# US 11,309,345 B2 · Protective film composition and method of manufacturing semiconductor package by using the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,309,345 B2 - Document ID: US11309345B2 - Status: Granted - Kind: B2 - Application number: 17/091,236 - Filed: 2020-11-06 - Published: 2021-02-25 - Granted: 2022-04-19 - Earliest claimed: 2018-02-05 - Assignees: Samsung Electronics Co., Ltd.; Dongjin Semichem Co., Ltd. - Applicants: Samsung Electronics Co., Ltd. - Inventors: Myoung-chul Eum; Hye-kyoung Lee; Chang-kun Kang; Jae-hyun Kim; Kyeong-il Oh; Seung-keun Oh; Chi-hwan Lee - Web page: https://patentgrep.com/patent/US11309345B2 ## CPC - H10F 39/811: {Interconnections} - C08F 220/1806: {C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate} - C08F 220/301: {and one oxygen in the alcohol moiety} - C08F 220/302: {and two or more oxygen atoms in the alcohol moiety} - C08F 220/306: {and polyethylene oxide chain in the alcohol moiety} - C09D 133/08: Homopolymers or copolymers of acrylic acid esters - C09D 133/10: Homopolymers or copolymers of methacrylic acid esters - C09D 133/14: of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen - H10F 39/024: {of coatings or optical elements} - H10F 39/026: {Wafer-level processing} - H10F 39/182: {Colour image sensors} - H10F 39/8063: {Microlenses} - H10F 39/809: {of hybrid image sensors} - H10P 54/00: Cutting or separating of wafers, substrates or parts of devices - H10P 72/74: {using temporarily an auxiliary support} - H10P 72/7402: {Wafer tapes, e.g. grinding or dicing support tapes} - C08F 220/1807: {C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate} - C08F 220/1808: {C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate} - C08F 220/1811: {C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate} - C08F 220/1818: {C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate} - C08F 220/281: {and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate} - C08F 220/282: {and containing two or more oxygen atoms} - C08F 220/283: {and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate} - C08F 220/305: {and containing a polyether chain in the alcohol moiety} - C08K 5/544: containing nitrogen - H10P 72/7416: {used during dicing or grinding} - H10P 72/7422: {used to protect an active side of a device or wafer} - H10W 46/00: Marks applied to devices, e.g. for alignment or identification - H10W 46/301: {for alignment} - H10W 70/60: Insulating or insulated package substrates; Interposers; Redistribution layers (leadframes H10W70/40) - H10W 72/29: Bond pads specially adapted therefor - H10W 72/874: {On different surfaces} - H10W 72/9413: {on encapsulations} - H10W 72/9415: {relative to the surface, e.g. recessed, protruding} - H10W 72/942: {relative to underlying supporting features, e.g. bond pads, RDLs or vias} - H10W 74/114: {by a substrate and the encapsulations} - H10W 74/142: {the encapsulations exposing the passive side of the semiconductor body} - H10W 74/47: comprising organic materials, e.g. plastics or resins - H10W 90/734: {between a chip and a stacked insulating package substrate, interposer or RDL} - H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10 ## Abstract A protective film composition includes a polymer having the following formula: each of a, b, and c is a mole fraction; a+b+c=1; 0.05≤a/(a+b+c)≤0.3; 0.1≤b/(a+b+c)≤0.6; 0.1≤c/(a+b+c)≤0.6; each of R1, R2, and R3 is a hydrogen atom or a methyl group; R4 is a hydrogen atom, a butyrolactonyl group, or a substituted or unsubstituted C3 to C30 alicyclic hydrocarbon group; and R5 is a substituted or unsubstituted C6 to C30 linear or cyclic hydrocarbon group. A method of manufacturing a semiconductor package includes forming a sawing protective film on a semiconductor structure by using the protective film composition and sawing the sawing protective film and the semiconductor structure from the sawing protective film. ## Claims ### Claim 1 A method of manufacturing a semiconductor package, the method comprising: forming a semiconductor structure; and forming a protective film on the semiconductor structure by using a protective film composition, wherein the protective film composition comprises: a polymer having Formula (1); and a solvent, wherein each of a, b, and c is a mole fraction; a+b+c=1; 0.05≤a/(a+b+c)≤0.3; 0.1≤b/(a+b+c)≤0.6; 0.1≤c/(a+b+c)≤0.6; each of R1, R2, and R3 is a hydrogen atom or a methyl group; R4 is a hydrogen atom, a butyrolactonyl group, or a substituted or unsubstituted C3 to C30 alicyclic hydrocarbon group; and R5 is a substituted or unsubstituted C6 to C30 linear or cyclic hydrocarbon group. ### Claim 2 (depends on 1) The method according to claim 1, wherein the semiconductor structure comprises an image sensor that comprises a sensor array region comprising a plurality of microlenses, and the forming of the protective film comprises: coating the protective film composition on the plurality of microlenses; and applying heat to the protective film composition coated on the plurality of microlenses. ### Claim 3 (depends on 2) The method according to claim 2, wherein, in the forming of the protective film, the protective film is formed to have concave surfaces in direct contact with the plurality of microlenses. ### Claim 4 (depends on 1) The method according to claim 1, wherein the semiconductor structure comprises: an image sensor including a sensor array region comprising a plurality of microlenses; and a logic device arranged to vertically overlap the image sensor, and wherein the forming of the protective film comprises coating the protective film composition on the plurality of microlenses. ### Claim 5 (depends on 1) The method according to claim 1, wherein the semiconductor structure comprises: an image sensor including a sensor array region comprising a plurality of microlenses; a logic device vertically overlapping the image sensor; and a memory device spaced apart from the image sensor with the logic device therebetween and vertically overlapping the image sensor, and wherein the forming of the protective film comprises coating the protective film composition on the plurality of microlenses. ### Claim 6 (depends on 1) The method according to claim 1, further comprising: sawing the protective film and the semiconductor structure from a surface of the protective film. ### Claim 7 (depends on 1) The method according to claim 1, further comprising: sawing, the protective film and the semiconductor structure from a surface of the protective film; and removing the protective film by using an alkaline aqueous solution after the sawing of the protective film and the semiconductor structure. ### Claim 8 (depends on 1) The method according to claim 1, further comprising: individualizing the semiconductor structure into a plurality of semiconductor dies and dividing the protective film into a plurality of protective patterns, the plurality of protective patterns covering the plurality of semiconductor dies; transferring a semiconductor die selected from among the plurality of semiconductor dies onto a support tape while the semiconductor die is covered with a protective pattern selected from among the plurality of protective patterns; and removing the protective pattern covering the semiconductor die by using an alkaline aqueous solution while the semiconductor die is on the support tape. ### Claim 9 (depends on 8) The method according to claim 8, wherein the transferring of the selected semiconductor die comprises transferring the selected semiconductor die by picking up a top surface of the protective pattern covering the selected semiconductor die. ### Claim 10 (depends on 1) The method according to claim 1, wherein the semiconductor structure comprises: a substrate comprising a first surface and a second surface opposite the first surface; and an image sensor on the first surface, the method further comprising: after the forming of the protective film, reducing a thickness of the substrate by winding the substrate from the second surface of the substrate while the protective film covers the image sensor. ### Claim 11 (depends on 1) The method according to claim 1, wherein at least one of R4 and R5 comprises an ether group, a carbonyl group, an ester group, or a hydroxyl group. ### Claim 12 (depends on 1) The method according to claim 1, wherein at least one of R4 and R5 comprises at least one heteroatom selected from among O, S, or N. ### Claim 13 (depends on 1) The method according to claim 1, wherein R5 has a structure selected from among the following structures: wherein the symbol “*” represents a binding site; m is an integer selected from 2 to 15; n is an integer selected from 1 to 10; R6 is a hydrogen atom, a methyl group, or a t-butyl group; and R7 is a methyl group, a phenyl group, a C1 to C10 alkyl group-substituted phenyl group, or a C3 to C10 alkylcarbonyl group. ### Claim 14 (depends on 1) The method according to claim 1, herein the protective film composition further comprises a silane compound. ### Claim 15 A method of manufacturing a semiconductor package, the method comprising: forming a semiconductor structure that comprises a sensor array region comprising a plurality of microlenses; forming a protective film on the plurality of microlenses by using a protective film composition; and individualizing the semiconductor structure into a plurality of semiconductor dies and dividing the protective film into a plurality of protective patterns, by sawing the protective film and the semiconductor structure from a surface of the protective film, wherein the protective film composition comprises: a polymer having Formula (1); and a solvent, wherein each of a, b, and c is a mole fraction; a+b+c=1; 0.05≤a/(a+b+c)≤0.3; 0.1≤b/(a+b+c)≤0.6; 0.1≤c/(a+b+c)≤0.6; each of R1, R2, and R3 is a hydrogen atom or a methyl group; R4 is a hydrogen atom, a butyrolactonyl group, or a substituted or unsubstituted C3 to C30 alicyclic hydrocarbon group; and R5 is a substituted or unsubstituted C6 to C30 linear or cyclic hydrocarbon group. ### Claim 16 (depends on 15) The method according to claim 15, further comprising: removing the plurality of protective patterns by using an alkaline aqueous solution. ### Claim 17 (depends on 15) The method according to claim 15, further comprising: transferring selected semiconductor dies from among the plurality of semiconductor dies onto a support tape while each of the selected semiconductor dies is covered with selected protective patterns from among the plurality of protective patterns; and removing the selected protective patterns covering the selected semiconductor dies by using an alkaline aqueous solution while the selected semiconductor dies are on the support tape. ### Claim 18 (depends on 15) The method according to claim 15, wherein at least one of R4 and R5 comprises an ether group, a carbonyl group, an ester group, or a hydroxyl group. ### Claim 19 (depends on 15) The method according to claim 15, wherein at least one of R4 and R5 comprises at least one heteroatom selected from among O, S, or N. ### Claim 20 (depends on 15) The method according to claim 15, wherein the protective film composition further comprises a silane compound.