CN117062890A - 用于低间隙底部填充应用的助熔剂相容性环氧-酚类粘合剂组合物 - Google Patents

用于低间隙底部填充应用的助熔剂相容性环氧-酚类粘合剂组合物 Download PDF

Info

Publication number
CN117062890A
CN117062890A CN202180096089.4A CN202180096089A CN117062890A CN 117062890 A CN117062890 A CN 117062890A CN 202180096089 A CN202180096089 A CN 202180096089A CN 117062890 A CN117062890 A CN 117062890A
Authority
CN
China
Prior art keywords
cycloaliphatic
epoxy
phenol
flux
phenolic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202180096089.4A
Other languages
English (en)
Inventor
杨展航
L·M·斯里哈
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of CN117062890A publication Critical patent/CN117062890A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—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
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/73—Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L24/80 - H01L24/90
    • H01L24/92—Specific sequence of method steps
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/13001—Core members of the bump connector
    • H01L2224/13099—Material
    • H01L2224/131—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • 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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector 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
    • H01L2224/16221—Disposition the bump connector 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
    • H01L2224/16225—Disposition the bump connector 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
    • H01L2224/16227—Disposition the bump connector 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 the bump connector connecting 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
    • H01L2224/01—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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/2919—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • 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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector 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
    • H01L2224/32221—Disposition the layer connector 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
    • H01L2224/32225—Disposition the layer connector 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
    • 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
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • 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
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/81009—Pre-treatment of the bump connector or the bonding area
    • H01L2224/8101—Cleaning the bump connector, e.g. oxide removal step, desmearing
    • H01L2224/81011—Chemical cleaning, e.g. etching, flux
    • 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
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/8119—Arrangement of the bump connectors prior to mounting
    • H01L2224/81191—Arrangement of the bump connectors prior to mounting wherein the bump connectors are disposed only on the semiconductor or solid-state body
    • 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
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/8119—Arrangement of the bump connectors prior to mounting
    • H01L2224/81192—Arrangement of the bump connectors prior to mounting wherein the bump connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body
    • 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
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/8119—Arrangement of the bump connectors prior to mounting
    • H01L2224/81193—Arrangement of the bump connectors prior to mounting wherein the bump connectors are disposed on both the semiconductor or solid-state body and another item or body to be connected to the semiconductor or solid-state body
    • 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
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/818—Bonding techniques
    • H01L2224/81801—Soldering or alloying
    • H01L2224/81815—Reflow soldering
    • 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
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/81905—Combinations of bonding methods provided for in at least two different groups from H01L2224/818 - H01L2224/81904
    • H01L2224/81907—Intermediate bonding, i.e. intermediate bonding step for temporarily bonding the semiconductor or solid-state body, followed by at least a further bonding step
    • 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
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H01L2224/83855—Hardening the adhesive by curing, i.e. thermosetting
    • H01L2224/83862—Heat curing
    • 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
    • H01L2224/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
    • H01L2224/92—Specific sequence of method steps
    • H01L2224/921—Connecting a surface with connectors of different types
    • H01L2224/9212—Sequential connecting processes
    • H01L2224/92122—Sequential connecting processes the first connecting process involving a bump connector
    • H01L2224/92125—Sequential connecting processes the first connecting process involving a bump connector the second connecting process involving a layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—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
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L24/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—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
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • 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
    • H01L2924/30—Technical effects
    • H01L2924/35—Mechanical effects
    • H01L2924/351—Thermal stress

Abstract

本发明提供可用作低间隙底部填充料的助熔剂相容性环氧‑酚粘合剂组合物和可用于其中的新型酚。助熔剂相容性环氧‑酚粘合剂组合物包含：环氧组分，所述环氧组分包含具有环脂族、脂环族或混合环脂族‑芳族主链的环氧化合物；多官能酚类组分；以及催化剂。助熔剂相容性组合物可用作底部填充密封剂，其(1)快速填充半导体器件(如倒装芯片组件)中的底部填充空间，(2)使器件能够通过短时间热固化牢固地连接至电路板并且具有良好的生产率，并且(3)显示出优异的耐焊料回流性。

Description

用于低间隙底部填充应用的助熔剂相容性环氧-酚类粘合剂 组合物
技术领域
本公开涉及用于低间隙底部填充应用的助熔剂相容性环氧-酚类粘合剂组合物，并且涉及可用于其中的新型酚。
背景技术
以下讨论被提供仅用以帮助读者理解本公开，而不是承认描述或构成现有技术。
近年来，更小型电子设备的普及使得半导体器件的尺寸减小成为期望的。因此，芯片(chip)封装的尺寸减小至基本上裸晶片(die)本身的尺寸。新型封装设计具有更多功能、更精细的间距、低间隙、更薄封装和扩展的下游市场的趋势不仅带来了更高的可靠性要求，也已经产生了前几代底部填充技术不存在的许多新挑战。
将集成电路附接至有机基材板的倒装芯片方法使用集成电路上的一系列金属焊料突起(solder bump)，所述金属焊料突起与板上的金属结合位点形成互连。集成电路的有源侧(active side)被颠倒翻转，以便在集成电路上的突起与基材上的金属结合位点之间形成接触。当组件被加热至高于焊料的熔融温度时，有机焊接助熔剂用于去除金属氧化物并且促进焊料的润湿。这种将集成电路附接至基材的工艺被称为回流焊接。助熔剂的目的是清洁金属表面以改善电连接。取决于所选择的材料，焊料或更低熔点合金可以包括基材上的金属结合位点、集成电路上的突起、或者这两者。较高熔点合金也可以类似地存在于无铅焊料中。类似地，较高熔点合金可以存在于主要由环境问题驱动的无铅焊料中。
对于小间隙底部填充，来自助熔剂的残留物难以从窄间隙中去除。因此，大多数倒装芯片应用的助熔剂选择是免清洗助熔剂，在该免清洗助熔剂中，助熔剂残留物在焊料回流(solder reflow)工艺之后不从板上去除。这些免清洗助熔剂可以在芯片放置之前分配至板上的金属结合位点上。为了在回流工艺之前保持芯片与板的对准，可以将粘性助熔剂施加至芯片上的突起。将包含焊料突起的集成电路浸入助熔剂中至设定深度，以将所需量的粘性助熔剂仅施加至突起的表面。然后，将芯片对准并放置到基材上，以便经助熔剂涂覆的突起接触基材的适当的金属结合位点。粘性助熔剂被配制成含有较高固体含量，这有助于芯片在回流之前粘合至基材。因此，粘性助熔剂充当临时胶，以在将组件放置进回流焊炉期间将芯片保持适当的对准。常用的粘性助熔剂是免清洗表面安装工艺中使用的焊膏用助熔剂载体(vehicle)。
尽管免清洗焊膏用助熔剂载体的配制物不同，但典型组合物包含50％松香、40％溶剂、5-8％增稠剂和2-5％助熔剂活化剂(如有机酸和胺)。虽然助熔剂的大部分溶剂在回流工艺期间蒸发，但焊膏成分的松香酯和其他非挥发性残留物保留。
在焊料回流以将集成电路附接至基材之后，倒装芯片组件中的集成电路与有机基材之间的间隙通过毛细作用被底部填充密封剂或粘合剂填充。密封剂的目的是减轻由硅集成芯片(热膨胀系数(CTE)＝2.5ppm/℃)与有机基材(CTE＝15-20ppm/℃)之间的热膨胀系数的差异引起的焊料互连件上的热机械应力。
倒装芯片组件中使用的典型底部填充密封剂由环氧树脂、固化剂和无机填料组成，以在固化时产生交联的热固性聚合物。已固化聚合物的性质(如CTE和弹性模量)有助于减轻使用期间焊接接合处上的热机械应力，其通过热循环测试来测试。典型的热循环测试涉及在-55℃和125℃下将倒装芯片组件重复暴露于两种不同的液体，其中在各温度下十分钟停留时间。因此，底部填充密封剂的总体目的是通过减轻焊接接合处上的热机械应力来提高倒装芯片组件的使用寿命和可靠性。
几种工艺和材料性质特征决定底部填充密封剂的材料选择。首先，环氧底部填充密封剂应当在生产期间在芯片下方快速流动。可以优化密封剂的粘度、表面张力和粒径分布，以在封装步骤期间实现芯片下方的高效流动。为了进一步减少底部填充时间，可以加热基材以降低未固化密封剂的粘度并且提高材料的流动速度。通常在分配密封剂之前将基材板的表面加热至70℃，以实现此效果。其次，环氧底部填充密封剂应当相对快速地固化。典型的底部填充密封剂是被设计成在130-170℃的温度下固化(即，形成不可逆交联结构)的环氧配制物。最后，环氧底部填充密封剂应当在热循环测试期间牢固地粘合至芯片和基材两者。如果环氧树脂与芯片或基材表面脱离或分层，则将无法实现互连件上的适当应力消除。
免清洗助熔剂残留物与环氧底部填充密封剂之间的相互作用对于实现最大粘合性和期望的倒装芯片可靠性是重要的。用作倒装芯片工艺的粘性助熔剂的典型焊膏用助熔剂组合物包含松香或类似树脂。在将集成电路回流焊接至基材之后，松香和助熔剂的其他非挥发性有机成分的残留物保留在基材上。尽管这些免清洗残留物在其腐蚀性方面对组件是无害的，但已经已知这些残留物会引起空隙和焊料挤出，从而对器件的粘合性和电气完整性产生不利影响。由于底部填充密封剂的粘合性差，该结果会导致与芯片表面的提早分层。该密封剂与芯片的分层可以使用扫描声学显微镜(SAM)来检测和测量，其允许检测芯片表面与环氧底部填充料之间空隙的存在。
因此，与底部填充密封剂的助熔剂相容性是底流(underflow)工艺性能的重要标准。
在经受重复焊料回流条件时显示稳定的Tg并且具有低吸湿性的助熔剂相容性底部填充粘合剂将是非常期望的。保持稳定的Tg对于较高温度下的良好粘合性是重要的。
发明内容
本公开提供可用作底部填充密封剂的助熔剂相容性组合物，其(1)快速填充半导体器件(如倒装芯片组件)中的底部填充空间，(2)使器件能够通过短时间热固化牢固地连接至电路板并且具有良好的生产率，并且(3)显示出优异的热循环性质。该组合物包含环氧树脂组分、酚类组分和催化剂。本公开还提供可用于该组合物中的新型酚类。
使用本公开的组合物，半导体器件(如倒装芯片组件)可以(1)由于提高的固化速度和延长的可用使用寿命而被快速地且在没有生产线停工时间的情况下组装，并且(2)通过组合物的短时间热固化牢固地连接至电路板，其中所得到的安装好的结构显示出优异的热冲击性质或热循环性质。
因此，本公开提供通常用于低间隙底部填充应用的助熔剂相容性环氧-酚粘合剂组合物。该组合物包含：
环氧组分，所述环氧组分包含具有环脂族、脂环族或混合环脂族-芳族、脂环族-芳族主链的环氧化合物；
酚类组分，如多官能酚；以及
催化剂。
环氧组分可以是具有环脂族、脂环族、混合环脂族-芳族或脂环族-芳族主链的环氧化合物。
酚类组分可以是例如由通用结构I、结构II、结构III和/或结构IV表示的多官能酚：
其中X是任选地具有脂族侧链的环脂族、脂环族或混合环脂族-芳族的单环、双环或多环环结构，并且酯基的氧可以直接连接至所述环或所述脂族侧链；
X1是任选地包含杂原子O或S的亚烷基或支化亚烷基；
R3是H、烷基或环烷基；
L1和L2独立地选自共价键、任选地包含杂原子O或S的亚烷基、支化亚烷基和亚环烷基；
R1和R2是H、甲基或OH，条件是每个环中的R1或R2中的至少一个是OH；并且
结构I、结构II、结构III和结构IV中存在的酯基可以是伯酯基或仲酯基。
或者，酚组分可以选自结构V、结构VI和/或结构VII：
其中R是脂族、环脂族、脂环族、混合芳族-环脂族或聚合物主链；此外，在结构V和结构VII中，R可以是稠环；
R1和R2是H、烷基或OH，条件是R1或R2中的至少一个是OH；
n＝1-10；并且
结构V中连接至酚环的稠环是任选存在的，并且在存在时可以是芳族的、环脂族的、脂环族的或杂环的。
催化剂可以选自咪唑类、被取代的咪唑类、潜伏性咪唑类(latent imidazoles)、封装型咪唑类(encapsulated imidazoles)、苯酚官能化的咪唑类和萘酚官能化的咪唑类、以及脒和胍类型催化剂或苯酚官能化的咪唑催化剂。
本公开的益处和优点将从以下具体实施方式中将变得更加明显。
具体实施方式
如上所述，本公开提供通常用于低间隙底部填充应用的助熔剂相容性环氧-酚粘合剂组合物。该组合物宽泛地包含环氧组分、酚类组分和催化剂。
环氧组分可以选自具有环脂族、脂环族、混合环脂族-芳族、或混合脂环族-芳族主链的环氧化合物。特别有用的环氧树脂是下式中所示的EP4088S、Eponex1510、HP7200、Hyloxy modifier 107及其混合物，但也可以使用具有环脂族、混合环脂族-芳族主链和/或芳族主链的其他树脂。实例包括由Sugai Chemical Industry供应的单官能和双官能十氢萘缩水甘油醚、基于环脂族主链(如金刚烷环结构)的单官能和多官能缩水甘油醚，包括单官能和多官能十氢萘缩水甘油醚、单官能和多官能DCPD缩水甘油醚、氢化双酚A的二缩水甘油醚、单官能和多官能金刚烷基缩水甘油醚、环脂族缩水甘油酯、环状单烯和多烯的单官能和多官能环氧化合物、及其混合物。
酚类组分可以是多官能酚，并且可以选自其式在下文给出的那些：
这些多官能酚(酚1-4)是新型的，并且构成本公开的另一方面。
除了以上新型酚以外，某些已知的脂环族酚也可以用作组合物的酚类组分。合适的酚由DIC International Chemicals以商品名称PhenoliteTM苯酚酚醛清漆树脂销售。特别合适的已知酚是DCPD酚醛清漆和甲酚酚醛清漆。还有用的是双酚A酚醛清漆、苯酚酚醛清漆、三嗪酚醛清漆、二烯丙基双酚A、二羟基萘(所有异构体)、2-烯丙基苯基酚醛清漆、二羟基二苯甲酮(所有异构体)、三羟基二苯甲酮(所有异构体)、Rezicure 3000、双(4-羟基苯基)硫醚、以及双(4-羟基苯基)砜。
酚类组分还可以是由通用结构I、结构II、结构III和/或结构IV表示的多官能酚：
其中X是任选地具有脂族侧链的环脂族或脂环族的单环、双环或多环环结构；并且酯基的氧直接连接至所述环或所述侧链；
X1是任选地包含杂原子O或S的亚烷基或支化亚烷基；
R3是H、烷基或环烷基；
L1和L2独立地选自共价键、任选地包含杂原子O或S的亚烷基、支化亚烷基和亚环烷基；
R1和R2独立地是H、甲基或OH，条件是每个环中的R1或R2中的至少一个是OH；并且
结构I、结构II、结构III和结构IV中存在的酯官能团可以是伯酯基或仲酯基。
助熔剂相容性环氧-酚粘合剂配混物中使用的酚可以选自结构V、结构VI和/或结构VII的化合物：
其中R是脂族、环脂族、脂环族、混合芳族-环脂族或聚合物主链；此外，在结构V和结构VII中，R可以是稠环；
R1和R2是H、烷基或OH，条件是R1或R2中的至少一个是OH；
n＝1-10；并且
结构V中连接至酚环的稠环是任选存在的，并且在存在时可以是芳族的、环脂族的、脂环族的或杂环的。
以上酰亚胺或邻苯二甲酰亚胺官能的酚可以通过脂族、脂环族、芳族、芳烷基胺与单官能或多官能酸酐的酰亚胺化来获得。酸酐可以选自：甲基六氢邻苯二甲酸酐、纳迪克酸酐(甲基-5-降冰片烯-2,3-二羧酸酐；“MNA”)或5-降冰片烯-2,3-二羧酸酐、六氢-4-甲基邻苯二甲酸酐(MHHPA)、甲基四氢邻苯二甲酸酐(MTHPA)、甲基环己烯-1,2-二羧酸酐、甲基双环[2.2.1]庚烷-2,3-二羧酸酐、双环[2.2.1]庚烷-2,3-二羧酸酐、(2-十二烯-1-基)琥珀酸酐、戊二酸酐、柠康酸酐、甲基琥珀酸酐、2,2-二甲基琥珀酸酐、2,2-二甲基戊二酸酐、3-甲基戊二酸酐、3,3-四亚甲基戊二酸酐、3,3-二甲基戊二酸酐、羟基邻苯二甲酸酐的几种异构体、或其混合物。
可以用于酰亚胺化反应的多官能酸酐包括聚丙烯-接枝-马来酸酐、聚乙烯-接枝-马来酸酐、丁二烯-马来酸酐共聚物、苯乙烯-马来酸酐共聚物、以及马来酸酐、衣康酸酐和柠康酸酐的其他共聚物和三元共聚物。
可以用于酰亚胺化反应的胺和胺官能酚包括但不限于：氨基苯酚的几种异构体；儿茶酚胺；氨基萘酚；二聚体二胺；TCD-二胺(3(4),8(9)-双(氨基甲基)-三环癸烷)；环己胺；脂族、环脂族和脂环族伯二胺。
环氧-酚粘合剂组合物还可以包含马来酰亚胺树脂，所述马来酰亚胺树脂可以是双马来酰亚胺、下文表示的结构VIII和结构IX的多官能马来酰亚胺或酚官能马来酰亚胺：
其中L选自共价键、任选地具有杂原子O或S的亚烷基、亚环烷基和支化亚烷基；L也可以含有酯键或碳酸酯键；并且
结构VIII中的稠环是任选存在的，并且在存在时是芳族的、环脂族的、脂环族的或杂环的。
马来酰亚胺树脂可以通过单官能或多官能伯胺与马来酸酐的酰亚胺化反应来获得，或者可以通过单官能或多官能脂族、环脂族、脂环族或芳烷基醇与6-马来酰亚胺基己酸的费歇尔酯化(Fisher esterification)来获得。酚官能马来酰亚胺也可以通过氨基苯酚的几种异构体、氨基萘酚、儿茶酚胺或侧链胺官能酚与马来酸酐的酰亚胺化反应来获得。
可以使用各种催化剂，其中包括咪唑类、被取代的咪唑类、潜伏性咪唑类、封装型咪唑类、苯酚官能化的咪唑类和萘酚官能化的咪唑类。发现咪唑催化剂Technicure EMI-24CN是特别期望的固化剂。例如，在4％浓度下，具有该催化剂的环氧-酚粘合剂组合物显示出Tg与其他性能性质的良好平衡。可以使用可从Evonik Corporation获得的以商品名称Curezol销售的潜伏性咪唑、来自A&C catalysts的封装型咪唑、以及苯酚或萘酚官能化的咪唑(如Aradur 3123)。优选的催化剂包括Technicure EMI 24-CN、Curezol2-PHZ-S、Curezol 2-PZ、Curezol 2PZ-azine、Aardur 3123、以及胺和多胺官能咪唑。
环氧组分与酚类组分的比率可以是1:1至1:0.05。该比率优选为1:0.2，并且更优选为1:0.1。环氧组分与酚类组分的组合通常占粘合剂组合物的约50％，余量选自固化剂、促进剂、催化剂、流动改性剂、填料、粘合促进剂和触变剂。
在某些实施方案中，粘合剂组合物还可以包含一种或多种流动添加剂、粘合促进剂、导电添加剂、流变改性剂等、以及其中任何两种或更多种的混合物。各种添加剂可以根据需要包含在组合物中，例如有机填料或无机填料、触变剂、硅烷偶联剂、稀释剂、改性剂、着色剂(如颜料和染料)、表面活性剂、防腐剂、稳定剂、增塑剂、润滑剂、消泡剂、流平剂等；然而，不限于这些。特别是，组合物优选地包含选自有机填料或无机填料、触变剂和硅烷偶联剂的添加剂。这些添加剂可以以总组合物的约0.1重量％至约50重量％、更优选地总组合物的约2重量％至约10重量％的量存在。
触变剂可以包括但不限于滑石、气相法二氧化硅、超细的经表面处理的碳酸钙、细颗粒氧化铝、片状氧化铝；层状化合物(如蒙脱石)、针状化合物(如硼酸铝晶须)等。其中，滑石、气相法二氧化硅和细氧化铝是特别期望的。这些试剂可以以总组合物的约1重量％至约50重量％、更优选地约1重量％至约30重量％的量存在。
硅烷偶联剂可以包括但不限于γ-氨基丙基三乙氧基硅烷、γ-巯基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-缩水甘油氧基丙基三甲氧基硅烷等。
如本文所使用的，“流动添加剂”是指硅聚合物、丙烯酸乙酯/丙烯酸2-乙基己酯共聚物、酮肟的磷酸酯的烷醇铵盐(alkylol ammonium salt)等、以及组合。这些添加剂中的几种可从商业来源(如BYK和Evonik Corporation)获得。
本公开提供以下非限制性且非穷举性实施例。
实施例
如表1所示，在酚-环氧配制物中筛选几种咪唑催化剂。当使用合适的咪唑促进剂时，所测试的配制物中的一些显示出较高的Tg。液体咪唑催化剂(Technicure EMI-24CN)看起来在降低固化温度方面表现最佳。该催化剂的低粘度是额外的优点。
表1：酚固化的环氧体系的初始配制物筛选
发现具有环脂族主链的环氧树脂显示出良好的助熔剂相容性。以纯(neat)形式针对助熔剂相容性进行筛选的环氧树脂中的一些包括EP4088S、Eponex1510、HP7200L、Hyloxymodifier 107、以及以上的混合物。所有这些环氧树脂均具有环脂族或混合环脂族-芳族主链。助熔剂相容性研究是如下进行的：使用含有约5％助熔剂的环氧树脂，将混合物加热至约80℃长达约30分钟，并且将混合物高速混合。在冷却至室温并且储存后，它们产生清澈的混合物，而没有任何混浊。
对于酚类组分，如以下实施例中所述，制备含有环脂族或脂族主链的几种多官能酚。
实施例1：四官能酚1的合成
在配备有热电偶、机械搅拌器和冷凝器的1L 3颈烧瓶中，在甲苯600mL中放置4,8-双(羟基甲基)三环[5.2.1.02,6]癸烷(49.2g，250mmol)、双酚酸(143.5g，500mmol)、PTSA(3g，1.5％)。将混合物与水共沸蒸馏搅拌12小时。在冷却至环境温度后，滗析甲苯，并且将剩余固体溶解于1L乙酸乙酯中。将溶液用水洗涤一次，用碳酸氢钠水溶液洗涤两次，并且用水洗涤一次。在溶液经无水Na2SO4干燥后，使用旋转蒸发器在减压下蒸发溶剂。在高真空下在80℃下去除最后痕量的溶剂长达数小时，以产生为紫色固体的酚1(152g，83％)。
实施例2：四官能酚2的合成
在配备有热电偶、机械搅拌器和冷凝器的1L 3颈烧瓶中，在甲苯400mL中放置3-甲基-1,5-戊二醇(8.94g，75mmol)、双酚酸(43.11g，150mmol)、PTSA(1.1g，2.2％)。将混合物与水共沸蒸馏搅拌12小时。在冷却至环境温度后，滗析甲苯，并且将剩余固体溶解于600mL乙酸乙酯中。将溶液用水洗涤一次，用碳酸氢钠水溶液洗涤两次，并且用水洗涤一次。在溶液经无水Na2SO4干燥后，使用旋转蒸发器在减压下蒸发溶剂。在高真空下在80℃下去除最后痕量的溶剂长达数小时，以产生为紫色固体的酚2(38g，88％)。
实施例3：双官能酚3的合成
在配备有热电偶、机械搅拌器和冷凝器的1L 3颈烧瓶中，在甲苯600mL中放置4,8-双(羟基甲基)三环[5.2.1.02,6]癸烷(54.4g，277mmol)、4-羟基苯甲酸(76.55g，554mmol)、PTSA(2.6g，2％)。将混合物与水共沸蒸馏搅拌12小时。在冷却至环境温度后，滗析甲苯，并且将剩余固体溶解于1L乙酸乙酯中。将溶液用水洗涤一次，用碳酸氢钠水溶液洗涤两次，并且用水洗涤一次。在溶液经无水Na2SO4干燥后，使用旋转蒸发器在减压下蒸发溶剂。在高真空下在80℃下去除最后痕量的溶剂长达数小时，以产生为紫色固体的酚3(95g，77％)。
实施例4：四官能酚4的合成
在配备有热电偶、机械搅拌器和冷凝器的1L 3颈烧瓶中，在甲苯600mL中放置4,8-双(羟基甲基)三环[5.2.1.02,6]癸烷(35g，177mmol)、3,4-二羟基苯基乙酸(59.96g，356mmol)、PTSA(1.9g，2％)。将混合物与水共沸蒸馏搅拌48小时。在冷却至环境温度后，滗析甲苯，并且将剩余固体溶解于1L乙酸乙酯中。将溶液用水洗涤一次，用碳酸氢钠水溶液洗涤两次，并且用水洗涤一次。在溶液经无水Na2SO4干燥后，使用旋转蒸发器在减压下蒸发溶剂。在高真空下在80℃下去除最后痕量的溶剂长达数小时，以产生为棕色固体的酚4(79g，82％)。
如下表2所示，制备并且筛选几种不含填料(unfilled)的环氧-酚配制物。
表2：不含填料的环氧-酚类配制物
上表2示出几种环氧-酚类不含填料的配制物及其固化和Tg概况。咪唑催化剂的量在所有这些配制物中保持恒定在4重量％。发现使用Hyloxy modifier 107有益于较低的粘度。然而，该环脂族环氧树脂不利地影响Tg。与使用二烯丙基双酚A的配制物相比，使用四官能酚1看起来显著地提高Tg(表2中的配制物5相比于6)。
由于环脂族环氧树脂以纯形式显示出良好的助熔剂相容性，因此通过将它们与其他环氧树脂共混制备几种含填料的配制物，以获得Tg、粘度与助熔剂相容性的平衡。开发几种至少部分地含有具有环脂族主链的环氧树脂的环氧-酚类配制物以改善助熔剂相容性。与不含填料的配制物形成对比，当使用二氧化硅作为填料时，与对应的不含填料的配制物相比，含填料的配制物显示出Tg显著降低。为了获得在120-140℃范围内的Tg，通过添加具有环脂族-脂族主链的多官能酚来对配制物进行改性，以制备表3中所示的配制物。
表3：使用助熔剂相容性环氧树脂的环氧-酚类含填料的配制物
表4中示出表3的几种含填料配制物的Tg和粘度概况。环氧-酚类化学的一个显著特征是在第二DSC Tg温变(ramp)后观察到Tg的增加，即使DSC峰值温度较低也是如此。该结果可以归因于第二加热期间的额外交联。当经受多重焊料回流条件时，增加的Tg可以有益于器件的可靠性。
表4：原型配制物的固化概况、粘度和Tg
/>

Claims (17)

1.用于低间隙底部填充应用的助熔剂相容性环氧-酚粘合剂，包含：
环氧组分，所述环氧组分包含具有环脂族、脂环族或混合环脂族-芳族、脂环族-芳族主链的环氧化合物；
多官能酚类组分；以及
催化剂。
2.如权利要求1所述的助熔剂相容性环氧-酚粘合剂，其中所述环氧化合物选自EP4088S、Eponex1510、HP7200L、Hyloxy modifier 107、单官能和多官能十氢萘缩水甘油醚、单官能和多官能DCPD缩水甘油醚、氢化双酚A的二缩水甘油醚、单官能和多官能金刚烷基缩水甘油醚、环脂族缩水甘油酯、衍生自环脂族单胺和二胺的缩水甘油基化合物、环状单烯和多烯的单官能和多官能环氧化合物、及其混合物。
3.如权利要求1所述的助熔剂相容性环氧-酚粘合剂，其中所述催化剂选自咪唑类、被取代的咪唑类、潜伏性咪唑类、封装型咪唑类、苯酚官能化的咪唑类和萘酚官能化的咪唑类。
4.如权利要求3所述的助熔剂相容性环氧-酚粘合剂，其中所述催化剂选自TechnicureEMI 24-CN、Curezol 2-PHZ-S、Curezol 2-PZ、Curezol2PZ-azine、Aardur 3123、Ajicure系列、Technicure系列、Resicure系列、Technirez系列、以及胺和多胺官能咪唑。
5.如权利要求1所述的助熔剂相容性环氧-酚粘合剂，其中所述酚选自结构I、结构II、结构III和/或结构IV：
其中X是任选地具有脂族侧链的环脂族或脂环族的单环、双环或多环环结构；酯基的氧直接连接至所述环或所述脂族侧链；
X1是任选地包含杂原子O或S的亚烷基或支化亚烷基；
R3是H、烷基或环烷基；
L1和L2独立地选自共价键、任选地包含杂原子O或S的亚烷基、支化亚烷基和亚环烷基；
R1和R2独立地是H、甲基或OH，条件是每个环中的R1或R2中的至少一个是OH；并且
结构I、结构II、结构III和结构IV中存在的所述酯基可以是伯酯基或仲酯基。
6.如权利要求1所述的助熔剂相容性环氧-酚粘合剂，其中所述多官能酚类组分选自以下酚类化合物：
DCPD酚醛清漆、甲酚酚醛清漆、双酚A酚醛清漆、苯酚酚醛清漆、三嗪酚醛清漆、二烯丙基双酚A、二羟基萘(所有异构体)、2-烯丙基苯基酚醛清漆、二羟基二苯甲酮(所有异构体)、三羟基二苯甲酮(所有异构体)、Rezicure 3000、双(4-羟基苯基)硫醚、以及双(4-羟基苯基)砜。
7.如权利要求1所述的助熔剂相容性环氧-酚粘合剂，其中所述酚类组分选自结构V、结构VI和/或结构VII：
其中R是脂族、环脂族、脂环族、混合芳族-环脂族或聚合物主链；此外，在结构V和结构VII中，R可以是稠环；
R1和R2是H、烷基或OH，条件是R1或R2中的至少一个是OH；
n＝1-10；并且
结构V中连接至酚环的所述稠环是任选存在的，并且在存在时可以是芳族的、环脂族的、脂环族的或杂环的。
8.如权利要求1所述的助熔剂相容性环氧-酚粘合剂，还包含马来酰亚胺树脂。
9.如权利要求8所述的助熔剂相容性环氧-酚粘合剂，其中所述马来酰亚胺树脂是双马来酰亚胺、结构VIII和结构IX的多官能马来酰亚胺：
其中L选自共价键、任选地具有杂原子O或S的亚烷基、亚环烷基和支化亚烷基；L也可以含有酯键或碳酸酯键；并且
结构VIII中的稠环是任选存在的，并且在存在时是芳族的、环脂族的、脂环族的或杂环的。
10.如权利要求9所述的助熔剂相容性环氧-酚粘合剂，其中所述双马来酰亚胺或多官能马来酰亚胺是通过单官能或多官能伯胺与马来酸酐的酰亚胺化获得的或者通过单官能或多官能脂族、环脂族、脂环族或芳烷基醇与6-马来酰亚胺基己酸的费歇尔酯化获得的。
11.如权利要求1所述的助熔剂相容性环氧-酚粘合剂，其中环氧树脂与酚的比率为1:1至1:0.05。
12.如权利要求1所述的助熔剂相容性环氧-酚粘合剂，其还包含固化剂、促进剂、催化剂、流动改性剂、填料、粘合促进剂和触变剂。
13.酚，所述酚选自：
14.酚，所述酚选自结构I、结构II、结构III和结构IV中的一种或多种：
其中X是任选地具有脂族侧链的环脂族或脂环族的单环、双环或多环环结构；并且酯基的氧直接连接至所述环或所述脂族侧链；
X1是任选地具有杂原子O或S的亚烷基或支化亚烷基；
R3是H、烷基或环烷基；
L1和L2独立地选自共价键、任选地包含杂原子O或S的亚烷基、支化亚烷基和亚环烷基；
R1和R2独立地是H、甲基或OH，条件是每个环中的R1或R2中的至少一个是OH；并且
结构I、结构II、结构III和结构IV中存在的所述酯基可以是伯酯基或仲酯基。
15.酚，所述酚选自结构V、结构VI和结构VII中的一种或多种：
其中R是脂族、环脂族、脂环族、混合芳族-环脂族或聚合物主链；此外，在结构V和结构VII中，R可以是稠环；
R1和R2是H、烷基或OH，条件是R1或R2中的至少一个是OH；
n＝1-10；并且
结构V中连接至酚环的所述稠环是任选存在的，并且在存在时可以是芳族的、环脂族的、脂环族的或杂环的。
16.酚，所述酚选自结构VIII和结构IX中的一种或多种：
其中L选自共价键、任选地具有杂原子O或S的亚烷基、亚环烷基和支化亚烷基；L也可以含有酯键或碳酸酯键；并且
结构VIII中的稠环是任选存在的，并且在存在时是芳族的、环脂族的、脂环族的或杂环的。
17.如权利要求1所述的助熔剂相容性环氧-酚粘合剂，其中：
所述环氧化合物选自EP4088S、Eponex1510、HP7200L、Hyloxy modifier107、及其混合物；
所述多官能酚选自：
所述催化剂选自Technicure EMI 24-CN、Curezol 2-PHZ-S、Curezol2-PZ、Curezol2PZ-azine和Aardur 3123。
CN202180096089.4A 2020-06-01 2021-08-09 用于低间隙底部填充应用的助熔剂相容性环氧-酚类粘合剂组合物 Pending CN117062890A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202063032764P 2020-06-01 2020-06-01
PCT/US2021/045140 WO2022211838A1 (en) 2020-06-01 2021-08-09 Flux-compatible epoxy-phenolic adhesive compositions for low gap underfill applications

Publications (1)

Publication Number Publication Date
CN117062890A true CN117062890A (zh) 2023-11-14

Family

ID=82197310

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202180096089.4A Pending CN117062890A (zh) 2020-06-01 2021-08-09 用于低间隙底部填充应用的助熔剂相容性环氧-酚类粘合剂组合物

Country Status (6)

Country Link
US (1) US20240010890A1 (zh)
JP (1) JP2024515506A (zh)
KR (1) KR20230164059A (zh)
CN (1) CN117062890A (zh)
TW (1) TW202212316A (zh)
WO (1) WO2022211838A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7401016B1 (ja) 2023-05-15 2023-12-19 東洋インキＳｃホールディングス株式会社 封止シート及び、樹脂組成物層を有するディスプレイ

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62270618A (ja) * 1986-05-19 1987-11-25 Nippon Telegr & Teleph Corp <Ntt> エポキシ樹脂組成物
JP4870265B2 (ja) * 2001-01-19 2012-02-08 帝人化成株式会社 ポリカーボネート樹脂
KR20130037661A (ko) * 2010-03-08 2013-04-16 아지노모토 가부시키가이샤 수지 조성물
WO2011130671A2 (en) * 2010-04-16 2011-10-20 Valspar Sourcing, Inc. Coating compositions for packaging articles and methods of coating
EP3560968A4 (en) * 2016-12-20 2020-05-27 DIC Corporation RESIN COMPOSITION, HARDENED PRODUCT AND LAMINATE

Also Published As

Publication number Publication date
JP2024515506A (ja) 2024-04-10
WO2022211838A1 (en) 2022-10-06
KR20230164059A (ko) 2023-12-01
TW202212316A (zh) 2022-04-01
US20240010890A1 (en) 2024-01-11

Similar Documents

Publication Publication Date Title
JP4238124B2 (ja) 硬化性樹脂組成物、接着性エポキシ樹脂ペースト、接着性エポキシ樹脂シート、導電接続ペースト、導電接続シート及び電子部品接合体
TWI598372B (zh) Adhesive composition
KR100980383B1 (ko) 다이 부착용 이중 경화 ｂ-스테이지 가능형 접착제
CN109439254B (zh) 一种可返修的高可靠性填充胶
KR100556981B1 (ko) 전자부품
KR20120130705A (ko) 실페닐렌 구조 및 실록산 구조를 갖는 중합체 및 이의 제조 방법, 접착제 조성물, 접착 시트 및 반도체 장치 보호용 재료, 및 반도체 장치
JPWO2013125086A1 (ja) 半導体用接着剤、フラックス剤、半導体装置の製造方法及び半導体装置
JP2008274300A (ja) 硬化性樹脂組成物
WO2016148121A1 (ja) フリップチップ実装体の製造方法、フリップチップ実装体、および先供給型アンダーフィル用樹脂組成物
KR20200020666A (ko) 반도체용 접착제, 반도체 장치의 제조 방법 및 반도체 장치
US10808103B2 (en) Resin composition, laminate including the resin composition, semiconductor wafer with resin composition layer, substrate for mounting semiconductor with resin composition layer, and semiconductor device including the semiconductor wafer with resin composition layer
WO2007038753A2 (en) Compositions effective to suppress void formation
US20240010890A1 (en) Flux-compatible epoxy-phenolic adhesive compositions for low gap underfill applications
JP2006505674A (ja) 有機酸含有組成物およびその使用方法
JP2009256466A (ja) 電子部品用接着剤
KR102360805B1 (ko) 접착제 조성물, 그의 경화물을 포함하는 반도체 장치 및 그것을 사용한 반도체 장치의 제조 방법
JP6048524B2 (ja) 接着剤組成物
JP4079125B2 (ja) エポキシ樹脂組成物並びに半導体装置及びその製造方法
JPWO2013125087A1 (ja) 半導体用接着剤、フラックス剤、半導体装置の製造方法及び半導体装置
JP7276105B2 (ja) アンダーフィル用のシート状樹脂組成物、及びそれを用いた半導体装置
JP6638380B2 (ja) 先供給型アンダーフィル材及びその硬化物、並びに電子部品装置及びその製造方法
JP7275996B2 (ja) 熱硬化接着剤シート、半導体装置および半導体装置の製造方法
JP2006143795A (ja) 液状樹脂組成物、それを用いた半導体装置の製造方法及び半導体装置
KR20230017861A (ko) 저-갭 언더필 적용을 위한 플럭스-상용성 에폭시-무수물 접착제 조성물
JP5596468B2 (ja) 半導体素子の接合方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication