Formulations containing mixed resin systems and the use thereof for wafer-level underfill for 3D TSV packages

Patent metadata

Field	Value
Publication number	US-10242923-B2
Application number	US-201815945772-A
Country	US
Kind code	B2
Filing date	Apr 5, 2018
Priority date	Oct 7, 2015
Publication date	Mar 26, 2019
Grant date	Mar 26, 2019

Abstract

Provided herein are mixed resin systems and the use thereof for wafer-level underfill (WAUF) for three-dimensional TSV packages. In one aspect, there are provided compositions comprising (1) an epoxy resin, (2) a maleimide, nadimide or itaconamide, (3) an acrylate and (4) a filler. In certain aspects, the epoxy resin is a siloxane-modified resin. In certain aspects, the invention relates to underfill films prepared from invention compositions. In certain aspects, the invention relates to articles comprising the underfill films described herein.

First claim

That which is claimed is:

1. A composition comprising:
an epoxy resin;
a maleimide, nadimide or itaconimide;
an acrylate; and
a filler;

wherein:
said epoxy resin is a thermosetting resin which can cure into a three-dimensional polymer network;
said maleimide, nadimide or itaconimide is monomeric or oligomeric and can undergo radical cure to form a polymeric network;
said acrylate is monomeric or oligomeric and can undergo radical cure to form a polymeric network; and
said filler modulates the coefficient of thermal expansion (CTE) of the resulting composition;

wherein:
said composition, when cured, has a:
DSC onset of 100° C. 205° C.;
Melt viscosity in the range of 200 Poise-40,000 Poise, and
gelling temperature of 130° C. 180° C., as measured by Ares Rheometer at 10 Rad frequency with a 10° C./min ramp rate using a sample 1 inch in diameter and 1 mm thick.

2. The composition of claim 1 wherein said epoxy resin comprises a polymeric backbone having one or more epoxide groups thereon.

3. The composition of claim 2 wherein said epoxy resin is selected from bisphenol A epoxy resins, bisphenol F epoxy resins, naphthalene epoxy resins, novolac epoxy resins, siloxane-modified epoxy resins, cycloaliphatic epoxy resins, biphenyl epoxy resins, DCPD epoxy resins, or modified epoxy resins, as well as combinations of any two or more thereof.

4. The composition of claim 3 wherein said siloxane modified epoxy resin has the structure:
—(O—Si(Me) 2 -O—Si(Me)(Z)—O—Si(Me) 2 -O—Si(Me) 2 ) n —

wherein:
Z is —O—(CH 2 ) 3 —O-Ph-CH 2 -Ph-O—(CH 2 —CH(OH)—CH 2 —O-Ph-CH 2 -Ph-O—) n —CH 2 -oxiran e, and
n falls in the range of about 1-4.

5. The composition of claim 4 wherein said siloxane modified epoxy resin is produced by contacting a combination of the following components under conditions suitable to promote the reaction thereof
Me 2 Si(OMe) 2
+
(MeO) 3 Si—(CH 2 ) 3 —O—CH 2 -oxirane

+
oxirane-CH 2 —O-Ph-CH 2 -Ph-O—(CH 2 —CH(OH)—CH 2 —O-Ph-CH 2 -Ph-O—) n —CH 2 -oxirane,

wherein “n” falls in the range of about 1-4.

6. The composition of claim 1 wherein said maleimide, nadimide or itaconimide, has the structure:

respectively, wherein:
m is 1-15,
p is 0-15,
each R 2 is independently selected from hydrogen or lower alkyl (such as C 1-5 ), and
J is a monovalent or a polyvalent radical comprising organic or organosiloxane radicals, and
combinations of two or more thereof.

7. The composition of claim 6 wherein J is a monovalent or polyvalent radical selected from:
hydrocarbyl or substituted hydrocarbyl species typically having in the range of about 6 up to about 500 carbon atoms, where the hydrocarbyl species is selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, alkylaryl, arylalkyl, aryalkenyl, alkenylaryl, arylalkynyl or alkynylaryl, provided, however, that X can be aryl only when X comprises a combination of two or more different species;
hydrocarbylene or substituted hydrocarbylene species typically having in the range of about 6 up to about 500 carbon atoms, where the hydrocarbylene species are selected from alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, arylene, alkylarylene, arylalkylene, arylalkenylene, alkenylarylene, arylalkynylene or alkynylarylene,
heterocyclic or substituted heterocyclic species typically having in the range of about 6 up to about 500 carbon atoms,
polysiloxane, or
polysiloxane-polyurethane block copolymers, as well as

combinations of one or more of the above with a linker selected from covalent bond, —O—, —S—, —NR—, —NR—C(O)—, —NR—C(O)—O—, —NR—C(O)—NR—, —S—C(O)—, —S—C(O)—O—, —S—C(O)—NR—, —O—S(O) 2 —, —O—S(O) 2 —O—, —O—S(O) 2 —NR—, —O—S(O)—, —O—S(O)—O—, —O—S(O)—NR—, —O—NR—C(O)—, —O—NR—C(O)—O—, —O—NR—C(O)—NR—, —NR—O—C(O)—, —NR—O—C(O)—O—, —NR—O—C(O)—NR—, —O—NR—C(S)—, —O—NR—C(S)—O—, —O—NR—C(S)—NR—, —NR—O—C(S)—, —NR—O—C(S)—O—, —NR—O—C(S)—NR—, —O—C(S)—, —O—C(S)—O—, —O—C(S)—NR—, —NR—C(S)—, —NR—C(S)—O—, —NR—C(S)—NR—, —S—S(O) 2 —, —S—S(O) 2 —O—, —S—S(O) 2 —NR—, —NR—O—S(O)—, —NR—O—S(O)—O—, —NR—O—S(O)—NR—, —NR—O—S(O) 2 —, —NR—O—S(O) 2 —O—, —NR—O—S(O) 2 —NR—, —O—NR—S(O)—, —O—NR—S(O)—O—, —O—NR—S(O)—NR—, S(O) 2 —O—, —O—NR—S(O) 2 —NR—, —O—NR—S(O) 2 —, —O—P(O)R 2 —, —S—P(O)R 2 —, or —NR—P(O)R 2 —;
where each R is independently hydrogen, alkyl or substituted alkyl.

8. The composition of claim 6 wherein J is oxyalkyl, thioalkyl, aminoalkyl, carboxylalkyl, oxyalkenyl, thioalkenyl, aminoalkenyl, carboxyalkenyl, oxyalkynyl, thioalkynyl, aminoalkynyl, carboxyalkynyl, oxycycloalkyl, thiocycloalkyl, aminocycloalkyl, carboxycycloalkyl, oxycloalkenyl, thiocycloalkenyl, aminocycloalkenyl, carboxycycloalkenyl, heterocyclic, oxyheterocyclic, thioheterocyclic, aminoheterocyclic, carboxyheterocyclic, oxyaryl, thioaryl, aminoaryl, carboxyaryl, heteroaryl, oxyheteroaryl, thioheteroaryl, aminoheteroaryl, carboxyheteroaryl, oxyalkylaryl, thioalkylaryl, aminoalkylaryl, carboxyalkylaryl, oxyarylalkyl, thioarylalkyl, aminoarylalkyl, carboxyarylalkyl, oxyarylalkenyl, thioarylalkenyl, aminoarylalkenyl, carboxyarylalkenyl, oxyalkenylaryl, thioalkenylaryl, aminoalkenylaryl, carboxyalkenylaryl, oxyarylalkynyl, thioarylalkynyl, aminoarylalkynyl, carboxyarylalkynyl, oxyalkynylaryl, thioalkynylaryl, aminoalkynylaryl or carboxyalkynylaryl, oxyalkylene, thioalkylene, aminoalkylene, carboxyalkylene, oxyalkenylene, thioalkenylene, aminoalkenylene, carboxyalkenylene, oxyalkynylene, thioalkynylene, aminoalkynylene, carboxyalkynylene, oxycycloalkylene, thiocycloalkylene, aminocycloalkylene, carboxycycloalkylene, oxycycloalkenylene, thiocycloalkenylene, aminocycloalkenylene, carboxycycloalkenylene, oxyarylene, thioarylene, aminoarylene, carboxyarylene, oxyalkylarylene, thioalkylarylene, aminoalkylarylene, carboxyalkylarylene, oxyarylalkylene, thioarylalkylene, aminoarylalkylene, carboxyarylalkylene, oxyarylalkenylene, thioarylalkenylene, aminoarylalkenylene, carboxyarylalkenylene, oxyalkenylarylene, thioalkenylarylene, aminoalkenylarylene, carboxyalkenylarylene, oxyarylalkynylene, thioarylalkynylene, aminoarylalkynylene, carboxy arylalkynylene, oxyalkynylarylene, thioalkynylarylene, aminoalkynylarylene, carboxyalkynylarylene, heteroarylene, oxyheteroarylene, thioheteroarylene, aminoheteroarylene, carboxyheteroarylene, heteroatom-containing di- or polyvalent cyclic moiety, oxyheteroatom-containing di- or polyvalent cyclic moiety, thioheteroatom-containing di- or polyvalent cyclic moiety, aminoheteroatom-containing di- or polyvalent cyclic moiety, or a carboxyheteroatom-containing di- or polyvalent cyclic moiety.

9. The composition of claim 1 further comprising an organic diluent.

10. The composition of claim 1 wherein said composition comprises:
at least 1 wt % of said epoxy resin,
at least 6 wt % of said maleimide, nadimide or itaconimide,
at least 4 wt % of said acrylate, and
at least 30 wt % of said filler.

11. The composition of claim 10 , further comprising one or more of:
at least 1 wt % of a fluxing agent,
at least 0.1 wt % of an adhesion promoter; and/or
at least 4 wt % of a toughening agent.

12. The composition of claim 1 wherein said composition comprises:
in the range of about 1 up to 20 wt % of said epoxy resin,
in the range of about 6 up to 16 wt % of said maleimide, nadimide or itaconimide,
in the range of about 4 up to 12 wt % of said acrylate, and
in the range of about 30 up to 75 wt % of said filler.

13. The composition of claim 12 , further comprising one or more of:
at least 1 wt % of a fluxing agent,
at

Assignees

• Henkel IP & Holding GmbH
• Henkel Ag & Co Kgaa

Inventors

• Bai Jie
• Huang Qiaohong
• Jiang Hong
• Murata Youko
• Horiguchi Yusuke
• Kim Younsang
• Takano Tadashi

Classifications

• H10W74/15

  on active surfaces of flip-chip devices, e.g. underfills · CPC title

• H10W74/012

  of encapsulations on active surfaces of flip-chip devices, e.g. forming underfills · CPC title

• H10W74/47 Primary

  comprising organic materials, e.g. plastics or resins · CPC title

• H01L21/563

  Electricity · mapped topic

• C08L33/04

  Homopolymers or copolymers of esters {(C08L43/04 takes precedence)} · CPC title