WO2009082833A1

WO2009082833A1 - Functional fluoride anti-bleed agents with reactive groups an application in organic based curable compositions

Info

Publication number: WO2009082833A1
Application number: PCT/CN2007/003806
Authority: WO
Inventors: Hao Kong
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2007-12-26
Filing date: 2007-12-26
Publication date: 2009-07-09
Also published as: TW200927862A

Abstract

This invention relates to functional fluoride anti-bleed agents with reactive groups and their application in curable compositions. There is provided a curable composition for bonding articles such as semiconductor chips and devices onto a substrate, comprising at least one monomer and/or oligomer and a quantity of a functional fluoride anti-bleed agent sufficient to decrease the resin bleed upon application of said composition to the substrate, wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20, and X contains a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted vinyl group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof. Due to the functional fluoride anti-bleed agent, the adhesive composition shows good performance in bleeding control and can reduce the occurrence of die top delamination in semiconductor packages.

Description

Functional Fluoride Anti-bleed Agents with Reactive Groups and Application in Organic Based Curable Compositions

Field of the Invention

[001] This invention generally relates to anti-bleed agents, and more particularly, functional fluoride anti-bleed agents with reactive groups, and to their applications in curable compositions, particularly in organic based adhesive, coating and encapsulant materials. Such anti-bleed agents are useful within the semiconductor packaging industry in compositions such as die attach adhesives, which can be used to bond semiconductor chips and devices onto various substrates, or underfill encapsulants and the like, to decrease the bleed-out of the compositions components during semiconductor packaging operations, such as, adhesive dispensing, chip/die attaching, dwelling, and curing.

Background Arts of the Invention

[002] Organic based materials, such as die attach polymeric materials, have gained increasing popularity, in part for their ability to accommodate larger die sizes and to facilitate processing at lower temperatures. However, problems with bonded semiconductor devices resulting from "bleed-out", also referred to "bleed" or "resin bleed", or separation of the resin vehicle from the polymer adhesive, sometimes occur from the monomer(oligomer) as well as any other small molecule present (See, e.g., U.S. Pat. No. 5,783,621, issued on July 21, 1998).

[003] In some organic based materials, particularly in semiconductor packaging die attach adhesives or underfill, organic fluorides have been used as one of the best anti-bleed agents for resin bleed control. However, fluorides currently typically carry no functional groups other than -OH. The lack of reactivity with bulk resin system may cause self-bleed or volatile formation during or after cure. Such self-bleed or volatility may cause delamination between various packaging interfaces.

[004] U.S. Pat. No. 4,483,898, issued to Schonborn, et. al. on November 20, 1984, discloses the use of alcohols, amides, amines, carboxylic acid, and esters containing two to about twelve carbon atoms a? ?l!egedly being effective for the inhibition of spreading of liquid on substrates. The inhibition of the spreading of a liquid on a solid surface was the specific focus of this patent. The effective amount of the inhibitor contemplated by this patent is 0.05 to 5% by weight of the liquid. The '898 patent discloses that the inhibitor in the liquid forms a layer (film) when in contact with the surface, resulting from some kind of interaction between the inhibitor and the surface.

[005] Although there are some anti-bleed agents for resin bleed control, there is still a need in the art for compositions and methods useful for reducing the bleeding out of the components from the bulk adhesive by well reducing or eliminating self-bleed or volatile formation during semiconductor packaging such as, adhesive dispensing, chips/die attaching, dwelling, and curing.

Summary of the Invention

[006] This invention relates to functional fluorides as resin bleed-out resistant or retardant chemicals, and their use in curable compositions, particularly in semiconductor packaging or assembly adhesives or underfill, wherein the functional fluorides can copolymerize or react with other chemicals in the bulk adhesive resin to reduce or eliminate self-bleed and/or volatile emissions. Said curable compositions include but not limited to, die attach adhesive, underfill and the like.

[007] In one embodiment of the present invention, there are provided compositions of organic based adhesive materials for bonding articles such as semiconductor chips and devices onto various substrates, comprising at least one monomer and/or oligomer and a quantity of a functional fluoride anti-bleed agent sufficient to decrease the resin bleed upon application of said composition to the substrate, wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro-group-containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20. Preferably, X may contain a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted vinyl group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof. In one aspect, R may have a formula CF₃(CF₂),,, wherein n is an integer from 1 to about 100 or more; preferably, from about 1 to about 20; more preferably, from about 1 to about 16; most preferably, from about 1 to about 9. In another aspect, the fluorine (F) atom may be substituted by one selected from the group consisting of H, O, N, P and S atom. The composition may be useful in die attach adhesive, underfill and the like. The monomer(s) and/or oligomer(s) useful in said compositions may be those known in the art, comprising epoxies, acrylates, methylacrylates, maleimides, cyanate esters, liquid BMI, silanes, propargyl, vinyl, cyclic silicones, benzoxazines, vinyl amides, vinyl amines, bisoxazolines, styrenics, cinnamyls, maleates, fumarates, oxetanes, epoxidized rubbers monomers or oligomers, or the combination thereof. [008] In certain temperature, pressure, or other conditions, the functional groups in X can react with one or more functional groups in curable components, which reactions are used to bond the fluorides into the adhesive and thus reduce the chemical migration. The reactions can be polymerization together with the monomers and/or oligomers. For example, the acrylate group in X can polymerize with many vinyl -group-containing monomers and/or oligomers, by radical polymerization mechanism, such as vinyl, acrylate, maleimide, BMI, etc. monomers and/or oligomers. The oxane group can polymerize with hydroxyl, amine, oxane, etc. containing monomers and/or oligomers in adhesive. The reaction also can be reactions among the functional groups in X and those functional groups in adhesive, including any components in adhesive, by means of any kinds of reactions, including addition reaction, condensation reaction, acid-base reaction, oxidation reaction, and so on. These reactions type can be the only reaction with some component in adhesive, and also, more commonly, can exist as reactions combination in adhesive. That is to say, some functional groups can react with one or more functional groups. Therefore, the functional groups in X are not necessarily the same groups with those in adhesive.

[009] In another embodiment of the present invention, there are provided compositions of organic based adhesive materials for bonding articles such as semiconductor chips and devices onto various substrates, comprising at least one epoxy monomer and/or oligomer and a quantity of a functional fluoride anti-bleed agent sufficient to decrease the resin bleed upon application of said composition to the substrate, wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20, and preferably, X contains a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof. In a further embodiment of the present invention, the composition may further comprise a curing agent, a catalyst, a filler or the combination thereof. In one aspect, R may have a formula CF₃(CF₂),,, wherein n is an integer from 1 to about 100 or more; preferably, from about 1 to about 20; more preferably, from about 1 to about 16; most preferably, from about 1 to about 9.

[010] In still another embodiment of the present invention, there are provided compositions of organic based adhesive materials for bonding articles such as semiconductor chips and devices onto various substrates, comprising: at least one (methyl)acrylate monomer and/or oligomer; a quantity of a functional fluoride anti-bleed agent sufficient to decrease the resin bleed upon application of said composition to the substrate, wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20, and preferably R contains a substituted or unsubstituted vinyl group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof; and an optional curing agent, an optional liquid bismaleimide (BMI), and an optional radical initiator. In a further embodiment of the present invention, the composition may further comprise a filler. In one aspect, R may have a formula CF₃(CF₂)_n, wherein n is an integer from 1 to about 100 or more; preferably, from about 1 to about 20; more preferably, from about 1 to about 16; most preferably, from about 1 to about 9. [Oi l] In some preferred embodiments of the present invention, the functional fluoride anti-bleed agent with an epoxy group may be (2,2,3,3,4,4,5, 5,6,6,7,7,8, 8,9,9,9-Heptadecafluorononyl) oxirane having the following chemical structure (commercially available from Sigma-Aldrich (China) Ltd., Cat. No. 474088):

[012] In some additional preferred embodiments of the present invention, the functional fluoride anti-bleed agent with an amino group may be one or more selected from the group consisting of 4-(Perfluorooctyl)aniline (Sigma-Aldrich (China) Ltd., Cat. No., 28623) and 1H,1H,2H,2H,3H,3H- Perfluoroundecylamine or 3-(Perfluorooctyl)propylamine (Sigma-Aldrich (China) Ltd., Cat. No. 04636), which respectively have the following chemical structures:

4-(Perfluorooctyl)aniline (28623)

1 H, 1 H,2H,2H,3H,3H-Perfluoroundecylamine or 3-(Perfluorooctyl)propylamine (04636)

[013] In still some preferred embodiments of the present invention, the functional fluoride anti-bleed agent with a vinyl group may be one or more selected from the group consisting of lH,lH,2H-Perfluoro-l-decene (Sigma-Aldrich (China) Ltd., Cat. No. 370576), 1H,1H,2H,2H- Perfluorodecyl acrylate (Sigma-Aldrich (China) Ltd., Cat. No. 474487), 2,2,3,3,4,4,4-Heptafluorobutyl acrylate (Sigma-Aldrich (China) Ltd., Cat. No. 443751), and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12- Heneicosafluorododecyl acrylate (Sigma-Aldrich (China) Ltd., Cat. No. 474355), which respectively have the following chemical structures: lH,lH,2H-Perfluoro-l-decene (370576)

H₂C=CH(CF₂)CF₃

1H,1H,2H,2H-Perfluorodecyl acrylate (474487)

2,2,3,3,4,4,4-Heptafluorobutyl acrylate (443751)

O I l H C -OCH₂CF₂CF₂CF₃

C =C / \

H H

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12- Heneicosafluorododecyl acrylate (474355)

O

CH₂=C-C-OCH₂CH₂(CF₂)C₎CF₃ H [014] In yet still preferred embodiments, exemplary functional fluoride anti-bleed agent with maleimide group(s) according to the present invention comprise 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12,13,13, 14,14,15, 15, 16,16,17, 17-Heneicosafluorododecyl maleimide, which has the following chemical structure:

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12,13,13,14, 14,15,15,16,16,17,17-Heneicosafluorododecyl maleimide

2CF₃

[015] In some embodiments, the amount of the fluorides used in the present invention, is in the range from about 0.0001% to about 20% by weight of whole bulk resin, preferably from about 0.0001% by weight to about 5% by weight, more preferably from about 0.01% by weight to about

5% by weight, still more preferably from about 0.05% by weight to about

4% by weight, even more preferably from about 0.2% by weight to about 2% by weight, most preferably 0.5% by weight to 2% by weight.

[016] In additional embodiments of the present invention, there is provided a method for reducing resin bleed of organic based curable compositions upon application to a substrate, said method comprising adding to the said organic based adhesive materials a quantity of functional fluoride anti-bleed agent, wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20, and preferably X contains a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted vinyl group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxahe group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof. In one aspect, R may have a formula CF₃(CF₂)_n, wherein n is an integer from 1 to about 100 or more; preferably, from about 1 to about 20; more preferably, from about 1 to about 16; most preferably, from about 1 to about 9. In further additional embodiments, the functional fluoride anti-bleed agent is in the range from about 0.0001% to about 20% by weight of whole organic based adhesive materials, preferably from about 0.0001% by weight to about 5% by weight, more preferably from about 0.01% by weight to about 5% by weight, still more preferably from about 0.05% by weight to about 4% by weight, even more preferably from about 0.2% by weight to about 2% by weight, most preferably 0.5% by weight to 2% by weight. The specific fluoride may be selected from those described above. Said organic based curable compositions include but not limited to, die attach adhesives, underfill and the like.

[017] In one embodiment, the present invention further provides a method for producing an article with a component bonded to a substrate, the method comprising applying an organic based curable compositions comprising at least one monomer and/or oligomer and a quantity of functional fluoride anti-bleed agent onto at least a part of the substrate surface, and bonding the component to the adhesive-coated substrate surface, wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20, and preferably X contains a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted vinyl group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof. In one aspect, R may have a formula CF₃(CF₂),,, wherein n is an integer from 1 to about 100 or more; preferably, from about 1 to about 20; more preferably, from about 1 to about 16; most preferably, from about 1 to about 9. In one aspect, the functional fluoride anti-bleed agent is in the range from about 0.0001% to about 20% by weight of whole organic based adhesive materials, preferably from about 0.0001% by weight to about 5% by weight, more preferably from about 0.01% by weight to about 5% by weight, still more preferably from about 0.05% by weight to about 4% by weight, even more preferably from about 0.2% by weight to about 2% by weight, most preferably 0.5% by weight to 2% by weight. The specific fluoride may be selected from those described above. In another aspect, the method further comprises a step of thermally curing the adhesive at a temperature above room temperature, the step being performed after contacting the substrate with the adhesive. In still another aspect, the component bonded to a substrate may be a semiconductor component. In another embodiment, the invention provides an article produced by the method, the article comprising a substrate, a component on the substrate and the adhesive in accordance with the present invention by which the component bonded to the substrate. The said component may be a semiconductor component.

[018] In a further embodiment, there is provided the use of the functional fluorides as an anti-bleed agent in an adhesive, for example, die attach adhesive, underfill, etc., wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20, and preferably X contains a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted vinyl group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof. In one aspect, R may have a formula CF₃(CF₂)_H, wherein n is an integer from 1 to about 100 or more; preferably, from about 1 to about 20; more preferably, from about 1 to about 16; most preferably, from about 1 to about 9. In one aspect, the functional fluoride anti-bleed agent is in the range from about 0.0001% to about 20% by weight of whole organic based adhesive materials, preferably from about 0.0001% by weight to about 5% by weight, more preferably from about 0.01% by weight to about 5% by weight, still more preferably from about 0.05% by weight to about 4% by weight, even more preferably from about 0.2% by weight to about 2% by weight, most preferably 0.5% by weight to 2% by weight. The specific fluoride may be selected from those described above.

[019] The disclosed herein fluorides with functionally reactive -groups can readily polymerize or react with ingredients in bulk adhesive, and therefore reduce or eliminate self-bleed and/or volatile emission. As a result of using functional fluoride anti-bleed agents as components, the adhesive composition can show good performance in bleeding control and reduce the occurrence of die top delamination in semiconductor packages.

A Brief Description of the Figures

[020] Figure 1. A comparing view on bleeding control effect of uncured samples in TVl (test vehicle on epoxy platform) after dwelling the dot dispensed samples on Ag, Cu, and PPF (Ni/Pd/Au) surfaces at room temperature in atmosphere for 30 minutes.

[021] Figure 2. A comparing view on bleeding control effect of cured samples in TVl after curing the dot dispensed samples on Ag, Cu, and PPF (Ni/Pd/Au) surfaces at the condition of ramping to 175 ⁰C in 30 minutes and soaking for another 15 minutes.

[022] Figure 3. A comparing view on bleeding control effect of cured samples in TV2 (test vehicle on radical curable platform) after curing the dot dispensed samples on Ag, Cu, and PPF (Ni/Pd/Au) surfaces at the condition of ramping to 175 ⁰C in 30 minutes and soaking for another 15 minutes.

[023] Figure 4. A schematic illustrative view of an article produced by the method of the invention.

Detailed Description of the Invention

[024] Unless defined otherwise herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although any methods and materials similar or equivalent to those described herein may find use in the practice of the present invention, the preferred methods and materials are described herein. Accordingly, the terms defined immediately below are more fully described by reference to the Specification as a whole. Also, as used herein, the singular "a", "an" and "the" includes the plural reference unless the context clearly indicates otherwise. Numeric ranges are inclusive of the numbers defining the range.

Definitions

[025] As used herein, the term "bleed", "bleed-out" or "resin bleed" refers to separation of the monomer(oligomer) vehicle phase and filler, as well as the self-bleed or volatile formation of the anti-bleed agent during or after staging or cure, resulting in spread of resin away from the die bond area. [026] As used herein, the term "an anti-bleed agent" means a variety of additives which, acting alone or in combination, reduce and/or inhibit the propensity of monomer(oligomer) vehicle phase and filler to separate.

[027] As used herein, the term "functional fluoride anti-bleed agents" refers to poly-fluorinated anti-bleed agents with reactive groups, such as epoxy, amino, vinyl, maleimide, silane, oxane, cyanate ester groups, etc.

[028] Terms such as "epoxy", "substituted or unsubstituted expoxy", "amine", "substituted or unsubstituted amino", "vinyl", "substituted or unsubstituted vinyl", "monomer" and "oligomer" are intended herein to have their commonly accepted meaning in the art to which this invention pertains.

Detailed Description

[029] The present invention provides compositions for bonding articles such as semiconductor chips and devices onto various substrates, comprising at least one monomer and/or oligomer and a quantity of a functional fluoride anti-bleed agent sufficient to decrease the resin bleed upon application of said composition to the substrate. Said compositions include but not limited to, die attach adhesive, underfill, and the like. The monomer(s) and/or oligomer(s) may be selected from epoxies, acrylates, methylacrylates, maleimides, cyanate esters, liquid BMI, silanes, propargyl, vinyl, cyclic silicones, benzoxazines, vinyl amides, vinyl amines, bisoxazolines, styrenics, cinnamyls, maleates, fumarates, oxetanes, epoxidized rubbers monomers and/or oligomers, or the like, or the combination thereof.

[030] In some embodiments, the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20, and preferably X contains a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted vinyl group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof. In one aspect, R may have a formula CF₃(CF₂)_n, wherein n is an integer from 1 to about 100 or more; preferably, from about 1 to about 20; more preferably, from about 1 to about 16; most preferably, from about 1 to about 9.

[031] In some embodiments, the monomer and/or oligomer may be epoxy monomer and/or oligomer. Exemplary epoxy monomer and/or oligomer contemplated for use in the practice of the present invention include, but not limited to liquid epoxy, liquid epoxy combination, and solid epoxy in solution. For example, the epoxy monomer and/or oligomer may selected from substituted (e.g., amine or hydroxyl substituted) or unsubstituted epoxy, such as, 1,2-epoxypropane, 1,3-epoxypropane, butylene oxide, n-hexyl propylene epoxide or the like. Examples of commercially available epoxy monomer(oligomer) may be Araldite DY 027 (Chemica Inc. 316 West 130^th Street, Los Angeles, CA, 90061, USA), Cardula N-10 (Vantlco Inc., 281 Fields Lane, Brewster, NY 10509, USA), Epiclon EXA-830CRP (Resolution Performance Products, P. O. Box 4500, Houston, TX 77210, USA), or the combination thereof.

[032] In one embodiment of the present invention, the functional fluoride anti-bleed agent comprises at least a fluoride anti-bleed agent with an epoxy group and the monomer and/or oligomer comprises at least an epoxy monomer and/or oligomer.

[033] In other embodiments, the monomer and/or oligomer may be (meth)acrylate monomer and/or oligomer. The (meth)acrylate monomer and/or oligomer contemplated for use in the practice of the present invention include, but not limited to liquid (meth)acrylate, liquid (meth)acrylates combination and solid (meth)acrylate monomer(oligomer) in solution. For example, the (meth)acrylate monomer and/or oligomer may

5 be selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ethyl hexyl (meth)acrylate, isobutyl acrylate or the like. Examples of commercially available (meth)acrylate monomer(oligomer) may be SR248, SR355, or their combination (commercially available from Sartomer Inc. (Shanghai), 500 Fu Te 2^nd East l o Road, Wai Gao Qiao Free Trade Zone, Shanghai, 200131 ).

[034] In some embodiments, the monomer and/or oligomer may be cyanate ester monomer and/or oligomer. The cyanate ester may comprise various suitable cyanate ester known in the art, including isocyanates. Suitable cyanates include, for example, ethylene diisocyanate; 1,4-tetramethylene

15 diisocyanate; 1,4 and/or 1 ,6-hexamethylene diisocyanate; 1,12-dodecane diisocyanate; cyclobutane-l,3-diisocyanate; cyclohexane-1,3- and 1 ,4-diisocyanate and mixtures of these isomers; l-isocyanato-3,3,5- trimethyl-5-isocyanatomethyl cyclohexane; 2,4- and 2,6-hexahydrotolylene diisocyanate and mixtures of these isomers; hexahydro-1.,3- and/or

20 1 ,4-phenylene diisocyanate; perhydro-2,4'- and/or 4,4'-diphenyl methane diisocyanate; 1,3- and 1,4-phenylene diisocyanate; 2,4- and 2,6-toluene diisocyanate and mixtures of these isomers; diphenyl methane-2,4'- and/or 4,4'-diisocyanate; naphthylene-l,5-diisocyanate; 1,3- and 1,4-xylylene diisocyanate, 4,4'-methylene-bis(cyclohexyl isocyanate), 4,4'-isopropyl-

25 bis(cyclohexyl isocyanate), 1,4-cyclohexyl diisocyanate and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI); 2,4- and 2,6-toluene diisocyanate; diphenylmethane diisocyanate; hexamethylene diisocyanate; dicyclohexylmethane diisocyanate; isophorone diisocyanate; 1 -methyoxy-2,4-phenylene diisocyanate; l-chlorophenyl-2,4-diisocyanate; p-(l -isocyanatoethyl)-phenyl isocyanate; m-(3-isocyanatobutyl)-phenyl isocyanate and 4-(2-isocyanate-cycloKexyl-methyl)-phenyl isocyanate, isophorone diisocyanate, toluene diisocyanate and mixtures thereof.

[035] The monomer and/or oligomer may also be silane monomer and/or oligomer. The silanes may include non-functional silanes and functionalized silanes including amino-functional, epoxy-functional, acrylate-functional and other functional silanes, which are known in the art. Exemplary functionalized silanes include γ-glycidoxypropyl-trimethoxysilane, γ-glycidoxypropyltriethoxysilane, 7-glycidoxypropyl-methyldiethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropylmethyldiethoxysilane, 5,6-epoxyhexyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, and the like. Other exemplary functionalized silanes include trimethoxysilylpropyldiethylene-triamine, N-methylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltrimethoxysilane, aminoethylaminoethylaminopropyl-trimethoxysilane, N-methylamino-propyltrimethoxysilane, methylamino-propyltrimethoxysilane, aminopropylmethyl-diethoxysilane, aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, oligomeric aminoalkylsilane, m-aminophenyltrimethoxysilane, phenylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, aminoethylaminoisobutylmethyldimethoxysilane, and the like. Additional exemplary functional silanes include (3-acryloxypropyl)-trimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercapto-propyltriethoxysilane, and olefinic silanes, such as vinyltrialkoxysilane, vinyltriacetoxysilane, alkylvinyldialkoxysilane, allyltrialkoxysilane, hexenyltrialkoxysilane and the like.

[036] The monomer(oligomer)s can also be monofunctional monomer(oligomer)s, such as alkoxylated tetrahydrofurfuryl acrylate, 2(2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, lauryl acrylate, issoctyl acrylate, tridecyl acrylate, caprolactone acrylate, lauryl methacrylate, isobonyl methacrylate; and difunctional monomer(oligomer)s, such as difunctional cyclohexane dimethanol diacrylate, tetraethylene glycol diacrylate, or multiple functional monomer(oligomer)s, such as trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, di-trimethylolpropane tetraacrylate, pentacarylate ester, and so on. (e.g., commercially available from Sartomer Inc. (Shanghai), 500 Fu Te 2^nd East Road, Wai Gao Qiao Free Trade Zone, Shanghai, 200131).

[037] In one embodiment of the present invention, there are provided compositions for bonding articles such as semiconductor chips and devices onto various substrates, comprising at least one epoxy monomer and/or oligomer and a quantity of a functional fluoride anti-bleed agent sufficient to decrease the resin bleed upon application of said composition to the substrate, wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20, and preferably X contains a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof. In one aspect, R may have a formula CF₃(CF₂)_n, wherein n is an integer from 1 to about 100 or more; preferably, from about 1 to about 20; more preferably, from about 1 to about 16; most preferably, from about 1 to about 9. In a further embodiment of the present invention, the composition may further comprise a curing agent, a catalyst, a filler or the combination thereof.

[038] In another embodiment of the present invention, there are provided compositions for bonding articles such as semiconductor chips and devices onto various substrates, comprising: at least one acrylate monomer and/or oligomer; a quantity of a functional fluoride anti-bleed agent sufficient to decrease the resin bleed upon application of said composition to the substrate, wherein the functional fluoride anti -bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20, and preferably X contains a substituted or unsubstituted vinyl group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof; and optional a curing agent, optional liquid BMI, and optional radical initiator. In one aspect, R may have a formula CF₃(CF₂)_n, wherein n is an integer from 1 to about 100 or more; preferably, from about 1 to about 20; more preferably, from about 1 to about 16; most preferably, from about 1 to about 9. In a further embodiment of the present invention, the composition may further comprise a filler.

[039] The catalysts used in the practice of the present invention may include, for example, amine catalysts and/or acid catalysts such as Lewis acid, Lewis base, imidazole, phenol, or the like or the combination thereof. Exemplary amine catalysts may include, but are not limited to, primary amine, secondary amine and the combination. The preferred amine catalyst is primary amine, for example,^' N,N'-(4-methyl-l ,3-phenylene)-bis-l- pyrrolidine-carboxamide. Exemplary acid catalysts may include, but are not limited to carboxylic acid, acid anhydride and their combination. For example, the acid catalyst may be glutaric acid. Typically, the catalyst is present in the range of from 0.001% to about 20 % by weight of the whole bulk resin, preferably from 0.05% to about 10 % by weight.

[040] The curing agent used in the practice of the present invention may include, for example, Lewis acid, Lewis base, imidazole, anhydride, or the combination thereof. Typically, the curing agent is present in the range of from 0.05% to about 50 % by weight of the whole bulk resin.

[041] The radical initiator used in the practice of the present invention may include, but is not limited to peroxide, persulphate, azocompound and their combination. The preferred radical initiator may include peroxide, such as methyl ethyl ketone peroxides, tertiary- amyl peroxy-2-ethylhexyl carbonate, tertiary-butyl peroxyacetate, dicumyl peroxide and so on; mostly preferred peroxide is dicumyl peroxide. Typically, the radical initiator is present in the range of about 0.01% - 20% by weight of the bulk resin, preferably from 0.05% to about 5% by weight.

[042] The fillers used in the practice of the present invention may include, but are not limited to organic and inorganic filler, such as silica filler, silver filler, glass filler, oxide filler, metal coated oxide filler, in spherical or flat shape. Presently preferred filler is silica filler, silver filler or their combination, in various shapes. Typically, the filler is present in a range from about 1% to about 99% by weight of the whole bulk resin. More preferred filler range is from 5% to about 95 % by weight of the whole bulk resin. Mostly preferred filler range is from 10 % to about 90 % by weight of the whole bulk resin. [043] In some aspects, exemplary functional fluoride anti-bleed agent with epoxy group include without limitation, fluorides with straight chain monofunctional fluoride epoxy, e.g. epoxy groups having 2 to about 16 or more carbon atoms. The preferred functional fluoride anti-bleed agent with epoxy group according to the present invention is (2,2,3,3,4,4,5,5,6,6, 7,7,8,8,9,9,9-Heptadecafluorononyl)oxirane (commercially available from Sigma-Aldrich (China) Ltd., Cat. No. 474088) having the following chemical structure:

[044] In some aspects, exemplary functional fluoride anti-bleed agent with amino group include without limitation, fluorides with amino group, e.g., methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, anilino group or the like. The preferred functional fluoride anti-bleed agent with amine group according to the present invention is 4-(Perfluorooctyl)aniline, (Sigma-Aldrich (China) Ltd., Cat. No., 28623) and 1H,1H,2H,2H,3H,3H-Perfluoroundecylamine or 3-(Perfluorooctyl)proρylamine (Sigma-Aldrich (China) Ltd., Cat. No. 04636), which respectively have the following chemical structures: 4-(Perfluorooctyl)aniline (28623)

1 H, 1H,2H,2H,3H,3H-Perfluoroundecylamine or 3-(Perfluorooctyl)propylamine (04636)

CF₃(CF₂)₆CF₂^_/\^NH₂

[045] In other aspects, exemplary functional fluoride anti-bleed agent with vinyl group include without limitation, fluorides with vinyl group(s) or acrylate groups. The preferred functional fluoride anti-bleed agent with vinyl group according to the present invention is 1H,1H,2H-Perfluoro -1-decene (Sigma-Aldnch (China) Ltd., Cat. No. 370576), 1H,1H,2H,2H- Perfluorodecyl acrylate (Sigma-Aldrich (China) Ltd., Cat. No. 474487), 2,2,3,3,4,4,4-Heptafluorobutyl acrylate (Sigma-Aldrich (China) Ltd., Cat. No. 443751), and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12- Heneicosafluorododecyl acrylate (Sigma- Aldrich (China) Ltd., Cat. No. 474355), which respectively have the following chemical structures:

1 H, 1 H,2H-Perfluoro- 1 -decene (370576)

H₂C=CH(CF₂)CF₃

1H,1H,2H,2H-Perfluorodecyl acrylate (474487)

2,2,3,3,4,4,4-Heptafluorobutyl acrylate (443751)

O I l H C -OCH₉CF₉CF₂CF₃

C = C H H 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12- Heneicosafluorododecyl acrylate (474355)

O

CH₂=C-C-OCH₂CH₂(CF₂)₉CF₃ H

[046] In still other aspects, exemplary functional fluoride anti-bleed agents with vinyl group include without limitation, fluorides with maleimide group(s). The preferred functional fluoride anti-bleed agent with maleimide group(s) according to the present invention is 3,3,4,4,5,5,6,6,7,7,8,8, 9,9,10,10,11, 11, 12,12,12,13,13,14,14,15,15,16,16,17,17-Heneicosafluorodo decyl maleimide, which has the following chemical structure:

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12,13,13,14, 14, 15, 15, 16, 16, 17, 17-Heneicosafluorododecyl maleimide

[047] Typically, the quantity of various functional fluoride anti-bleed agents may fall into the range from about 0.0001 % by weight to about

20% by weight of the bulk resin, preferably from about 0.0001 % by weight to about 5% by weight, more preferably from about 0.01% by weight to about 5% by weight, still more preferably from about 0.05% by weight to about 4% by weight, even more preferably from about 0.2% by weight to about 2% by weight, most preferably 0.5% by weight to 2% by weight. In one aspect, the quantity of various functional fluoride anti-bleed agents may be 0.1%, 0.5%, 1%, 1.5%, 2% or 3% by weight of the adhesive.

[048] In some embodiments of the present invention, there is provided a method for reducing resin bleed of organic based curable compositions upon application to a substrate, said method comprising adding to the said organic based adhesive materials a quantity of functional fluoride anti-bleed agent, wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20, and preferably X contains a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted vinyl group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof. In one aspect, R may have a formula CF₃(CF₂),,, wherein n is an integer from 1 to about 100 or more; preferably, from about 1 to about 20; more preferably, from about 1 to about 16; most preferably, from about 1 to about 9. In further additional embodiments, the functional fluoride anti-bleed agent is in the range from about 0.0001 % by weight to about 20% by weight of the adhesive, preferably from about 0.0001 % by weight to about 5% by weight, more preferably from about 0.01% by weight to about 5% by weight, still more preferably from about 0.05% by weight to about 4% by weight, even more preferably from about 0.2% by weight to about 2% by weight, most preferably 0.5% by weight to 2% by weight.

[049] In one embodiment, the present invention further provides a method for producing an article with a component bonded to a substrate, the method comprising applying an organic based curable compositions comprising at least one monomer and/or oligomer and a quantity of functional fluoride anti-bleed agent onto at least a part of the substrate surface, and bonding the component to the adhesive-coated substrate surface, wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20, and preferably X contains a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted vinyl group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof. In one aspect, R may have a formula CF₃(CF₂),,, wherein n is an integer from 1 to about 100 or more; preferably, from about 1 to about 20; more preferably, from about 1 to about 16; most preferably, from about 1 to about 9. In one aspect, the functional fluoride anti-bleed agent is in the range from about 0.0001% to about 20% by weight of whole organic based adhesive materials, preferably from about 0.0001 % by weight to about 5% by weight, more preferably from about 0.01% by weight to about 5% by weight, still more preferably from about 0.05% by weight to about 4% by weight, even more preferably from about 0.2% by weight to about 2% by weight, most preferably 0.5% by weight to 2% by weight.. In another aspect, the method further comprises a step of thermally curing the adhesive at a temperature above room temperature, the step being performed after contacting the substrate with the adhesive. In still another aspect, the component bonded to a substrate may be a semiconductor component, such as a die. In another embodiment, the invention provides an article produced by the method, the article comprising a substrate, a component on the substrate and the adhesive in accordance with the present invention by which the component bonded to the substrate. The said component may be a semiconductor component. The said substrate may be selected from Ag/Cu, bare copper, Ni/Pd/Au substrate or the like.

[050] In a further embodiment, there is provided the use of the functional fluorides as an anti-bleed agent in an adhesive, for example, die attach adhesive, underfill, etc., wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, preferably, from about 1 to about 20, and preferably X contains a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted vinyl group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group, or the like, or the combination thereof. In one aspect,, R may have a formula CF₃(CF₂)_O, wherein n is an integer from 1 to about 100 or more; preferably, from about 1 to about 20; more preferably, from about 1 to about 16; most preferably, from about 1 to about 9. In one aspect, the functional fluoride anti-bleed agent is in the range from about 0.0001% to about 20% by weight of whole organic based adhesive materials, preferably from about 0.0001 % by weight to about 5% by weight, more preferably from about 0.01% by weight to about 5% by weight, still more preferably from about 0.05% by weight to about 4% by weight, even more preferably from about 0.2% by weight to about 2% by weight, most preferably 0.5% by weight to 2% by weight. In one aspect, the adhesive compositions having the present functional fluorides as an anti-bleed agent are used to attach a semiconductor component to a substrate in order to reduce or eliminate self-bleed and/or volatile emission during semiconductor packages.

[051] The invention will now be further described with reference to the following non-limiting examples.

Examples

The test procedure for the anti-bleeding performance

[052] The test procedure used for testing the anti-bleeding performance of the resultant adhesive compositions is described as follows:

1. Specimen Preparation using EFD hand dispenser (From EFD Inc., a Nordson Company, 977 Waterman Avenue, East Province, RI 02914- 1342 USA) 1.1 Record the temperature, humidity and wafer lot used in the lab on the Bleed Test Report Form.

1.2 Switch on the EFD dispenser.

1.3 Connect the adhesive syringe to the dispenser. Use a #21 gauge (ID 0.20 inch) needle to begin with. 1.4 Weigh a 1 " x 3" glass slide and record the weight on the Test

Report Form.

1.5 Dispense 5 dots on a glass slide. Weigh the slide and calculate an average weight of each dot. Record the weight on the Test Report Form. Adjust the air pressure to achieve the desired dispense weight of 1.5mg.

1.6 Once the right parameters for dispensing a 1.5 mg dot have been obtained, remove one aluminum tray from the plasma cleaner (close plasma cleaner door after removing) and dispense a dot of adhesive in the middle of each of the 10 die. 1.7 Within 5 minutes, put aluminum tray with adhesive on die into an oven which is preheated to the cure temperature. Cure via the cure schedule listed on the inspection plan for the adhesive.

1.8 Repeat step 1.3 through 1.7 for each new adhesive batch tested, making sure that the following time limits are adhered to: 1.8.1 Dies are not in plasma cleaner for more than 20 minutes after being cleaned.

1.8.2 Dies are not exposed to ambient conditions for more than 5 minutes.

1.8.3 Parts are placed in curing oven within 5 minutes after dispensing.

2 Bleed Measurement

2.1 Set the magnification of the RAM OMIS II microscope at 3Ox. 2.2 Measure the diameter of the adhesive lot and of the bleed which surrounds the adhesive. Since bleed is not usually perfectly round, take the longest distance as the diameter.

3 Calculation and Report

3.1 Bleed measurements on the Control Sample are done together with the samples.

3.2 Test specimens for new adhesive lots are prepared using dies from the same v/afer used for the Control Sample.

3.3 Measure the diameter of the adhesive lot and of the bleed which surrounds the adhesive. Since bleed is not usually perfectly round, take the longest distance as the diameter.

3.4 Calculate the % Bleed as:

Measured Bleed, % = 100 x (D2 - D1)/D1 wherein:Dl = Diameter of Adhesive, D2 = Diameter of Bleed

3.5 A variation in wafer lot and the environment will likely influence the bleed test results and make direct data questionable. For this reason, bleed results of new adhesive lot should be normalized based on bleed result from the Control Sample.

3.5.1 Calculate Normalized Bleed using the attached template or formulas as below: Normalized Bleed, % = Measured Bleed / Normalization

Factor, wherein, Normalization Factor = Measured Bleed / 100%. Example:

Measured Bleed of New Adhesive Lot = 150% Measured Bleed of Control Lot= 120% Normalization Factor = 120/100 = 1.2 Normalized Bleed Result = 150 / 1.2 = 125% 3.6 Report the Normalized Bleed Result on Test Report. Example 1 Adhesive compositions of the invention

[053] One fluoride with epoxy group (474088, (2,2,3,3,4,4,5,5,6,6,7,7,8,8, 9,9,9 -Heptadecafluorononyl) oxirane), and two fluorides with amine groups, 28623((4-(Perfluorooctyl)aniline), and 04636 (1H,1H,2H,2H, 3H,3H-Perfluoroundecylamine or 3-(Perfluorooctyl)propylamme)) are selected for epoxy platform adhesive application. For radical polymerization platform, four fluorides with vinyl groups are tested. They are 370576(lH,lH,2H-Perfluoro-l-decene), 474487(1 H, 1H,2H,2H- Perfluorodecyl acrylate), 443751(2,2,3, 3, 4,4,4-Heptafluorobutyl acrylate), and 474355 (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12- Heneicosafluorododecyl acrylate).

[054] All organic fluorides are purchased from Sigma-Aldrich (China) Ltd., No 398 Huaihai Middle Road, Shanghai, China, 200020.

[055] Two adhesive formulations, as test vehicle on epoxy platform (TVl) and radical curable platform (TV2), are prepared respectively. As shown in Table 1 and Table 2, the test vehicles are manufactured by mixing all the components, except silver fillers, using hand mixing for 5 to 10 minutes at room temperature until homogenous mixtures are obtained. Then the mixtures are mixed by an EXAKT 50 three roll mill (EXAKT Apparatebau GmBH & Co. KG, Robart-Koch-Strasse 5, 22851 Norderstedt, Germany) at 60 rpm for twice each. After that, the silver fillers are added into the homogenous formulation, and give another 10 minutes hand mixing, until no dry filler powder found. The adhesive formulations are degassed in a vacuum chamber to allow air bubbles to be released from the mixtures. When the adhesive test vehicles are ready, the functional fluorides are added to various formulations, in 1 oz jars, according to the designed ratio, as shown in Table 3 and Table 4. After well dispersed with helping by hand mixing carefully for 5 minutes at least, the samples are used to test the bleeding performance on different substrates, Ag/Cu, bare copper and Ni/Pd/Au, with comparison with test vehicles adhesive formulations.

[056] The selected organic fluorides with epoxy, amino, and vinyl groups respectively have been tested for the anti-bleed effect in related die attcich adhesive formulations, showing decreased bleeding effect on selected Ag/Cu, bare copper and Ni/Pd/Au substrates. This is particularly useful in semiconductor packaging materials and their applications.

[057] From the comparative views on bleeding control effect of uncured samples in TVl (Figure 1 and Figure 2) and TV2 (Figure 3) after dwelling or curing the dot dispensed samples on Ag, Cu, and PPF (Ni/Pd/Au) surfaces. Compared with the control samples, those functional anti-bleed agents in test vehicles formulations decrease bleeding on those surfaces obviously.

[058] As shown in Fig. 1, when uncured, compared with the control sample (1), those functional anti-bleed agents in test vehicle (TVl) formulations decrease bleeding on those surfaces obviously.

[059] As shown in Fig. 2, when cured, compared with the control sample (1), those functional anti-bleed agents in test vehicle (TVl) formulations decrease bleeding on all those surfaces obviously.

[060] As shown in Fig. 3, when cured, compared with the control sample (1), those functional anti-bleed agents in test vehicle (TV2) formulations decrease bleeding on all those surfaces obviously. Table 1. TVl, test vehicle for epoxy platform

TVl Composition - -

Components parts by weight Vendor TVl

N₅N' -(4-methyl- 1 ,3 -phenylene)

-bis- 1 -pyrrolidine-carboxamide Chemica Inc. 1.16

Araldite DY 027, Oxirane, mono[(C8- 10-alkyloxy)methyl] derives,

C8 and ClO alkyl glycidyl ethers Vantlco Inc. 3.86

Cardula N- 10, Glycidyl Resolution Performance neodecanoate Products 11.58

Epiclon EXA-830CRP,

Epichlorohydrin phenolformaldehyde resin Dainippon Ink& Chemical 12.36

Spectrum Laboratory

Glutaric Acid Products 1.54

Silica filler Gelest Inc. 7.72

Silver filler Ferro Metal Group 61.78

Total - 100.00

Chemica Inc. 316 West 13(TStreet, Los Angeles, CA, 90061, USA

Vantlco Inc., 281 Fields Lane, Brewster, NY 10509, USA

Resolution Performance Products, P. O. Box 4500, Houston, tx 77210, USA

Dainippon Ink & Chemicals Inc. 3-7-20, Ninonbashi, Chuo-Ku, Tokyo, 103-8233,

Japan

Spectrum Laboratory Products Inc., 14422 S. San Pedro Street, Gardena, CA, 90248

Gelest Inc. 11 East Steel Rd. Morrisville, PA, 19067

Ferro Metal Group, 3900 South Clinton Avenue, South Plainfield, NJ, 07080, USA

Table 2. TV2, test vehicle for radical curable platform

TV2 Composition

Components parts by weight Vendor TV2

Silica filler Gelest Inc. 35.18

SR248, Neopentyl Glycol

Dimethacrylate Esters Sartomer Inc (Shanghai) 8.54

National Starch &

Liquid BMI Chemical 22.11

SR355, Neopentyl Glycol

Dimethacrylate Esters Sartomer Inc (Shanghai) 5.53 Dicumyl peroxide Sigma-Aldrich China 0.5

Silver filler Ferro Metal Group 28.14

Total IQQ

Gelest Inc. 11 East Steel Rd. Morrisville, PA, 19067

Sartomer Inc. (Shanghai), 500 Fu Te 2^nd East Road, Wai Gao Qiao Free

Trade Zone, Shanghai, 200131.

National Starch & Chemical, P.O. Box 6500, 10 Finderne Avenue,

Bridgewater, NJ, 08807 USA

Ferro Metal Group, 3900 South Clinton Avenue, South Plainfield, NJ, υ7O8O, USA

Table 3. Compositions of epoxy platform samples

Composition for samples - -

Parts by weight 1 2 3 4

TVl 100 99.5 99.5 99.5

474088 - 0.5 - -

04636 - - 0.5 -

28623 - - - 0.5

Total 100.00 100.00 100.00 100.00

Table 4. Compositions of radical curable platform samples

(acrylate / maleimide hybrid)

Composition for samples - - -

Parts by weight 1 2 3 4 5

TV 2 100 98 98 98.5 98.5

370576 - 2 - - -

474487 - - 2 - -

443751 - - - 1.5 -

474355 - - - - 1.5

Total 100 100 100 100 100

Example 2 The anti-bleed performance of the adhesive compositions with different amounts of the functional fluoride anti-bleed agent

[061] The adhesive compositions were formulated as described in Example 1 except that the amount of the functional fluoride anti-bleed agent (28623) was varied. The bleeding control effect of uncured samples in TVl after dwelling or curing the dot dispensed samples on Ag, Cu, and PPF (Ni/Pd/Au) surfaces is shown in Table 5. As can be seen in Table 5, the bleeding control effect is increased as the amount of the functional fluoride anti-bleed agent is increased.

Table 5 The effect of the amount of the functional fluoride anti-bleed agent on the performance of the compositions

Oven cure 1 2 3 4 5 6 7

TVl 100 99.9 99.8 99.6 99.2 98 96

28623 0.1 0.2 0.4 0.8 2 4

Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00

Bleed% on Ag 500 139.8 45.5 23.3 ^"13.8 6.9 7.2

Bleed% on Cu 176.2 85.4 43.4 10.3 12.1 0.8 4.5

Bleed% on PPF 153.2 78.3 26 16.1 15.7 12.6 6.6

Example 3

The application of the adhesive for die attach [062] This example shows an article or a process of producing the article, the article comprising a semiconductor component bonded to a substrate by one of the resultant adhesive compositions prepared in the Example 1, as schematically illustrated in Fig. 4.

[063] At least a part of the substrate surface is applied with adhesive composition sample 2 in Table 3 in a coating thickness of 1-2 mm, and then a die is applied to the adhesive-coated substrate surface. The die is bonded to the substrate after the adhesive is cured at a temperature, for example, 120^°C for 20 mintues, 110^°C for 10 mintues, 150^°C for 30 minutes, 180 ^°C for 50 minutes and so on.

[064] Those skilled in the art readily appreciate that the present invention is well adapted to achieve the purposes and obtain the advantages mentioned, as well as those inherent herein. It will be readily apparent to one skilled in the art that varying substitutions and modifications may be made to the invention disclosed herein without departing from the scope and spirit Ox tiic iiivCiu-on.

Claims

What is claimed:

1. A curable composition for bonding or encapsulating an article onto a substrate, comprising: at least one monomer and/or oligomer; and a quantity of one or more functional fluoride anti-bleed agent sufficient to decrease the resin bleed upon application of said composition to the substrate.

O I. The cυiϊiposiliυa of claim i, wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more.

3. The composition of claim 2, wherein the carbon number of R is froϊn about 1 to about 20.

>.

4. The composition of claim 2, wherein X contains a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted vinyl group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group.

5. The composition of any one of claims 2-4, wherein R has a formula CF₃(CF₂),_! with n being an integer from 1 to about 100 or more.

6. The composition of claim 5, wherein n is an integer from about 1 to about 20.

7. The composition of any one of preceding claims, wherein the quantity of the functional fluoride anti-bleed agent is in the range from about 0.0001 -20% by weight of the adhesive composition.

8. The composition of any one of preceding claims, wherein the monomer and/or oligomer comprises epoxies, acrylates, methylacrylates, maleimides, cyanate esters, liquid BMI, silanes, propargyls, vinyls, cyclic silicones, benzoxazines, vinyl amides, vinyl amines, bisoxazolines, styrenics, cinnamyls, maleates, fumarates, oxetanes, epoxidized rubbers and the combination thereof.

9. The composition of any one of the preceding claims, further comprising a filler.

10. The composition of claim 9, wherein the filler is silica filler, silver filler, or the combination thereof.

11. The composition of claim 9 or 10, wherein said filler is in the range of from about 1-99% by weight of the adhesive composition.

12. The composition of any one of the preceding claims, wherein the functional fluoride anti-bleed agent is selected from the group consisting of (2,2,3,3,4,4,5,5,6,6, 7,7,8,8,9,9,9-Heρtadecafluorononyl)oxirane

4-(Perfluorooctyl)aniline

IH, 1H,2H,2H,3H,3H-Perfluoroundecylamine or 3 -(Perfluorooctyl)propylamine

CF₃(CF₂)₆CF_;

1 H, 1 H,2H-Perfluoro- 1 -decene

H₂C=CH(CF₂)CF₃ ,

1 H, 1 H,2H,2H-Perfluorodecyl acrylate

O Il

CH₂=C-C-OCH₂CH₂(CF₂)₇CF₃ H

2,2,3, 3, 4,4,4-Heptafluorobutyl acrylate

H C -OCH₂CF₂CF₂CF₃

C = C H H ,

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12- Heneicosafluorododecyl acrylate

O

CH₂-C C OCH₂CH₂(CF₂)gCF₃ H

, and

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12,13,13,14, 14,15,15,16,16,17,17-Heneicosafluorododecyl maleimide ₂CF₃

13. A method for reducing resin bleed of organic based curable compositions upon application to a substrate, comprising adding to the said organic based adhesive materials a quantity of functional fluoride s anti-bleed agent, wherein the functional fluoride anti-bleed agent has the formula R-X, where X is(are) reactive functional group(s), R is a fluoro group containing organic chain, with carbon number from about 1 to about 100 or more, and X contains a substituted or unsubstituted epoxy, a substituted or unsubstituted amino, a substituted or unsubstituted vinylo group, a substituted or unsubstituted maleimide group, a substituted or unsubstituted silane group, a substituted or unsubstituted oxane group, or a substituted or unsubstituted cyanate ester group.

14. The method of claim 13, wherein R has a formula CF₃(CF₂)_n with n being an integer from 1 to about 100 or more. 5

15. The method of claims 13 or 14, wherein the organic based adhesive materials comprises at least an epoxy monomer and/or oligomer, and the functional fluoride anti-bleed agent is (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9- Heptadecafluoroncnyl)oxirane having the following chemical structure:

, 4-(Perfluorooctyl)aniline or 1H,1H,2H,2H,3H,3H-Perfluoroundecylamine or 3-(Perfluorooctyl)propylamine, which respectively have the following chemical structures: 4-(Perfluorooctyl)aniline

1 H, 1 H_;2H,2H3H,?H-Perf!v.orev.ndecy!amine or 3 -(Perfluorooctyl)propyl amine

CF₃(CF₂)₆CF₂^_/\^,NH₂

or the combination thereof.

16. The method of claims 13 or 14, wherein the organic based adhesive materials comprises at least (methyl)acrylate monomer and/or oligomer and the functional fluoride anti-bleed agent with an vinyl group comprises lH,lH,2H-Perfluoro-l-decene, 1H,1H,2H,2H-Perfluorodecyl acrylate, 2,2,3,3,4,4,4-Heptafluorobutyl acrylate, and 3,3,4,4,5,5,6,6,7,7,8, 8,9,9,10,10,11,11,12,12,12-Heneicosa-fluorododecyl acrylate, which respectively have the following chemical structures:

lH,lH,2H-Perfluoro-l-decene

H₂C=CH(CF₂)CF₃

1 H, 1 H,2H,2H-Perfluorodecyl acrylate

O

Il

CH₂=C-C-OCH₂CH₂(CF₂)₇CF₃ H 2,2,3,3,4,4,4-Heptafluorobutyl acrylate

O I l H C -OCH₂CF₀CF₂CF₃

C =C / \

H H

or the combination thereof.

17. The method of claims 13 or 14, wherein the functional fluoride anti-bleed agent with an maleimide group comprises 3,3,4,4,5,5,6,6,7,7, 8,8,9,9,10,10,11,11 ,12,12,12,13,13,14,14,15,15,16,16,17,17-Heneicosafϊuor ododecyl maleimide, which has the following chemical structure: 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11 ,12,12,12,13,13,14,

14,15,15,16,16,17,17-Heneicosafluorododecyl maleimide

18. The method of any one of claims 13-17, wherein the functional fluoride anti-bleed agent is present in a range of from about 0.0001% to about 20%.

19. A method for producing an article with a component bonded to a substrate, the method comprising applying the composition of any one of claims 1-12 onto at least a part of the substrate surface, and bonding the component to the adhesive-coated substrate surface.

20. The method of claim 19, further comprising a step of thermally curing the adhesive after contacting the substrate with the composition.

21. The method of claims 19 or 20, wherein the component bonded to the substrate is a semiconductor component.

22. An article produced bv the method of anv one of H aims 19-71