Resin compositions for underfill film for three dimensional through silica via (TSV) packages and compositions useful for the preparation thereof

1. A composition comprising:

(i) at least 1 wt % of a maleimide, nadimide or itaconimide;

(ii) at least 15 wt % of an epoxy resin,

(iii) at least 5 wt % of a toughening agent; and

(iv) at least 40 wt % of a filler;

provided, however, that said composition contains substantially no acrylate resin;

wherein:

said maleimide, nadimide or itaconimide is monomeric or oligomeric and can undergo radical cure to form a polymeric network;

said epoxy resin is a thermosetting resin which can cure into a three-dimensional polymer network;

said toughening agent reduces the material brittleness of said composition, and increases the impact resistance thereof; and

said filler modulates the coefficient of thermal expansion (CTE) of the resulting composition; and

wherein said composition, when cured, has a:

differential scanning calorimetry (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 using a rheometer at 10

rad frequency with a 10° C./min ramp rate using a sample 1 inch in diameter and 1 mm thick

wherein said epoxy resin comprises a siloxane modified epoxy resin having 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 -oxirane, and

n falls in the range of about 1-4.

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

3. The composition of claim 1 wherein said epoxy resin further comprises a resin selected from bisphenol A epoxy resins, bisphenol F epoxy resins, naphthalene epoxy resins, novolac 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 1 wherein said siloxane modified epoxy resin is produced by contacting a combination of the following components under conditions suitable to promote the reaction thereof

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

5. The composition of claim 1 wherein said toughening agent is a medium to high molecular weight thermoplastic polymer of epichlorohydrin and bisphenol A.

6. The composition of claim 5 wherein said toughening agent is a phenoxy resin having the structure of polyhydroxyl ether, and having terminal hydroxyl groups as well as repeating hydroxyls along the backbone thereof.

7. The composition of claim 6 wherein said phenoxy resin has the structure:

wherein n falls in the range of about 50 up to about 150.

8. 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,

and

J is a monovalent or a polyvalent radical comprising organic or

organosiloxane radicals, and

combinations of two or more thereof.

9. The composition of claim 8 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 J can be aryl only when J 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—, —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.

10. The composition of claim 8 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.

11. The composition of claim 1 , further comprising a cyanate ester resin, a benzoxazine, an aromatic ester, an aromatic alkene, an aromatic alkyne, an aromatic nitrile, or a combination of any two or more thereof.

12. The composition of claim 1 , further comprising one or more of:

at least 1 wt % of a fluxing agent, and/or

at least 0.1 wt % of an adhesion promoter.

13. An underfill film comprising the reaction product of curing the composition of claim 1 .

14. The underfill film of claim 13 wherein said film absorbs less than 2% by weight moisture when exposed to 85° C. at 85% relative humidity for about 2 days.

15. The underfill film of claim 13 wherein the film is a B-staged film, which, after cure, has a Tg, as determined by thermomechanical analysis (TMA), of greater than about 80° C.

16. The underfill film of claim 13 wherein the die shear of said film at 260° C. is at least 5 kg/cm 2 as tested with SiN die/PI die/SiO 2 (size: 3.81×3.81×700 mm 3 ), wherein the die is attached on a BT substrate at 120° C./1 kg force/5 seconds, then cured by ramping the temperature from room temperature to 175° C. over 30 minutes, then held at 175° C. for 5 hrs.

17. An article comprising an underfill film according to claim 13 adhered to a suitable substrate therefor,

wherein said suitable substrate is a polyethylene terephthalate, a polymethyl methacrylate, a polyethylene, a polypropylene, a polycarbonate, an epoxy resin, a polyimide, a polyamide, a polyester, glass, a Si die with silicon nitride passivation, a Si die with polyimide passivation, a BT substrate, bare Si, a SR4 substrate, or a SR5 substrate.

18. The article of claim 17 wherein said article is a flip chip package, a stacked die, a hybrid memory cube, or a TSV device.

19. The article of claim 17 wherein the adhesion of said underfill film to said substrate is at least 5 kg/cm 2 as tested with SiN die/PI die/SiO 2 (size: 3.81×3.81×700 mm 3 ), wherein the die is attached on a BT substrate at 120° C./1 kg force/5 seconds, then cured by ramping the temperature from room temperature to 175° C. over 30 minutes, then held at 175° C. for 5 hrs.

20. A method for preparing an underfill film, said method comprising curing the composition of claim 1 after application thereof to a suitable substrate.