金屬羧酸鹽與氟醇的混合液來製造為佳。Furthermore, in the manufacturing method of the sealing layer of the present invention, the organic metal oxide contained in the sealing layer is preferably manufactured using a mixture of metal alkoxide or metal carboxylate and fluoroalcohol.

本發明之封止層，只要可將上述所說明的各種原料均勻地分散混合，則可採用任何方法來調製･製造；作為一般的調製方法，可舉出將既定摻混量之原料藉由混合機等充分混合後，藉由混合輥、捏合機、擠出機等進行熔融混練後，藉由冷卻、粉碎而予以顆粒化的方法。The sealing layer of the present invention can be prepared and manufactured by any method as long as the various raw materials described above can be uniformly dispersed and mixed; as a general preparation method, a predetermined blending amount of raw materials may be mixed by mixing After being thoroughly mixed with a machine, etc., it is melted and kneaded with a mixing roll, kneader, extruder, etc., and then cooled and pulverized to be pelletized.

《半導體裝置》 本發明之半導體裝置係至少由半導體元件及零件所構成的半導體裝置，其特徵為前述構件或半導體元件係由使用由環氧樹脂及有機金屬氧化物所構成的封止層形成用組成物，或僅使用有機金屬氧化物，依循前述說明之圖1A～圖1C所例示的本發明之封止方法所形成的封止層所被覆。"Semiconductor Device" The semiconductor device of the present invention is a semiconductor device composed of at least semiconductor elements and parts, characterized in that the aforementioned member or semiconductor element is made of a composition for forming a sealing layer composed of epoxy resin and organic metal oxide, or Only the organic metal oxide is used, and the sealing layer formed by the sealing method of the present invention illustrated in FIGS. 1A to 1C described above is covered.

作為半導體元件，具體而言，可舉出積體電路、大規模積體電路、主動元件、被動元件、固體攝像元件、分離式元件、使用SiC之半導體元件、功率電晶體等電力系統半導體、車載用電子零件等。此外，於本發明中，係省略與半導體本體之構造有關的詳細說明。Specific examples of semiconductor elements include integrated circuits, large-scale integrated circuits, active elements, passive elements, solid-state imaging elements, discrete elements, semiconductor elements using SiC, power transistors and other power system semiconductors, automotive Use electronic parts, etc. In addition, in the present invention, detailed descriptions related to the structure of the semiconductor body are omitted.

本發明之半導體裝置係至少具有半導體元件與由封止半導體元件之本發明之封止層的硬化物所構成的封止層。The semiconductor device of the present invention has at least a semiconductor element and a sealing layer composed of a cured product of the sealing layer of the present invention for sealing the semiconductor element.

作為本發明之半導體裝置，可適用向來周知之半導體裝置，不特別限制，就其具體類型，可舉出雙列直插封裝(DIP)、附引線之塑膠晶片載體(PLCC)、四方扁平封裝(QFP)、薄型四方扁平封裝(LQFP)、小外形J引線封裝(SOJ)、薄型小外形封裝(TSOP)、薄型四方扁平封裝(TQFP)、帶載體封裝(TCP)、球柵陣列(BGA)、晶片尺寸封裝(CSP)、四方扁平無引線封裝(QFN)、小外形無引線封裝(SON)、引線框-BGA(LF-BGA)、模具陣列封裝型BGA (MAP-BGA)、使用再配線之扇入晶圓級封裝(FIWLP)、扇出晶圓級封裝(FOWLP)或扇入面板級封裝(FIPLP)、扇出面板級封裝(FOPLP)等。惟，非限定於此等。As the semiconductor device of the present invention, conventionally known semiconductor devices can be applied and are not particularly limited. Specific types include dual in-line package (DIP), plastic chip carrier with leads (PLCC), quad flat package ( QFP), thin quad flat package (LQFP), small outline J-lead package (SOJ), thin small outline package (TSOP), thin quad flat package (TQFP), tape carrier package (TCP), ball grid array (BGA), Chip size package (CSP), quad flat no-lead package (QFN), small outline no-lead package (SON), lead frame-BGA (LF-BGA), mold array package type BGA (MAP-BGA), use rewiring Fan-in wafer-level packaging (FIWLP), fan-out wafer-level packaging (FOWLP) or fan-in panel-level packaging (FIPLP), fan-out panel-level packaging (FOPLP), etc. However, it is not limited to this.

就本發明之半導體裝置，例如可取供形成本發明之封止層的封止層形成用組成物，利用轉注成形、壓縮成形、射出成形等成形方法將該半導體封止用組成物進行硬化成形，而封止半導體元件等電子零件。例如，轉移方式之成形加工係以一般半導體等電子零件之樹脂封止所採用的成型方法(封止方法)，將在柱塞內暫時熔融的封止層形成用組成物填充於模腔內使其硬化而形成封止層的方法。又，壓縮方式之成形加工係指在模腔內直接放入液態半導體封止用組成物並予以熔融後，將固定有半導體元件的引線框或矽中介層、有機中介層、覆晶基板等浸漬於其中後，將樹脂進行硬化成型而形成封止層的方法。For the semiconductor device of the present invention, for example, a composition for forming a sealing layer for forming the sealing layer of the present invention can be taken, and the semiconductor sealing composition can be hardened and molded by a molding method such as transfer molding, compression molding, and injection molding. And seal electronic parts such as semiconductor components. For example, the molding process of the transfer method is a molding method (sealing method) used for resin sealing of electronic parts such as general semiconductors. The composition for forming a sealing layer temporarily melted in the plunger is filled in the cavity to make It hardens to form a sealing layer. In addition, the compression molding process refers to directly putting the liquid semiconductor sealing composition in the mold cavity and melting it, and then immersing the lead frame or the silicon interposer, the organic interposer, the flip chip substrate, etc., on which the semiconductor element is fixed. After that, the resin is cured and molded to form a sealing layer.

此外，可將供形成本發明之封止層的組成物溶於各種有機溶劑而調製成液狀的半導體封止層形成用塗佈液後，採用塗佈方式予以塗佈於半導體元件上。可適用之塗佈方式，除例如上述所說明之採轉移方式或壓縮方式之填充法外，亦可利用分配器法、旋轉塗佈法、澆鑄法、網版印刷法、模頭塗佈法、刮刀塗佈法、輥塗法、噴塗法、幕塗法、LB法(Langmuir-Blodgett法)、噴墨印刷法等濕式塗佈方式來形成封止層。其中，較佳為分配器法、旋轉塗佈法、模頭塗佈法、轉移方式、壓縮方式之填充法或噴墨印刷法。In addition, the composition for forming the sealing layer of the present invention can be dissolved in various organic solvents to prepare a liquid coating solution for forming a semiconductor sealing layer, and then applied to the semiconductor element by a coating method. Applicable coating methods, in addition to the transfer method or the compression method described above, can also use the dispenser method, spin coating method, casting method, screen printing method, die coating method, The sealing layer is formed by wet coating methods such as knife coating method, roll coating method, spray coating method, curtain coating method, LB method (Langmuir-Blodgett method), and inkjet printing method. Among them, the dispenser method, spin coating method, die coating method, transfer method, compression method of filling method or inkjet printing method are preferred.

藉由上述方法對本發明之封止層實施熱處理而予以硬化。就硬化條件，可由向來周知之條件適宜選出，例如，由反應速度而言，溫度(硬化溫度)較佳為25～180℃的範圍內，更佳為60～150℃的範圍內；時間(硬化時間)較佳為5～720分鐘的範圍內。此外，硬化能以一階段實施，亦能以多階段實施。The sealing layer of the present invention is heat-treated and hardened by the above method. The curing conditions can be appropriately selected from conventionally known conditions. For example, in terms of reaction speed, the temperature (curing temperature) is preferably in the range of 25 to 180°C, more preferably in the range of 60 to 150°C; time (curing The time) is preferably in the range of 5 to 720 minutes. In addition, hardening can be implemented in one stage or in multiple stages.

具體而言，本發明之半導體裝置可舉出在銅製引線框之支持構件上配載半導體晶片、電晶體、二極體、閘流體等主動元件、電容器、電阻器、線圈等被動元件等的元件，並將必要部分以本發明之封止層封止而成的半導體裝置等。就此種半導體裝置，係例如在銅製引線框上固定半導體元件，並將接合墊等元件的端子部與引線部以線接合或凸塊連接後，使用本發明之封止層予以封止而構成。 [實施例]Specifically, the semiconductor device of the present invention can include components in which active components such as semiconductor chips, transistors, diodes, thyristors, and passive components such as capacitors, resistors, and coils are mounted on the supporting member of a copper lead frame. , And the necessary parts are sealed with the sealing layer of the present invention to form a semiconductor device, etc. Such a semiconductor device is constructed by fixing a semiconductor element on a copper lead frame, connecting the terminal portion of the element such as a bonding pad and the lead portion by wire bonding or bumping, and then sealing it with the sealing layer of the present invention. [Example]

以下舉出實施例對本發明更具體地加以說明，惟本發明非限定於此等。此外，於實施例中係使用「份」或「%」之標示，除非特別合先敘明，否則表示「質量份」或「質量%」。此外，實施例中，於構成要素的末尾記載於括弧內之數字係表示記載於各圖的符號。The following examples are given to illustrate the present invention more specifically, but the present invention is not limited to these. In addition, in the examples, the indications of "parts" or "%" are used, unless otherwise specified, it means "parts by mass" or "% by mass". In addition, in the embodiment, the numbers described in parentheses at the end of the constituent elements indicate the symbols described in each figure.

實施例1 依循下述方法，製作評定耐腐蝕性的評定用晶片(TEG)。Example 1 According to the following method, an evaluation wafer (TEG) for evaluating corrosion resistance is produced.

《評定用晶片的製作所使用之構成材料》 以下示出下述各評定用晶片的製作所使用之各構成材料的細節。"Materials used in the manufacture of wafers for evaluation" The details of each constituent material used in the production of each wafer for evaluation described below are shown below.

大顆粒二氧化矽：Denka公司製 球狀二氧化矽「FB-15D」(d50=13.0μm) 小顆粒二氧化矽：Admatechs(股)製 球狀二氧化矽Regular Grade「SO-C5」(平粒粒徑1.3～1.7μm) 環氧樹脂：KYOCERA公司製 KE-G3000D 硬化劑：日本化藥公司製 Phenolaralkyl GPH65 硬化觸媒：四國化成公司製 2P4MHZ 著色劑：碳黑(三菱化學公司製 MA-100) 阻燃劑：四氯鄰苯二甲酸酐 偶合劑：信越化學公司製 KBM-503(3-甲基丙烯醯氧丙基三甲氧基矽烷) 〈有機金屬氧化物群〉 Ti金屬氧化物：例示化合物1 Cu金屬氧化物：例示化合物141 Bi金屬氧化物：例示化合物136。Large-grained silica: made by Denka Corporation Spherical silica "FB-15D" (d50=13.0μm) Small particles of silica: Admatechs (stock) product Spherical silica Regular Grade "SO-C5" (flat particle size 1.3～1.7μm) Epoxy resin: KE-G3000D manufactured by KYOCERA Hardener: Phenolaralkyl GPH65 manufactured by Nippon Kayaku Corporation Hardening catalyst: 2P4MHZ manufactured by Shikoku Chemical Co., Ltd. Coloring agent: carbon black (MA-100 manufactured by Mitsubishi Chemical Corporation) Flame retardant: tetrachlorophthalic anhydride Coupling agent: KBM-503 (3-methacryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. <Organic Metal Oxide Group> Ti metal oxide: Exemplary compound 1 Cu metal oxide: Exemplary compound 141 Bi metal oxide: Compound 136 is exemplified.

《評定用晶片(TEG)的製作》 [評定用晶片1的製作：比較例] (封止層形成用組成物1的調製) 調製由下述各添加劑所構成的封止層形成用組成物1。"Production of Evaluation Chip (TEG)" [Production of Evaluation Wafer 1: Comparative Example] (Preparation of composition 1 for forming sealing layer) A composition 1 for forming a sealing layer composed of the following additives was prepared.

前述環氧樹脂                                          92質量份 前述硬化劑                                             5質量份 前述阻燃劑                                             2質量份 前述偶合劑                                             1質量份 (測試用圖型化基板(13)的製作) 依循下述方法，製作由圖4所記載之構造所構成的耐腐蝕性評定用之測試用圖型化基板(13)。The aforementioned epoxy resin 92 parts by mass The aforementioned hardener 5 parts by mass The aforementioned flame-retardant agent 2 parts by mass The aforementioned coupling agent 1 part by mass (Production of patterned substrate (13) for testing) According to the following method, a test patterned substrate (13) for corrosion resistance evaluation composed of the structure described in FIG. 4 was produced.

作為測試用元件基板(14)，係使用厚度5cm的Corning公司製EagleXG無鹼玻璃，並以濕式洗淨進行清潔。其次，在測試用元件基板(14)上，將SiO2 以厚度成為10nm的方式藉由濺鍍法製成膜，而形成密接層。接著，於既定的位置，同樣地藉由濺鍍法將Cu形成為厚度1μm的膜。As the test element substrate (14), EagleXG alkali-free glass manufactured by Corning Corporation with a thickness of 5 cm was used and cleaned by wet washing. Next, on the test element substrate (14), SiO 2 was formed into a film by a sputtering method so that the thickness became 10 nm to form an adhesive layer. Next, at a predetermined position, Cu was formed into a film with a thickness of 1 μm by the sputtering method in the same manner.

其次，為了以光製程形成厚度20μm之L/S的梳型場電極(17)，而以厚度1μm賦予東京應化製造的光阻後，進行曝光與顯像，並以關東化學製造的Cu用蝕刻液進行圖型化。藉由進行剝離與純潤洗，而製成圖4所示之構成的測試用圖型化基板(13)。Secondly, in order to form an L/S comb-shaped field electrode (17) with a thickness of 20μm by an optical process, a photoresist manufactured by Tokyo Ohka was applied with a thickness of 1μm, and then exposed and developed. The etching solution is patterned. By performing peeling and pure rinsing, a patterned substrate (13) for testing with the configuration shown in FIG. 4 is produced.

圖4中，測試用圖型化基板(13)係於測試用元件基板(14)上形成有負電極(15)、正電極(16)及連接於此等電極的梳型場電極(17)。In Figure 4, the test patterned substrate (13) is formed on the test element substrate (14) with negative electrodes (15), positive electrodes (16) and comb-shaped field electrodes (17) connected to these electrodes .

(評定用晶片(TEG)的製作] 其次，如圖5所示，對測試用圖型化基板(13)的上層及下層，藉由上述調製之封止層形成用組成物1(比較例，未含有有機金屬氧化物)，在被覆梳型場電極全體的形態下以乾膜厚成為20μm之條件進行塗敷，並以150℃乾燥60分鐘而形成僅由半導體封止用組成物1所構成的封止層(20)，而製成評定用晶片1(19)。(Production of evaluation chip (TEG)) Next, as shown in Figure 5, the upper and lower layers of the patterned substrate (13) for testing were coated with the above-prepared composition 1 for forming a sealing layer (comparative example, not containing organometallic oxide). The comb-shaped field electrode is applied with a dry film thickness of 20 μm in the form of the entire comb-shaped field electrode, and dried at 150°C for 60 minutes to form a sealing layer (20) composed of only the semiconductor sealing composition 1 Qualified wafer 1 (19).

[評定用晶片2的製作：本發明] (封止層形成用組成物2的調製) 調製由下述各添加劑所構成的封止層形成用組成物2。半導體封止用組成物2係將由有機金屬化合物所構成的有機金屬氧化物群A(溶膠-凝膠液)直接添加於由環氧樹脂、硬化劑、阻燃劑及偶合劑所構成的塗佈液來調製塗佈液的方法(添加塗佈液)。[Production of wafer 2 for evaluation: the present invention] (Preparation of composition 2 for forming sealing layer) A composition 2 for forming a sealing layer composed of the following additives was prepared. For semiconductor sealing composition 2, organometallic oxide group A (sol-gel solution) composed of organometallic compounds is directly added to a coating composed of epoxy resin, hardener, flame retardant, and coupling agent A method of preparing a coating liquid (adding a coating liquid).

前述環氧樹脂                                          87質量份 前述硬化劑                                             5質量份 前述阻燃劑                                             2質量份 前述偶合劑                                             1質量份 〈有機金屬氧化物群A：溶膠-凝膠液〉 前述Ti金屬氧化物                                    2質量份 前述Cu金屬氧化物                                   1質量份 前述Bi金屬氧化物                                    2質量份 [評定用晶片(TEG)的製作] 其次，以與上述評定用晶片1(比較例)的製作同樣的方式，如圖5所示，將上述調製之含有有機金屬氧化物群A的封止層形成用組成物2，在被覆梳型場電極全體的形態下以乾膜厚成為20μm之條件塗敷於測試用圖型化基板(13)的上層及下層，並以150℃乾燥60分鐘而形成封止層(20)，而製成評定用晶片2。圖6示出圖5所示之評定用晶片(19)的俯視圖所記載之A-A’切剖面的剖面圖。The aforementioned epoxy resin 87 parts by mass The aforementioned hardening agent 5 parts by mass The aforementioned flame-retardant agent 2 parts by mass The aforementioned coupling agent 1 part by mass <Organic Metal Oxide Group A: Sol-Gel Solution> The aforementioned Ti metal oxide 2 parts by mass The foregoing Cu metal oxide 1 part by mass The foregoing Bi metal oxide 2 parts by mass [Production of Evaluation Wafer (TEG)] Next, in the same manner as the production of the above-mentioned evaluation wafer 1 (comparative example), as shown in FIG. 5, the composition 2 for forming a sealing layer containing the organometallic oxide group A prepared above was coated with a comb type The entire field electrode is applied to the upper and lower layers of the patterned substrate (13) for testing under the condition of a dry film thickness of 20μm, and dried at 150°C for 60 minutes to form a sealing layer (20). Evaluation chip 2. Fig. 6 is a cross-sectional view of the A-A' section described in the plan view of the evaluation wafer (19) shown in Fig. 5.

[評定用晶片3的製作：本發明] (有機金屬氧化物群A對測試用圖型化基板(13)的賦予) 在上述製作之圖4所示之構成的測試用圖型化基板(13)上，將由下述組成所構成的有機金屬氧化物群A(溶膠-凝膠液)以分配器塗佈成100μm厚。其次，為了乾燥而以110℃加熱30分鐘，且為了進行聚合反應，而照射1.5J/cm2 的準分子光，而形成含有有機金屬氧化物群的皮膜層。[Production of wafer 3 for evaluation: the present invention] (Provision of organometal oxide group A to patterned substrate for testing (13)) The patterned substrate for testing (13) with the configuration shown in Figure 4 produced above ), the organometal oxide group A (sol-gel solution) composed of the following composition was applied with a dispenser to a thickness of 100 μm. Next, it was heated at 110° C. for 30 minutes for drying, and 1.5 J/cm 2 of excimer light was irradiated for the polymerization reaction to form a coating layer containing the organometallic oxide group.

前述Ti金屬氧化物                                    2質量份 前述Cu金屬氧化物                                   1質量份 前述Bi金屬氧化物                                    2質量份 (封止層的形成) 其次，在形成有包含有機金屬氧化物群的皮膜層的測試用圖型化基板(13)上，以成為圖5所示構成的方式對上層及下層賦予由下述所示組成所構成的封止層形成用組成物3，以乾膜厚成為20μm的方式進行塗佈後，以150℃乾燥60分鐘形成封止層(20)，而製成評定用晶片3。The aforementioned Ti metal oxide 2 parts by mass The foregoing Cu metal oxide 1 part by mass The foregoing Bi metal oxide 2 parts by mass (Formation of sealing layer) Next, on the patterned substrate (13) for testing on which the film layer containing the organometallic oxide group is formed, the upper layer and the lower layer are provided with a seal composed of the following composition so as to become the structure shown in FIG. The composition 3 for forming a stop layer was applied so that the dry film thickness became 20 μm, and then dried at 150° C. for 60 minutes to form a sealing layer (20), thereby producing a wafer 3 for evaluation.

〈封止層形成用組成物3的調製〉 前述大顆粒二氧化矽                                 72質量份 前述小顆粒二氧化矽                                 15質量份 前述環氧樹脂                                          8質量份 前述硬化劑                                             0.5質量份 前述硬化促進劑                                       0.5質量份 前述阻燃劑                                             2質量份 前述偶合劑                                             1質量份 [評定用晶片4的製作：本發明] 於上述評定用晶片3的製作時，除將有機金屬氧化物群A之添加方法變更為下述方法以外係以同樣方式製成評定用晶片4。<Preparation of composition 3 for forming sealing layer> The aforementioned large particles of silicon dioxide 72 parts by mass The aforementioned small particles of silicon dioxide 15 parts by mass The aforementioned epoxy resin 8 parts by mass The aforementioned hardening agent 0.5 parts by mass The aforementioned hardening accelerator 0.5 parts by mass The aforementioned flame retardant agent 2 parts by mass The aforementioned coupling agent 1 part by mass [Production of Wafer 4 for Evaluation: The Invention] In the production of the evaluation wafer 3 described above, the evaluation wafer 4 was produced in the same manner except that the method of adding the organometallic oxide group A was changed to the following method.

(有機金屬氧化物群對填料的賦予) 依循下述方法，對填料表面藉由浸漬塗佈預先塗覆有機金屬氧化物群。(Addition of organic metal oxide group to filler) According to the following method, the filler surface is pre-coated with organometallic oxide group by dip coating.

如表I所示，填料係準備預先將天然石英以珠磨機粉碎成期望的大小之大顆粒二氧化矽，與由金屬矽構成的小顆粒二氧化矽，為達表面活性化，而使用HMDS(1,1,1,3,3,3-六甲基二矽氮烷)進行處理。As shown in Table I, the filler system is prepared to pulverize natural quartz with a bead mill into large particles of silicon dioxide of the desired size, and small particles of silicon dioxide composed of metallic silicon. To achieve surface activation, HMDS is used. (1,1,1,3,3,3-hexamethyldisilazane) for processing.

對於大顆粒二氧化矽，為了進行聚矽氧被覆，而進行使用聚矽氧之浸漬塗佈。另一方面，對於小顆粒二氧化矽的15質量份，係浸漬塗佈下述有機金屬氧化物群A(溶膠-凝膠液)的1質量份。For large particles of silica, in order to be coated with silicone, dip coating using silicone is performed. On the other hand, 15 parts by mass of the small-particle silica is dip-coated 1 part by mass of the organometallic oxide group A (sol-gel liquid) described below.

〈有機金屬氧化物群A〉 前述Ti金屬氧化物                                    0.4質量份 前述Cu金屬氧化物                                   0.2質量份 前述Bi金屬氧化物                                    0.4質量份 (封止層的調製) 如表I所示，調製由被覆有上述調製之聚矽氧被覆層的大顆粒二氧化矽72質量份、被覆有1質量之有機金屬氧化物群A(溶膠-凝膠液)的小顆粒二氧化矽15質量份、環氧樹脂8質量份、硬化劑1質量份、硬化觸媒0.5質量份、著色劑0.5質量份、阻燃劑2質量份所構成的封止層形成用組成物4。<Organic Metal Oxide Group A> The aforementioned Ti metal oxide 0.4 parts by mass The aforementioned Cu metal oxide 0.2 parts by mass The aforementioned Bi metal oxide 0.4 parts by mass (Modulation of sealing layer) As shown in Table I, 72 parts by mass of large particles of silica coated with the above-prepared polysiloxy coating layer and two small particles of 1 mass of organometal oxide group A (sol-gel solution) were prepared. The composition 4 for forming a sealing layer is composed of 15 parts by mass of silicon oxide, 8 parts by mass of epoxy resin, 1 part by mass of hardener, 0.5 part by mass of hardening catalyst, 0.5 part by mass of colorant, and 2 parts by mass of flame retardant.

(封止層的形成) 其次，在測試用圖型化基板(13)上，以成為圖5所示構成的方式對上層及下層賦予上述調製之封止層形成用組成物4，並以乾膜厚成為20μm的方式進行塗佈後，以150℃乾燥60分鐘而形成封止層(20)，而製成評定用晶片4。(Formation of sealing layer) Next, on the patterned substrate (13) for testing, the above-prepared sealing layer forming composition 4 was applied to the upper and lower layers to have the structure shown in FIG. 5, and the dry film thickness was 20 μm. After coating, it was dried at 150°C for 60 minutes to form a sealing layer (20), and the wafer 4 for evaluation was produced.

[評定用晶片5的製作：本發明] 除在上述評定用晶片4的製作時，浸漬塗佈於小顆粒二氧化矽的有機金屬氧化物群使用由下述組成所構成的有機金屬氧化物群B來替代有機金屬氧化物群A以外係以同樣方式製成評定用晶片5。[Production of Evaluation Wafer 5: The Invention] Except for the production of the above-mentioned wafer 4 for evaluation, the organometal oxide group dip-coated on small particles of silicon dioxide uses the organometal oxide group B composed of the following composition instead of the organometal oxide group A. The wafer 5 for evaluation was produced in the same manner.

(有機金屬氧化物群B) 前述Ti金屬氧化物                                    0.5質量份 前述Bi金屬氧化物                                    0.5質量份 [評定用晶片6的製作：本發明] 除在上述評定用晶片4的製作時，浸漬塗佈於小顆粒二氧化矽的有機金屬氧化物群使用由下述組成所構成的有機金屬氧化物群C來替代有機金屬氧化物群A以外係以同樣方式製成評定用晶片6。(Organic Metal Oxide Group B) The aforementioned Ti metal oxide 0.5 parts by mass The aforementioned Bi metal oxide 0.5 parts by mass [Production of Evaluation Wafer 6: The Invention] Except for the production of the above-mentioned wafer 4 for evaluation, the organometal oxide group dip-coated on small particles of silicon dioxide uses the organometal oxide group C composed of the following composition instead of the organometal oxide group A. In the same manner, a wafer 6 for evaluation was produced.

(有機金屬氧化物群C) 前述Bi金屬氧化物                                    1.0質量份 [評定用晶片7的製作：本發明] 除在上述評定用晶片4的製作時，浸漬塗佈於小顆粒二氧化矽的有機金屬氧化物群使用由下述組成所構成的有機金屬氧化物群D來替代有機金屬氧化物群A以外係以同樣方式製成評定用晶片7。(Organic Metal Oxide Group C) The aforementioned Bi metal oxide 1.0 parts by mass [Production of Evaluation Wafer 7: The Invention] Except for the production of the above evaluation wafer 4, the organometal oxide group dip-coated on the small particles of silicon dioxide uses the organometal oxide group D composed of the following composition instead of the organometal oxide group A. In the same manner, a wafer 7 for evaluation was produced.

(有機金屬氧化物群D) 前述Cu金屬氧化物                                   0.5質量份 前述Bi金屬氧化物                                    0.5質量份 《評定用晶片(TEG)的評定》 各準備2片上述製作之由圖5所記載之構造所構成的各評定用晶片(梳型場電極根數：240根)，依循下述方法來進行耐腐蝕性的評定。(Organic Metal Oxide Group D) The aforementioned Cu metal oxide 0.5 parts by mass The aforementioned Bi metal oxide 0.5 parts by mass "Evaluation of Evaluation Chip (TEG)" Two wafers for evaluation (number of comb-shaped field electrodes: 240) composed of the structure described in FIG. 5 were prepared, and the corrosion resistance was evaluated according to the following method.

將上述準備之各評定用晶片，在85℃、85%RH的環境條件下置入在裝置內配置有儲存有硫粉末之開放系統樣品瓶的恆溫槽內，在由電源(18)施加50V之偏壓的狀態下保存1000小時，目視觀察梳型場電極的腐蝕狀態。就此評定，係水分與硫成分(硫化氫)由外部環境侵入至封止層內，且於封止層內部，由阻燃劑成分產生鹵素(Cl- )的評定條件。Put each of the evaluation wafers prepared above into a constant temperature bath equipped with an open system sample bottle containing sulfur powder under the environmental conditions of 85℃ and 85%RH, and apply 50V from the power supply (18) Stored for 1000 hours in a biased state, and visually observed the corrosion state of the comb-shaped field electrode. In this evaluation, a sulfur-based moisture component (hydrogen sulfide) from the external environment intrusion into the passivation layer, and in the inner sealing layer is produced by flame retardant component halo (Cl -) The evaluation conditions.

具體而言，係對保存1000小時的各評定用晶片(19)，如圖6所示，自屬無鹼玻璃製之測試用元件基板(14)面(圖6的下表面側)，目視觀察240根梳型場電極(17)的形狀，如有梳型場電極(17)的面積，即使為部分性，但電極寬度仍縮成2/3以下的部位產生時，即判斷為「腐蝕產生」，計數發生腐蝕之梳型場電極(17)的根數，並將所得結果示於表I。Specifically, for each wafer (19) stored for 1000 hours, as shown in Fig. 6, the surface of the test element substrate (14) made of alkali-free glass (the lower surface side of Fig. 6) was visually observed The shape of 240 comb-shaped field electrodes (17), if the area of the comb-shaped field electrodes (17) is partial, but the electrode width is still reduced to 2/3 or less, it is judged as "corrosion ", count the number of comb-shaped field electrodes (17) that are corroded, and show the results in Table 1.

腐蝕率若未達2.0%係判定為「◎」；若為2.0%以上且未達5.0%係判定為「○」；若為5.0%以上則判定為「×」。If the corrosion rate is less than 2.0%, it is judged as "◎"; if it is more than 2.0% and less than 5.0%, it is judged as "○"; if it is more than 5.0%, it is judged as "×".

Figure 02_image037
Figure 02_image037

由表I所記載之結果，顯然本發明之評定用晶片2～7，相對於比較例之評定晶片1，未發生由硫成分、水分及阻燃劑所產生之鹵素等所造成的腐蝕，可知對電極的耐腐蝕性優異。From the results described in Table I, it is clear that the evaluation wafers 2-7 of the present invention, compared to the evaluation wafer 1 of the comparative example, did not undergo corrosion caused by sulfur components, moisture, and halogens generated by flame retardants. The counter electrode has excellent corrosion resistance.

就比較例之評定用晶片1，自超過200小時的時候起即開始產生腐蝕，具體而言為發生黑化，產生腐蝕及電蝕。由上述結果，顯然使用含有由本發明之有機金屬氧化物所構成的有機金屬氧化物群之封止層形成用組成物進行封止而形成的本發明之評定用晶片可確認能顯著防止腐蝕。As for the evaluation wafer 1 of the comparative example, corrosion began to occur after more than 200 hours, specifically, blackening, corrosion, and electric corrosion occurred. From the above results, it is apparent that the wafer for evaluation of the present invention formed by sealing with the composition for forming a sealing layer containing the organometallic oxide group composed of the organometallic oxide of the present invention can significantly prevent corrosion.

實施例2 [半導體裝置1的製作(比較例)：QFN形態之半導體裝置的製作] 依循下述方法，利用使用於實施例1所記載之評定用晶片1(比較例)的製作之封止層形成用組成物1，製作由圖7A及圖7B所記載之構造所構成的半導體裝置1(21、QFN封裝體、比較例)。Example 2 [Fabrication of Semiconductor Device 1 (Comparative Example): Fabrication of QFN Type Semiconductor Device] According to the following method, using the composition 1 for forming a sealing layer used in the production of the evaluation wafer 1 (comparative example) described in Example 1, a semiconductor device composed of the structure described in FIGS. 7A and 7B was produced 1 (21, QFN package, comparative example).

圖7A所記載之半導體裝置(21，QFN)，在元件基板(13)上配置有引線框(22)，且於中央的引線框(22)上，經由Ag製黏晶材(23)配置有半導體元件(3)。半導體之金屬銲點(7)與Cu製引線框(22)係藉由Cu製接合線(8)連接而成。在被覆此等各構成要素的形態下，將使用於實施例1所記載之評定用晶片1的製作的封止層形成用組成物1以轉移方式進行成形加工而形成封止層(4)。In the semiconductor device (21, QFN) described in FIG. 7A, a lead frame (22) is arranged on an element substrate (13), and a lead frame (22) in the center is arranged with an Ag bonding material (23) Semiconductor components (3). The metal solder joint (7) of the semiconductor and the Cu lead frame (22) are connected by a Cu bonding wire (8). In the form of covering these constituent elements, the sealing layer forming composition 1 used for the production of the evaluation wafer 1 described in Example 1 is subjected to a transfer method to form a sealing layer (4).

具體而言，係將經背面研磨而薄膜化的矽晶圓黏貼於切割膠帶上，並以切割機切割矽晶圓，而製成元件基板(13)。Specifically, a silicon wafer thinned by back grinding is pasted on a dicing tape, and the silicon wafer is cut by a dicing machine to form a device substrate (13).

其次，將半導體元件(3)以由Ag構成的黏晶材(23)黏貼於引線框(22)上，以150℃實施30分鐘的退火處理而使其硬化。Next, the semiconductor element (3) is attached to the lead frame (22) with a die-bonding material (23) made of Ag, and an annealing treatment is performed at 150°C for 30 minutes to harden it.

其次，以Cu製接合線(8)予以接合，而將引線框(22)與半導體元件(3)電性連接。Next, the Cu bonding wire (8) is used for bonding, and the lead frame (22) and the semiconductor element (3) are electrically connected.

接著，將具有固定有由上述構造所構成之半導體元件的引線框(22)或金屬銲點(7)、接合線(8)的元件基板裝設於模腔內，並將填充於柱塞的封止層形成用組成物1以轉移方式進行成形加工而形成封止層(4)並予以硬化。Next, a component substrate with a lead frame (22) or metal solder joints (7) and bonding wires (8) on which a semiconductor component constituted by the above-mentioned structure is fixed is installed in the mold cavity, and filled in the plunger The composition 1 for forming a sealing layer is molded by a transfer method to form a sealing layer (4) and hardened.

最後，藉由實施作為鍍敷處理之約2～10μm的鍍鎳處理，而製成比較例之半導體裝置1(21)。Finally, the semiconductor device 1 (21) of the comparative example was produced by performing a nickel plating treatment of about 2-10 μm as a plating treatment.

[半導體裝置2的製作：QFN形態(本發明)] 除在上述QFN形態之比較例之半導體裝置1的製作時，使用含有實施例1所記載之評定用晶片2(本發明)的製作中所使用之有機金屬氧化物群A的封止層形成用組成物2來替代比較例之封止層形成用組成物1以外係以同樣方式，使用方法1(類型A)作為封止方式，製成圖7所記載之封裝規格之QFN形態的本發明之半導體裝置2。[Production of semiconductor device 2: QFN form (present invention)] Except for the production of the semiconductor device 1 of the comparative example of the above-mentioned QFN form, a sealing layer containing the organometallic oxide group A used in the production of the evaluation wafer 2 (the present invention) described in Example 1 was used. The composition 2 was used in the same manner as the replacement of the sealing layer forming composition 1 of the comparative example, using method 1 (type A) as the sealing method, and the QFN form of the package specification described in FIG. 7 was produced. Semiconductor device 2.

[半導體裝置3的製作：QFN形態(本發明)] 對具有固定有與上述比較例之半導體裝置1的製作中所使用者相同的半導體元件之引線框或金屬銲點、接合線的元件基板上，藉由實施例1所記載之有機金屬氧化物群A，使用噴墨印刷法，以厚度成為200nm之條件被覆於接合線與金屬銲點的整個表面。 其次，將以有機金屬氧化物群A被覆接合線與金屬銲點的元件基板裝設於模腔內，將填充於柱塞的實施例1所記載之封止層形成用組成物3以轉移方式進行成形加工，製成使用以封止方法3(圖1C所記載之類型C)封止之封止層(4)所形成的本發明之半導體裝置3。[Production of semiconductor device 3: QFN form (present invention)] On a device substrate with a lead frame, metal solder joints, and bonding wires fixed to the same semiconductor device used in the manufacture of the semiconductor device 1 of the above-mentioned comparative example, the organic metal oxide group described in Example 1 A. Use the inkjet printing method to cover the entire surface of the bonding wire and the metal solder joint with a thickness of 200nm. Next, the device substrate covering the bonding wires and the metal pads with the organometal oxide group A was installed in the cavity, and the composition 3 for forming the sealing layer described in Example 1 filled with the plunger was transferred by a transfer method The forming process is performed to produce the semiconductor device 3 of the present invention formed using the sealing layer (4) sealed by the sealing method 3 (type C described in FIG. 1C).

[半導體裝置4的製作：QFN形態(本發明)] 使用由被覆有使用於實施例1所記載之評定用晶片4(本發明3)的製作之聚矽氧被覆層的大顆粒二氧化矽72質量份、被覆有1質量之有機金屬氧化物群A(溶膠-凝膠液)的小顆粒二氧化矽15質量份、環氧樹脂8質量份、硬化劑1質量份、硬化觸媒0.5質量份、著色劑0.5質量份、阻燃劑2質量份所構成的封止層形成用組成物4，以使用於上述半導體裝置2的製作之轉移方式進行成形加工，形成封止層(4)並予以硬化，而製成具有以屬本發明之封止方法的方法2(類型B)製作之封止層的本發明之半導體裝置4；該方法2係將填料(小顆粒二氧化矽)表面以有機金屬氧化物群A被覆者。[Production of semiconductor device 4: QFN form (present invention)] Using 72 parts by mass of large-particle silicon dioxide coated with a polysiloxy coating layer used in the production of the evaluation wafer 4 (the present invention 3) described in Example 1 and coated with 1 mass of organometallic oxide group A (Sol-gel liquid) 15 parts by mass of small particles of silica, 8 parts by mass of epoxy resin, 1 part by mass of hardener, 0.5 part by mass of hardening catalyst, 0.5 part by mass of coloring agent, 2 parts by mass of flame retardant The composition 4 for forming a sealing layer is formed and processed by the transfer method used in the production of the semiconductor device 2 described above to form a sealing layer (4) and harden it to form a sealing method according to the present invention. Method 2 (Type B) of the semiconductor device 4 of the present invention made of the sealing layer; Method 2 is to coat the surface of the filler (small particles of silicon dioxide) with organometallic oxide group A.

[半導體裝置5的製作：QFN形態(本發明)] 除在上述半導體裝置4的製作時，使用包含實施例1中所調製之有機金屬氧化物群B的封止層形成用組成物5來替代封止層形成用組成物4以外係以同樣方式，製成以屬本發明之封止方法的方法2形成封止層的本發明之半導體裝置5。[Production of semiconductor device 5: QFN form (present invention)] The same procedure was applied except that the sealing layer forming composition 5 containing the organometallic oxide group B prepared in Example 1 was used in place of the sealing layer forming composition 4 during the production of the above-mentioned semiconductor device 4. The semiconductor device 5 of the present invention in which the sealing layer is formed by the method 2 of the sealing method of the present invention is manufactured.

[半導體裝置6的製作：QFN形態(本發明)] 除在上述半導體裝置4的製作時，使用包含實施例1中所調製之有機金屬氧化物群C的封止層形成用組成物6來替代封止層形成用組成物4以外係以同樣方式，製成以屬本發明之封止方法的方法2形成封止層的本發明之半導體裝置6。[Production of semiconductor device 6: QFN form (present invention)] The same procedure was applied except that the sealing layer forming composition 6 containing the organometallic oxide group C prepared in Example 1 was used in place of the sealing layer forming composition 4 during the production of the above-mentioned semiconductor device 4. The semiconductor device 6 of the present invention in which the sealing layer is formed by the method 2 of the sealing method of the present invention is manufactured.

[半導體裝置7的製作：QFN形態(本發明)] 除在上述半導體裝置4的製作時，使用包含實施例1中所調製之有機金屬氧化物群D的封止層形成用組成物7來替代封止層形成用組成物4以外係以同樣方式，製成以屬本發明之封止方法的方法2形成封止層的本發明之半導體裝置7。[Production of semiconductor device 7: QFN form (present invention)] The same procedure was applied except that the sealing layer forming composition 7 including the organometallic oxide group D prepared in Example 1 was used in place of the sealing layer forming composition 4 during the production of the above-mentioned semiconductor device 4. The semiconductor device 7 of the present invention in which the sealing layer is formed by the method 2 of the sealing method of the present invention is manufactured.

《半導體裝置的評定》 針對上述製作之QFN規格的半導體裝置之半導體裝置1～7，依循下述方法進行耐腐蝕性的評定。"Assessment of Semiconductor Devices" For the semiconductor devices 1-7 of the QFN standard semiconductor devices manufactured above, the corrosion resistance was evaluated according to the following method.

準備100個各水準之半導體裝置，將其全部置入在裝置內配置有具有硫粉末作為腐蝕成分(G)的開放系統樣品瓶，且定為85℃、85%RH之環境條件的恆溫槽內，於實際運行狀態下保存1000小時。就此評定，係水分與硫成分(硫化氫)由外部環境侵入至封止層內，且於封止層內部，由阻燃劑成分產生鹵素(Cl- )的評定條件。Prepare 100 semiconductor devices of various levels and place them all in a constant temperature bath equipped with an open system sample bottle containing sulfur powder as the corrosive component (G) in the device and set at 85°C and 85%RH. , It can be stored for 1000 hours in the actual running state. In this evaluation, a sulfur-based moisture component (hydrogen sulfide) from the external environment intrusion into the passivation layer, and in the inner sealing layer is produced by flame retardant component halo (Cl -) The evaluation conditions.

其次，連續運行1000小時後，分別針對100個半導體裝置，確認在運行作動中有無發生異常(驅動不良)，並依循下述基準，判定半導體裝置的耐腐蝕性。Next, after 1000 hours of continuous operation, each of 100 semiconductor devices was checked for abnormality (driving failure) during operation, and the corrosion resistance of the semiconductor devices was judged according to the following criteria.

◎：100個半導體裝置中，於運行操作時發生異常之個體數為3個以下 ○：100個半導體裝置中，於運行操作時發生異常之個體數為4個以上且10個以下 △：100個半導體裝置中，於運行操作時發生異常之個體數為11個以上且20個以下 ×：100個半導體裝置中，於運行操作時發生異常之個體數為21個以上 將根據以上所得之結果示於表II。◎: Among 100 semiconductor devices, the number of abnormal entities during operation is 3 or less ○: Among the 100 semiconductor devices, the number of abnormal entities during operation is 4 or more and 10 or less △: Among 100 semiconductor devices, the number of abnormal entities during operation is 11 or more and 20 or less ×: Among 100 semiconductor devices, the number of individuals that have abnormalities during operation is 21 or more The results based on the above are shown in Table II.

Figure 02_image039
Figure 02_image039

由表II之記載，顯然本發明之半導體裝置在含硫成分的高溫高濕環境下長期間保存後，亦未發生由硫成分、水分及阻燃劑所產生之鹵素等所造成的腐蝕，且相對於比較例之半導體裝置1，本發明之半導體裝置2～7可確認正常地運行，可知耐腐蝕性極為優異。 [產業上可利用性]From the record in Table II, it is obvious that the semiconductor device of the present invention has not been corroded by sulfur components, moisture and halogens generated by flame retardants after being stored for a long period of time in a high temperature and high humidity environment containing sulfur components, and Compared with the semiconductor device 1 of the comparative example, the semiconductor devices 2 to 7 of the present invention can be confirmed to operate normally, and it can be seen that the corrosion resistance is extremely excellent. [Industrial availability]

本發明之封止方法可防止存在於封止構造中，或者由外部侵入之水分、鹵素成分、硫化氫氣體等所引起之構成半導體裝置之半導體元件或零件的腐蝕，而能夠適用於二極體、電晶體、積體電路等電子零件。The sealing method of the present invention can prevent corrosion of the semiconductor elements or parts constituting the semiconductor device caused by moisture, halogen components, hydrogen sulfide gas, etc., which are present in the sealing structure, and can be applied to diodes , Transistors, integrated circuits and other electronic parts.

1,21:半導體裝置 2:封裝基板 3:半導體元件 4,20:封止層 5:有機金屬氧化物 6:樹脂黏結劑 7:金屬銲點 8:接合線 9:半導體元件層合體 10:底部填充材 11:電路基板 12:焊料凸塊 13:測試用圖型化基板 14:元件基板 15:負電極 16:正電極 17:梳型場電極 18:電源 19:評定用晶片 22:引線框 23:黏晶材 F:填料 G:腐蝕成分 P:零件1,21: Semiconductor device 2: Package substrate 3: Semiconductor components 4, 20: Sealing layer 5: Organometallic oxide 6: Resin binder 7: Metal solder joints 8: Bonding wire 9: Semiconductor element laminate 10: Underfill material 11: Circuit board 12: Solder bump 13: Patterned substrate for testing 14: Component substrate 15: negative electrode 16: positive electrode 17: Comb-shaped field electrode 18: Power 19: Evaluation chip 22: Lead frame 23: Sticky crystal material F: filler G: Corrosive component P: Parts

[圖1A] 為表示藉由環氧樹脂與有機金屬氧化物、或有機金屬氧化物所形成之封止層之構成的方法1的一例的示意剖面圖。 [圖1B] 為表示藉由環氧樹脂與有機金屬氧化物、或有機金屬氧化物所形成之封止層之構成的方法2的一例的示意剖面圖。 [圖1C] 為表示藉由環氧樹脂與有機金屬氧化物、或有機金屬氧化物所形成之封止層之構成的方法3的一例的示意剖面圖。 [圖2] 為表示具有以本發明之方法1之封止方法所形成的封止層之半導體裝置的構造的一例的示意結構圖。 [圖3] 為表示具有以本發明之方法1之封止方法所形成的封止層之半導體裝置的構造的另一例的示意結構圖。 [圖4] 為表示在實施例中，具有供評定腐蝕性之梳型場電極的測試用圖型化基板之構成的示意結構圖。 [圖5] 為表示在實施例中，將測試用圖型化基板以本發明之封止層封止的評定用晶片(TEG)之構成的示意結構圖。 [圖6] 為表示圖5所記載之A-A'所示之評定用晶片(TEG)之構成的示意剖面圖。 [圖7A] 為實施例中所製作之半導體裝置(QFN)的示意剖面圖。 [圖7B] 為實施例中所製作之半導體裝置(QFN)的俯視圖。[FIG. 1A] is a schematic cross-sectional view showing an example of method 1 of the formation of a sealing layer formed by epoxy resin and organometallic oxide or organometallic oxide. [FIG. 1B] is a schematic cross-sectional view showing an example of method 2 of forming a sealing layer formed by epoxy resin and organometallic oxide or organometallic oxide. [FIG. 1C] is a schematic cross-sectional view showing an example of the method 3 of forming a sealing layer formed by epoxy resin and organometallic oxide or organometallic oxide. [FIG. 2] A schematic structural view showing an example of the structure of a semiconductor device having a sealing layer formed by the sealing method of method 1 of the present invention. 3 is a schematic structural view showing another example of the structure of a semiconductor device having a sealing layer formed by the sealing method of method 1 of the present invention. [Fig. 4] is a schematic structural diagram showing the structure of a patterned substrate for testing with comb-shaped field electrodes for evaluating corrosion in the embodiment. [FIG. 5] A schematic structural view showing the structure of an evaluation wafer (TEG) in which a patterned substrate for testing is sealed with the sealing layer of the present invention in an embodiment. [FIG. 6] A schematic cross-sectional view showing the structure of the evaluation wafer (TEG) shown in AA' described in FIG. 5. [FIG. 7A] is a schematic cross-sectional view of the semiconductor device (QFN) manufactured in the embodiment. [Fig. 7B] is a top view of the semiconductor device (QFN) manufactured in the embodiment.

1:半導體裝置 1: Semiconductor device

2:封裝基板 2: Package substrate

3:半導體元件 3: Semiconductor components

4:封止層 4: Sealing layer

5:有機金屬氧化物 5: Organometallic oxide

6:樹脂黏結劑 6: Resin binder

7:金屬銲點 7: Metal solder joints

8:接合線 8: Bonding wire

9:半導體元件層合體 9: Semiconductor element laminate

10:底部填充材 10: Underfill material

11:電路基板 11: Circuit board

12:焊料凸塊 12: Solder bump

G:腐蝕成分 G: Corrosive component

Claims (12)

一種封止方法，其係構成半導體裝置之半導體元件及零件的封止方法，其特徵為藉由以下任一種方法來形成封止層： (1)使用含有環氧樹脂與有機金屬氧化物的組成物之方法1； (2)使用含有環氧樹脂與由有機金屬氧化物被覆之填料的組成物之方法2；或 (3)將前述零件以有機金屬氧化物封止後，以環氧樹脂予以被覆之方法3。A sealing method, which is a method for sealing semiconductor elements and parts constituting a semiconductor device, characterized by forming a sealing layer by any of the following methods: (1) Method 1 of using a composition containing epoxy resin and organic metal oxide; (2) Method 2 of using a composition containing an epoxy resin and a filler coated with an organic metal oxide; or (3) Method 3 where the aforementioned parts are sealed with organometallic oxide and then coated with epoxy resin. 如請求項1之封止方法，其中前述有機金屬氧化物為具有下述通式(1)所示之結構的有機金屬氧化物；
Figure 03_image001
[式中，R表示氫原子、碳數1個以上之烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基；惟，R亦可包含氟原子作為取代基；M表示金屬原子；OR1 表示氟化烷氧基；x表示金屬原子的價數，y表示1與x之間的任意之整數；n表示聚縮合度]。The sealing method of claim 1, wherein the aforementioned organometallic oxide is an organometallic oxide having a structure represented by the following general formula (1);
Figure 03_image001
[In the formula, R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group with more than 1 carbon; however, R may also contain a fluorine atom as a substituent ; M represents a metal atom; OR 1 represents a fluorinated alkoxy group; x represents the valence of the metal atom, y represents an integer between 1 and x; n represents the degree of polycondensation]. 如請求項1或2之封止方法，其係具有以塗佈法形成前述封止層之步驟。Such as the sealing method of claim 1 or 2, which has a step of forming the aforementioned sealing layer by a coating method. 一種封止層，其特徵為至少由環氧樹脂及具有下述通式(1)所示之結構的有機金屬氧化物所構成；
Figure 03_image003
[式中，R表示氫原子、碳數1個以上之烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基；惟，R亦可包含氟原子作為取代基；M表示金屬原子；OR1 表示氟化烷氧基；x表示金屬原子的價數，y表示1與x之間的任意之整數；n表示聚縮合度]。A sealing layer characterized by being composed of at least epoxy resin and organometallic oxide having a structure represented by the following general formula (1);
Figure 03_image003
[In the formula, R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group with more than 1 carbon; however, R may also contain a fluorine atom as a substituent ; M represents a metal atom; OR 1 represents a fluorinated alkoxy group; x represents the valence of the metal atom, y represents an integer between 1 and x; n represents the degree of polycondensation]. 一種封止層，其特徵為由具有下述通式(1)所示之結構的有機金屬氧化物所構成；
Figure 03_image005
[式中，R表示氫原子、碳數1個以上之烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基；惟，R亦可包含氟原子作為取代基；M表示金屬原子；OR1 表示氟化烷氧基；x表示金屬原子的價數，y表示1與x之間的任意之整數；n表示聚縮合度]。A sealing layer characterized by being composed of an organometallic oxide having a structure represented by the following general formula (1);
Figure 03_image005
[In the formula, R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group with more than 1 carbon; however, R may also contain a fluorine atom as a substituent ; M represents a metal atom; OR 1 represents a fluorinated alkoxy group; x represents the valence of the metal atom, y represents an integer between 1 and x; n represents the degree of polycondensation]. 如請求項4或5之封止層，其中前述有機金屬氧化物中氟原子數相對於碳原子數與氟原子數之總數的比值F/(C+F)係滿足下式(a)所規定之條件；
Figure 03_image007
。Such as the sealing layer of claim 4 or 5, wherein the ratio F/(C+F) of the number of fluorine atoms in the organometallic oxide to the total number of carbon atoms and the total number of fluorine atoms meets the requirements of the following formula (a) The conditions;
Figure 03_image007
. 如請求項4至6中任一項之封止層，其中前述通式(1)中以M表示之金屬原子係由Ti、Zr、Sn、Ta、Fe、Zn、Bi、Cu、Mg、Mn、Co、Ni、Ag及Al選出的至少一種。Such as the sealing layer of any one of claims 4 to 6, wherein the metal atom represented by M in the general formula (1) is composed of Ti, Zr, Sn, Ta, Fe, Zn, Bi, Cu, Mg, Mn At least one selected from, Co, Ni, Ag and Al. 如請求項4至7中任一項之封止層，其係含有由前述有機金屬氧化物被覆之填料。The sealing layer according to any one of claims 4 to 7, which contains a filler coated with the aforementioned organometallic oxide. 一種封止層形成用之混合液，其特徵為含有下述通式(A)所示之化合物或具有下述通式(1)所示之結構的有機金屬氧化物與醇類；
Figure 03_image009
[式中，R表示氫原子、碳數1個以上之烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基；惟，R亦可包含氟原子作為取代基；M表示金屬原子；OR1 表示氟化烷氧基；x表示金屬原子的價數，y表示1與x之間的任意之整數；n表示聚縮合度]。A mixed solution for forming a sealing layer, characterized by containing a compound represented by the following general formula (A) or an organometallic oxide having a structure represented by the following general formula (1) and alcohols;
Figure 03_image009
[In the formula, R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group with more than 1 carbon; however, R may also contain a fluorine atom as a substituent ; M represents a metal atom; OR 1 represents a fluorinated alkoxy group; x represents the valence of the metal atom, y represents an integer between 1 and x; n represents the degree of polycondensation]. 一種封止層之製造方法，其係製造如請求項4至8中任一項之封止層的封止層之製造方法，其特徵為： 使用如請求項9之封止層形成用之混合液來製造。A method for manufacturing a sealing layer, which is a method for manufacturing a sealing layer such as the sealing layer of any one of claims 4 to 8, characterized by: It is manufactured using the mixed solution for forming a sealing layer as in Claim 9. 一種半導體裝置，其係至少由半導體元件及零件所構成的半導體裝置，其特徵為： 前述半導體元件或零件係由如請求項4至7中任一項之封止層所被覆。A semiconductor device, which is a semiconductor device composed of at least semiconductor elements and parts, characterized by: The aforementioned semiconductor elements or parts are covered by the sealing layer as in any one of claims 4 to 7. 如請求項11之半導體裝置，其中由前述封止層所被覆之前述零件為接合線或金屬銲點(land)。The semiconductor device according to claim 11, wherein the component covered by the sealing layer is a bonding wire or a metal land.
TW108140215A 2018-11-30 2019-11-06 Sealing method, sealing layer, mixed solution for forming sealing layer, manufacturing method of sealing layer, and semiconductor device TWI741405B (en)

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