Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
  • C08G64/0208—Aliphatic polycarbonates saturated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
  • C08G64/0291—Aliphatic polycarbonates unsaturated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/305—General preparatory processes using carbonates and alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/38—General preparatory processes using other monomers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J169/00—Adhesives based on polycarbonates; Adhesives based on derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
  • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
  • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents

Definitions

• a release layer formulation comprising an oligomeric component that comprises a unit of the Formula (I) and/or Formula (II): (Formula I), (Formula II); wherein: each * denotes a chiral carbon; n and m are independently an integer in the range of 1 to 15; each A and E are independently -O-, -NH-, an optionally substituted an optionally substituted an optionally substituted an optionally substituted , an optionally substituted an optionally substituted , an optionally substituted an optionally substituted or an optionally substituted each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are independently hydrogen,
• a release layer composition comprising an oligomeric component that comprises a unit of the Formula (I) and/or Formula (II): (Formula I), (Formula II); wherein: each * denotes a chiral carbon; n and m are independently an integer in the range of 1 to 15; each A and E are independently -O-, -NH-, an optionally substituted an optionally substituted an optionally substituted an optionally substituted , an optionally substituted , an optionally substituted an optionally substituted an optionally substituted an optionally substituted , an optionally substituted , an optionally substituted or an optionally substituted each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are independently hydrogen, halogen, C 1-10 alkyl, C 2-10 alkenyl or C 2-10 alkynyl; and each ss, tt, s and t are independently an chiral carbon
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are hydrogen.
• the release layer composition further comprises a polymeric component intermixed with the oligomeric component.
• the oligomeric component is present in the release layer composition in an amount that is greater than the amount of the polymeric component on a weight basis.
• the polymeric component comprises a unit of the formula (III) and/or Formula (IV): (Formula III) (Formula IV); wherein: each * denotes a chiral carbon; q and r are independently an integer in the range of 16 to 200; each G and J are independently -O-, -NH-, an optionally substituted an optionally substituted , an optionally substituted an optionally substituted an optionally substituted an optionally substituted an optionally substituted an optionally substituted an optionally substituted , an optionally substituted or an optionally substituted each R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 are independently hydrogen, halogen, C 1-10 alkyl, C 2-10 alkenyl or C 2-10 alkynyl; and each uu, vv, u and v are independently an integer in the range of 1 to 10.
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 are hydrogen.
• the chiral carbons in Formula (I) and Formula (II) are selected so that the oligomeric component has a cis:trans ratio in a range from about 20:80 to about 80:20.
• the oligomeric component comprises a number averaged molecular weight (Mn) of about 1000-5000 g/mol.
• the oligomeric component comprises a weight averaged molecular weight (Mw) of about 2000-7000 g/mol.
• the Mw:Mn ratio of the oligomeric component is about 1:1 to 4:1.
• the oligomeric component comprises a glass transition temperature (T g ) of about -50-200 °C.
• the release layer composition further comprises an amount of a catalyst that is effective to catalyze decomposition of the oligomeric component in the presence of radiation.
• the catalyst comprises an acid catalyst, a base catalyst, or a combination thereof.
• the acid catalyst is a photoacid generator (PAG).
• PAG photoacid generator
• the release layer formulation comprises about 1-20 wt% of the catalyst.
• the release layer composition further comprises an amount of a thermal sensitizing agent that is effective to enhance the decomposition rate of the oligomeric component in the presence of radiation. In some embodiments, the release layer composition further comprises an amount of a low molecular weight additive that vaporizes under conditions at which the oligomeric component decomposes in the presence of radiation. [0014] Various embodiments provide a release layer comprising a release layer formulation. [0015] Various embodiments provide an assembly, comprising a release layer disposed over a donor plate. In some embodiments, the assembly further comprises a plurality of components in contact with the release layer.
• Various embodiments provide a method of forming a transfer assembly, comprising: disposing a release layer over a donor plate, wherein the release layer comprises an oligomeric component that comprises a unit of the Formula (I) and/or Formula (II): (Formula I), (Formula II); wherein: each * denotes a chiral carbon; n and m are independently an integer in the range of 1 to 15; each A and E are independently -O-, -NH-, an optionally substituted an optionally substituted an optionally substituted an optionally substituted an optionally substituted , an optionally substituted an optionally substituted an optionally substituted an optionally substituted or an optionally substituted each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are independently hydrogen, halogen, C 1-10 alkyl, C 2-10 alkenyl or C 2-10 alkynyl;
• Various embodiments provide a method of transferring a plurality of components, comprising: disposing a transfer assembly over a receiving substrate, wherein the transfer assembly comprises a donor plate, a release layer disposed over the donor plate, and a plurality of components in contact with the release layer, and wherein the release layer comprises an oligomeric component that comprises a unit of the Formula (I) and/or Formula (II): (Formula I), (Formula II); wherein: each * denotes a chiral carbon; n and m are independently an integer in the range of 1 to 15; each A and E are independently -O-, -NH-, an optionally substituted an optionally substituted , an optionally substituted an optionally substituted an optionally substituted an optionally substituted an optionally substituted an optionally substituted an optionally substituted or an optionally substituted each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8
• FIG. 1 illustrates an embodiment of a process flow in which a release layer composition (B) is used to transfer components (C) from an optically transparent donor plate (A) to a target substrate (D).
• FIG. 2 illustrates examples of embodiments of monomeric carbonate structures.
• FIG. 3 illustrates examples of dimeric, trimeric, oligomeric and polymeric carbonate structures.
• FIG. 4 illustrates examples of oligomeric or polymeric component as block co-oligomers/polymers.
• FIG. 5 depicts H-NMR spectra of 1,1'-(1,2,3,4-Tetrahydro-1,4- naphthalenediyl) di-1H-imidazole-1-carboxylate (top) and its 1,4-dihydroxy-1,2,3,4- tetrahydronaphthalene precursor (bottom).
• FIG. 6 depicts a gel permeation chromatography trace with a UV and refractive index detector used for determination of molecular weight distribution of a synthesized polymer, according to some embodiments.
• FIG. 5 depicts H-NMR spectra of 1,1'-(1,2,3,4-Tetrahydro-1,4- naphthalenediyl) di-1H-imidazole-1-carboxylate (top) and its 1,4-dihydroxy-1,2,3,4- tetrahydronaphthalene precursor (bottom).
• FIG. 7 depicts an H-NMR spectrum and proton assignments for a polymer, according to some embodiments.
• FIG. 8 depicts a graph showing film thicknesses for polymers coated at variable spin rates, according to some embodiments.
• FIG.9 depicts an image of a polymer film coated on a fused silica substrate, according to some embodiments.
• FIG.10 depicts thermogravimetric analysis curves for the decomposition of release layer formulation before and after UV irradiation, according to some embodiments.
• FIG. 11 depicts a gas chromatography (GC) retention curve of the decomposition products of a release layer formulation, according to some embodiments.
• FIG. 31 gas chromatography
• FIG. 12A depicts a pyrolysis-GC-FTIR of a decomposition products of a release layer formulation at an early time, according to some embodiments.
• FIG. 12B depicts a pyrolysis-GC-FTIR of a decomposition products of a release layer formulation at a later time, according to some embodiments
• FIG.13A depicts an image of a 3D height data profile of the craters obtained by laser profilometry of a release layer heated after irradiation, according to some embodiments.
• FIG.13B depicts an image of a 3D height data profile of the craters obtained by laser profilometry of a release layer heated after irradiation, according to some embodiments.
• FIG.13C depicts an image of a 3D height data profile of the craters obtained by laser profilometry of a release layer heated after irradiation, according to some embodiments.
• FIG.14A depicts an image of a 3D height data profile of the craters obtained by laser profilometry of a release layer heated during irradiation, according to some embodiments.
• FIG.14B depicts an image of a 3D height data profile of the craters obtained by laser profilometry of a release layer heated during irradiation, according to some embodiments.
• FIG. 15 depicts an image of silicon chip components attached to a release layer, according to some embodiments.
• FIG.16A depicts an image of microLED components disposed over a donor plate with a release layer after laser induced forward transfer, according to some embodiments.
• FIG.16B depicts an image of microLED components disposed over a target substrate after laser induced forward transfer from the donor plate shown in FIG. 16A, according to some embodiments.
• FIG. 17A depicts an image of silicon die component transferred from a donor plate comprising a release layer onto a target substrate, according to some embodiments.
• FIG. 17B depicts an image of silicon die component transferred from a donor plate comprising a release layer onto a target substrate enlarged from that shown in FIG. 17A, according to some embodiments.
• a release layer composition as described herein may be used in a process for transferring and/or packaging semiconductor components.
• the release layer composition may enable one to simultaneously place as many components on a surface as desired, limited only by how large one wants to make the mechanical fixture for the substrates. These components can range in size from microns (such as microLEDs) up to centimeters (such as large ICs).
• FIG. 1 An optically transparent donor plate (A) is provided 102 and coated 104 (e.g., solvent coated) with a film of the release layer composition (B) to form a coated donor plate 106.
• the desired components (C) to be transferred are adhered 108 to the release layer (B) of the coated donor plate 106 by bringing the components (C) and release layer (B) into contact with applied pressure and/or heat to form a component loaded donor plate 110.
• components are attached to a carrier substrate (e.g., tape) prior to being loaded onto the release layer.
• uniform pressure may be applied to the carrier substrate and/or donor plate.
• pressure may be applied for, for about, for at least, or for at least about 1 minutes, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hours, 1.5 hours or 2 hours, or any range of values therebetween.
• the release layer and components while the release layer and components are contacted for loading the release layer may be heated to a temperature of, of about, of at most, or of at most about, 40°C, 50°C, 60°C, 80°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, or any range of values therebetween.
• the release layer is allowed to cool to room temperature before the pressure is removed.
• the carrier substrate may be removed (e.g., peeled off) to afford the component loaded donor plate 110.
• the component loaded donor plate 110 is then aligned 112 with a target substrate (D) surface prior to irradiation with light source 114 of the release layer (B) through the donor plate (A).
• Irradiation 118 induces a photochemical reaction in the release layer (B) that catalyzes the decomposition of the material into low molecular weight species that are then vaporized by the heat provided from the irradiation to form components (C) released from the donor plate (A) 120.
• the vaporization generates a force that pushes the components (C) to land 122 onto the target substrate (D), where they adhere to the surface to form a component loaded substrate 124.
• the process illustrated in FIG. 1 depends on the release layer delaminating in the presence of light of specific wavelength and energy (X-ray, UV, vis, IR) and, in the absence of such light, maintaining good adhesion.
• the release layer composition is also chemically homogenous, amorphous, and/or optically transparent to facilitate a homogeneous decomposition reaction and homogeneous vapor formation over the area of irradiation.
• the release layer is exposed to radiation of a wavelength of, of about, of at most, or of at most about, 100 nm, 150 nm, 200 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 320 nm, 340 nm, 350 nm, 370 nm, 380 nm, 400 nm or 450 nm, or any range of values therebetween for the purpose of activation and/or degradation.
• the release layer is heated to a temperature of, of about, of at most, or of at most about, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 180°C, 200°C, or any range of values therebetween for the purpose of activation and/or degradation.
• the components held and/or transferred by the release layer comprise a longest dimension (e.g., diameter, length, width, thickness) of, of about, of at least, or of at least about, 10 nm, 25 nm, 50 nm, 75 nm, 0.1 ⁇ m, 0.2 ⁇ m, 0.3 ⁇ m, 0.5 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, 20 ⁇ m, 30 ⁇ m, 50 ⁇ m, 60 ⁇ m, 80 ⁇ m, 100 ⁇ m, 150 ⁇ m, 200 ⁇ m, 300 ⁇ m, 400 ⁇ m, 500 ⁇ m, 600 ⁇ m, 700 ⁇ m, 800 ⁇ m, 900 ⁇ m, 1 mm, 2, mm, 3
• the indicated “optionally substituted” or “substituted” group may be substituted with one or more group(s) individually and independently selected from deuterium (D), halogen, hydroxy, C 1-4 alkoxy, C 1-8 alkyl, C 3-20 cycloalkyl, aryl, heteroaryl, heterocyclyl, C 1-6 haloalkyl, cyano, C 2-8 alkenyl, C 2-8 alkynyl, C 3-20 cycloalkenyl, aryl(alkyl), heteroaryl(alkyl), heterocyclyl(alkyl), acyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, C-thioamido, N-thioamido, S- sulfonamido, N-sulfonamido, N-sulfonamido, N
• C a to C b in which “a” and “b” are integers refer to the number of carbon atoms in a group.
• the indicated group can contain from “a” to “b”, inclusive, carbon atoms.
• a “C 1 to C 4 alkyl” group refers to all alkyl groups having from 1 to 4 carbons, that is, CH 3 -, CH 3 CH 2 -, CH 3 CH 2 CH 2 -, (CH 3 ) 2 CH-, CH 3 CH 2 CH 2 CH 2 -, CH 3 CH 2 CH(CH 3 )- and (CH 3 ) 3 C-. If no “a” and “b” are designated, the broadest range described in these definitions is to be assumed.
• alkyl refers to a fully saturated aliphatic hydrocarbon group.
• the alkyl moiety may be branched or straight chain.
• branched alkyl groups include, but are not limited to, iso-propyl, sec-butyl, t-butyl and the like.
• straight chain alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and the like.
• the alkyl group may have 1 to 30 carbon atoms (whenever it appears herein, a numerical range such as “1 to 30” refers to each integer in the given range; e.g., “1 to 30 carbon atoms” means that the alkyl group may consist of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 30 carbon atoms, although the present definition also covers the occurrence of the term “alkyl” where no numerical range is designated).
• the alkyl group may also be a medium alkyl having 1 to 12 carbon atoms.
• the alkyl group could also be a lower alkyl having 1 to 6 carbon atoms.
• An alkyl group may be substituted or unsubstituted.
• alkenyl used herein refers to a monovalent straight or branched chain radical of from two to thirty carbon atoms containing a carbon double bond(s) including, but not limited to, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl and the like. An alkenyl group may be unsubstituted or substituted.
• alkynyl used herein refers to a monovalent straight or branched chain radical of from two to thirty carbon atoms containing a carbon triple bond(s) including, but not limited to, 1-propynyl, 1-butynyl, 2-butynyl and the like.
• alkynyl group may be unsubstituted or substituted.
• hydroxy refers to a –OH group.
• halogen atom or “halogen” as used herein, means any one of the radio-stable atoms of column 7 of the Periodic Table of the Elements, such as, fluorine, chlorine, bromine and iodine.
• substituents e.g. haloalkyl
• “haloalkyl” may include one or more of the same or different halogens.
• C 1 -C 3 alkoxyphenyl may include one or more of the same or different alkoxy groups containing one, two or three atoms.
• a radical indicates species with a single, unpaired electron such that the species containing the radical can be covalently bonded to another species.
• a radical is not necessarily a free radical. Rather, a radical indicates a specific portion of a larger molecule.
• each center may independently be of R-configuration or S-configuration or a mixture thereof.
• the compounds provided herein may be enantiomerically pure, enantiomerically enriched, racemic mixture, diastereomerically pure, diastereomerically enriched, or a stereoisomeric mixture.
• each double bond may independently be E or Z, or a mixture thereof.
• any compound described in any compound described, all tautomeric forms are also intended to be included.
• a reference to the compound may be interpreted to include tautomer
• the valencies are to be filled with hydrogens or isotopes thereof, e.g., hydrogen- 1 (protium) and hydrogen-2 (deuterium).
• hydrogen- 1 protium
• hydrogen-2 deuterium
• the compounds described herein can be labeled isotopically. Substitution with isotopes such as deuterium may afford certain therapeutic advantages resulting from greater metabolic stability, such as, for example, increased in vivo half-life or reduced dosage requirements.
• Each chemical element as represented in a compound structure may include any isotope of said element.
• a hydrogen atom may be explicitly disclosed or understood to be present in the compound.
• the hydrogen atom can be any isotope of hydrogen, including but not limited to hydrogen-1 (protium) and hydrogen-2 (deuterium).
• reference herein to a compound encompasses all potential isotopic forms unless the context clearly dictates otherwise.
• the term “comprising” is to be interpreted synonymously with the phrases “having at least” or “including at least”.
• the term “comprising” means that the process includes at least the recited steps, but may include additional steps.
• the term “comprising” means that the compound, composition or device includes at least the recited features or components, but may also include additional features or components.
• the composition of the release layer may include an oligomer and/or polymer composition.
• the oligomer and/or polymer composition may include an oligomeric and/or polymeric component that is a unit containing a tetralin or cyclohexene core and a linkage.
• the oligomeric component comprises a unit of the Formula (I) and/or Formula (II).
• Formula (I) (Formula I), (Formula II) [0066]
• each * denotes a chiral carbon in the cyclohexyl ring.
• a chiral carbon is configured so that the cyclohexene ring is in a cis orientation.
• a chiral carbon is configured so that the cyclohexene ring is in a trans orientation.
• the polymeric component has a cis:trans ratio of, of about, of at least, of at least about, of at most, or of at most about, 0:100, 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5 or 100:0, or any range of values therebetween.
• n is an integer of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, or any range of values therebetween. For example, in some embodiments n is in the range of 1 to 15.
• m is an integer of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, or any range of values therebetween.
• m is in the range of 1 to 15.
• linkage A is independently -O-, -NH-, an optionally substituted an optionally substituted an optionally substituted an optionally substituted , an optionally substituted an optionally substituted an optionally substituted or an optionally substituted
• linkage E is independently -O-, -NH-, an optionally substituted an optionally substituted an optionally substituted an optionally substituted , an optionally substituted an optionally substituted an optionally substituted an optionally substituted or an optionally substituted
• each R 1 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 2 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 3 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 4 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 5 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 6 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 7 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 8 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 9 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 10 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each s is independently an integer in the range of 1 to 10.
• each t is independently an integer in the range of 1 to 10. In some embodiments, each ss is independently an integer in the range of 1 to 10. In some embodiments, each tt is independently an integer in the range of 1 to 10. In some embodiments, each s is independently an integer in the range of 1 to 10. In some embodiments, each t is independently an integer in the range of 1 to 10. [0067] In some embodiments, the release layer composition comprises a polymer material. In some embodiments, the release layer composition comprises a polymeric component that is intermixed with the oligomeric component. In some embodiments, the polymeric component forms a homogenous film with the oligomeric component. In some embodiments, the polymer component comprises a plurality of polymers.
• polymeric component can be used in amounts effective to modulate material properties and/or the release properties of the release layer film.
• polymeric components include a linear homopolymer, block copolymer, polymeric network, etc.
• the polymeric component acts as a matrix to support the oligomeric component, dictates the release layer’s physical properties and/or optical properties. Tailoring the material properties of the release layer by modifying the polymeric component may be advantageous as the properties of the release layer can be altered on a per application basis without having to redesign the oligomeric ingredient.
• different polymers can alter the processing conditions for adhering the components to the release layer.
• network polymers may aid to trap non-volatile residue from being transferred during gas evolution.
• the polymeric component is photochemically inert. In some embodiments, the polymeric component is photochemically active.
• potential polymeric components include: a polymeric component containing a tetralin or cyclohexene core and a linkage, polypropylene, poly(propyl carbonate), polyurethane, ABS block copolymer, polyesters, polyvinyl chloride, polystyrene, copolymers thereof, and combinations thereof.
• An example of a network polymer could be a polyethylene glycol polymer crosslinked by thiol-ene photochemistry after deposition onto the donor substrate.
• the polymeric component comprises a unit of the Formula (III) and/or Formula (IV).
• each * of the Formula (III) and/or Formula (IV) denotes a chiral carbon in the cyclohexene ring.
• a chiral carbon is configured so that the cyclohexene ring is in a cis orientation.
• a chiral carbon is configured so that the cyclohexyl ring is in a trans orientation.
• the polymeric component has a cis:trans ratio of, of about, of at least, of at least about, of at most, or of at most about, 0:100, 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5 or 100:0, or any range of values therebetween.
• q is an integer of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 120, 150, 200, 300, 400, 500, 600, 800 or 1000, or any range of values therebetween.
• q is in the range of 16-50 or 16-200.
• r is an integer of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 120, 150, 200, 300, 400, 500, 600, 800 or 1000, or any range of values therebetween.
• r is in the range of 16-50 or 16-200.
• linkage G is independently -O-, -NH-, an optionally substituted an optionally substituted an optionally substituted an optionally substituted an optionally substituted , an optionally substituted an optionally substituted an optionally substituted or an optionally substituted
• linkage J is independently -O-, -NH-, , , an optionally substituted an optionally substituted an optionally substituted , an optionally substituted an optionally substituted an optionally substituted an optionally substituted or an optionally substituted
• each R 11 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 12 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 13 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 14 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 15 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 16 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 17 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 18 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 19 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each R 20 is independently hydrogen, halogen, C 1-10 alkyl (e.g., C 1-3 alkyl), C 2-10 alkenyl or C 2-10 alkynyl.
• each uu is independently an integer in the range of 1 to 10.
• each vv is independently an integer in the range of 1 to 10.
• each u is independently an integer in the range of 1 to 10.
• each v is independently an integer in the range of 1 to 10.
• the tetralin core is an aromatic chromophore that facilitates film heating with irradiation (e.g., by a laser) with a wavelength approximately in the range of 240-300nm.
• the cyclohexene core may be indirectly heated through irradiation of a compound within the film that acts as a chromophore.
• the ability to undergo effective heating drives the decomposition kinetics to a microsecond timescale that facilitates a homogenous transfer force.
• the efficiency of the process illustrated in FIG. 1 depends on the core structure of the oligomeric component and/or the polymeric component (for embodiments in which the polymeric component contains a photochemically active component).
• the oligomeric or polymeric component includes a unit of the tetralin (i.e. bicyclic tetrahydronaphthalene) or cyclohexene core that is connected to a carbonate linkage.
• the structures can be monomeric as in the examples shown in FIG. 2, or dimeric, trimeric, oligomeric, or polymeric as shown in FIG. 3, as long as the component contains the cores and linkages described herein.
• FIG. 4 shows examples of oligomeric or polymeric component as diblock, triblock, or multiblock block co-oligomers/polymers.
• the aromatic portion of the tetralin i.e.
• tetrahydronapthalene or another compound serve as a chromophore for UV-irradiation that will serve to convert light into heat for decomposition and vaporization of decomposition products and/or volatile additives.
• the decomposed cores may be converted into unreactive and volatile products.
• tetralin i.e. tetrahydronapthalene
• carbonates when the carbonates are cleaved the tetrahydronaphthalene core will be converted into naphthalene, which is unreactive and volatile. This also drives the decomposition reaction to completion due to formation of an aromatic system.
• benzylic carbonates e.g.
• oligomeric or polymeric components with a tetralin i.e. tetrahydronapthalene unit and a carbonate linkage
• a tetralin i.e. tetrahydronapthalene
• carbonate linkage may be advantageous as the benzylic functionality stabilizes the cationic intermediate of carbonate cleavage and may result in a much faster and lower energy cleavage reaction.
• bis-carbonate core i.e. oligomeric or polymeric components with a tetralin (i.e. tetrahydronapthalene) or cyclohexene linked to two carbonate linkages
• the polymeric and/or oligomeric component has a number averaged molecular weight (Mn) of, of about, of at least, or of at least about, 1000 g/mol, 1500 g/mol, 1800 g/mol, 1900 g/mol, 2000 g/mol, 2100 g/mol, 2200 g/mol, 2300 g/mol, 2400 g/mol, 2600 g/mol, 2800 g/mol, 3000 g/mol, 3250 g/mol, 3500 g/mol, 3750 g/mol, 4000 g/mol, 4250 g/mol, 4500 g/mol, 5000 g/mol, 6000 g/mol, 7000 g/mol, 8000 g/mol, 10000 g/mol,
• the polymeric and/or oligomeric component has a weight averaged molecular weight (Mw) of, of about, of at least, or of at least about, 2000 g/mol, 2100 g/mol, 2200 g/mol, 2300 g/mol, 2400 g/mol, 2600 g/mol, 2800 g/mol, 3000 g/mol, 3250 g/mol, 3500 g/mol, 3750 g/mol, 4000 g/mol, 4250 g/mol, 4500 g/mol, 5000 g/mol, 5500 g/mol, 6000 g/mol, 6500 g/mol, 7000 g/mol, 8000 g/mol, 10000 g/mol, 15000 g/mol, 20000 g/mol, 25000 g/mol, 50000 g/mol, 100000 g/mol, 150000 g/mol, 200000 g/mol, 250000 g/mol, 500000 g/mol, 1000
• the polymeric and/or oligomeric component has a Mw:Mn ratio of, of about, of at least, or of at least about 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.75:1, 2:1, 2.25:1, 2.5:1, 3:1, or 4:1, or any range of values therebetween.
• the polymeric and/or oligomeric component has a glass transition temperature (T g ) of, of about, of at most, of at most about, of at least, or of at least about, 200 °C, 160 °C, 150 °C, 145 °C, 140 °C, 135 °C, 130 °C, 125 °C, 120 °C, 115 °C, 110 °C, 105 °C, 100 °C, 90 °C, 80 °C, 75 °C, 60 °C, 50 °C, 45 °C, 40 °C, 35 °C, 30 °C, 25 °C, 20 °C, 15 °C, 10 °C, 5 °C, 0 °C, -5 °C, -10 °C, -15 °C, -20 °C, -25 °C, -30 °C, -35 °C, -40 °C, -45 °C, -45 °
• the formulation comprises cis isomers of the polymeric and/or oligomeric component. In some embodiments, the formulation comprises trans isomers of the polymeric and/or oligomeric component. In some embodiments, the formulation comprises both cis and trans isomers of the polymeric and/or oligomeric component. In some embodiments, a mixture of the cis and trans isomers reduces or prevents crystallization of the polymeric and/or oligomeric component. [0076] In embodiments of the release layer compositions described herein, the decomposing material (e.g. the oligomeric component) is a majority ingredient (i.e. the ingredient that makes up the largest wt% or mass%) of the release layer formulation.
• the decomposing material e.g. the oligomeric component
• the oligomeric component is a majority ingredient (i.e. the ingredient that makes up the largest wt% or mass%) of the release layer formulation.
• the decomposing material e.g. the oligomeric component
• the decomposing material is a minority ingredient of the release layer formulation.
• a polymeric component can be the main ingredient of the release layer, while the oligomeric component is a minority ingredient.
• the release layer composition comprises, comprises about, comprises at least, comprises at least about, comprises at most, or comprises at most about, 1 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, 95 wt.% or 98 wt.% of the oligomeric component, or any range of values therebetween.
• the release layer composition comprises, comprises about, comprises at least, comprises at least about, comprises at most, or comprises at most about, 1 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, 95 wt.% or 98 wt.% of the polymeric component, or any range of values therebetween.
• the release layer composition comprises an (optional) thermal sensitizing agent, in the form of one or more additives that absorb light and convert it into heat.
• Thermal sensitizing agents may have a high photon absorption quantum yield, a low fluorescence/phosphorescence quantum yield, and/or a short excited state lifetimes that decay through non-irradiative pathways. They may be used in amounts effective to aid the heating rate during irradiation and thereby increase the rate of linkage decomposition and gas formation. These agents can also facilitate heating with lower power and longer wavelength lasers.
• the thermal sensitizing agent will form a homogenous film with the release layer formulation. In some embodiments, the thermal sensitizing agent will form a transparent film with the release layer formulation.
• the thermal sensitizing agent will form an opaque film with the release layer formulation.
• thermal sensitizing agents in some embodiments include, inorganic agents, gold plasmonic nanoparticles, silver plasmonic nanoparticles, gold nanowires, silver nanowires, carbon based agents, carbon nanotubes, carbon black, graphene, graphene oxide, organic based agents, and metallic agents.
• organic based thermal sensitizing agents include one or more of the following structural properties: aromaticity, fused multicyclic systems, S or N containing heterocycles, multicyclic systems, and/or multi-aromatic systems.
• organic based thermal sensitizing agents include melanin, eumelanin, indole, pyrrole, quinoline, purine, triphenyl methyl compounds (e.g. (methoxymethanetriyl)tribenzene), fused aromatic compounds (e.g. anthracene and pyrene), dibenzothiophene, thiophene, and derivatives thereof.
• an (optional) acid or base additive is included in the release layer composition in an amount effective to catalyze the oligomeric and/or polymeric decomposition.
• the acid additive is selected from a sulfonic acid (e.g., p-toluenesulfonic acid, methane sulfonic acid, heptadecafluorooctanesulfonic acid), a benzoic acid (e.g., benzoic acid, salicylic acid, nonyloxybenzoic acid, oxybis(benzoic acid)), a monocarboxylic acid (e.g., butyric acid, perfluorooctanoic acid), a multifunctional carboxylic acid (e.g., citric acid, malic acid, fumaric acid), derivatives thereof (e.g., butene-1,2-dio-1(p- toluenesulfonate)), and combinations thereof.
• a sulfonic acid e.g., p-toluenesulfonic acid, methane sulfonic acid, heptadecafluorooctanes
• the base additive is selected from an ammonium hydroxide (e.g., Tetrabutylammonium hydroxide), a tertiary amine (e.g., N,N-diisopropylethylamine), an amino base (e.g., 1,4-diazabicyclo[2.2.2]octane, Bis[2-(N,N-dimethylamino)ethyl] ether, Pentamethyldiethylenetriamine, 1,8- Diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazabicylco[4.4.0]dec-5-ene), a pyridine base (e.g., 4- (Dimethylamino)pyridine), derivatives thereof, and combinations thereof.
• an ammonium hydroxide e.g., Tetrabutylammonium hydroxide
• a tertiary amine e.g., N,N-diisopropylethylamine
• the acid additive is a photoacid generator (PAG).
• the PAG includes a chromophore unit and an acid precursor unit.
• the chromophore unit is selected from diphenyliodonium, triphenylsulfonium, and combinations thereof.
• the acid precursor unit is selected from trifluoromethanesulfonate (i.e., triflate), hexafluorophosphate, nitrate, p-toluenesulfonate, perfluoro-1-butanesulfonate, and combinations thereof.
• the PAG is an ionic PAG or a non-ionic PAG.
• the ionic PAG is selected from diphenyliodonium nitrate, bis(4-tert-butylphenyl) iodonium perfluoro-1-butanesulfonate, bis(4-tert-butylphenyl)iodonium p-toluenesulfonate, (4-phenylthiophenyl)diphenylsulfonium triflate, triarylsulfonium hexafluorophosphate, and combinations thereof.
• the non-ionic PAG is selected from N-hydroxynaphthalimide triflate, N- hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate, 2-(4-methoxystyryl)- 4,6,-bis(trichloromethyl)-1,3,5-tirazine, and combinations thereof.
• the PAG is (4-Phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, .
• the acid or base additive is included in the release layer composition in an amount of, of about, of at most, or of at most about, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt% or 20 wt%, or any range of values therebetween.
• the release layer composition comprises an (optional) low molecular weight additives that will vaporize under the conditions of the transfer.
• additives can be used in amounts that are effective to enhance the force generation during irradiation and thereby may aid in the lift or release of components from the release layer.
• a low molecular weight additive may also aid in altering the viscoelastic properties of the release layer, thereby facilitating faster bonding at lower temperatures.
• additives that absorb light and convert it into heat can be the main ingredient of the release layer. They may be used in amounts effective to aid the heating rate during irradiation and thereby increase the rate of oligomeric and/or polymeric decomposition and gas formation. These agents can also facilitate heating with lower power and longer wavelength lasers.
• additives include collodial metals, Si, SiO2, TiO2, SnO2, anthracene, naphthalene, dimethoxybenzene, tetrahydronaphthalene, diphenyl ether, phenylcyclohexane, tert-butylphenol, acetoxy-tetrahydronaphthalene, and derivatives thereof.
• the additives are configured to absorb at wavelengths of, of about, of at most, of at most about, of at least, or of at least about, 300 nm, 320 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1000 nm, 1100 nm, 1300 nm or 1500 nm, or any range of values therebetween.
• additives that vaporize under the conditions of the transfer can be the main ingredient of the release layer.
• Additives may be used in amounts effective to enhance the force generation during irradiation.
• the additive may be any organic molecule that does not contain heteroatoms besides oxygen.
• the additives may be used to modulate the physical properties for processing the release layer in its solid film state by lowering the films Tg, which may allow for reduced temperatures and pressures to be utilized while attaching components to be transferred.
• additives are vaporizable when irradiated.
• the additive has a molecular weight of, of about, of at most, or of at most about, 500 Da, 300 Da, 200 Da, 180 Da, 160 Da, 150 Da, 140 Da, 130 Da, 120 Da, 110 Da, 100 Da, 80 Da, 50 Da, 30 Da or 10 Da, or any range of values therebetween.
• the additive has a boiling point of, of about, of at most, or of at most about, 400 °C, 300 °C, 275 °C, 250 °C, 200 °C, 190 °C, 180 °C, 170 °C, 160 °C, 150 °C, 140 °C, 130 °C, 120 °C, 110 °C, 100 °C, 90°C, 80 °C, 70 °C, 60 °C, 50 °C or 40 °C, or any range of values therebetween.
• the additive has a flash point of, of about, of at least, or of at least about, 800 °C, 700 °C, 600 °C, 550 °C, 500 °C, 475 °C, 450 °C, 425 °C, 400 °C, 375 °C, 350 °C, 320 °C, 310 °C, 300 °C, 275 °C, 250 °C or 200 °C, or any range of values therebetween.
• the additive has a melting point of, of about, of at most, or of at most about, 250 °C, 200 °C, 150 °C, 140 °C, 130 °C, 120 °C, 110 °C, 100 °C, 90°C, 80 °C, 70 °C, 60 °C, 50 °C, 40 °C, 35 °C, 30 °C, 25 °C, 20 °C, 10 °C or 0 °C, or any range of values therebetween.
• the additive has a room temperature vapor pressure of, of about, of at most, or of at most about, 0.8 torr, 0.7, tore, 0.6 torr, 0.5 torr, 0.4 torr, 0.3 torr, 0.2 torr, 0.1 torr, 0.08 torr, 0.06 torr, 0.04 torr, 0.02 torr or 0.01 torr, or any range of values therebetween.
• the oligomer and/or polymer composition comprises a plurality of oligomeric and/or polymeric components. In some embodiments, at least two oligomeric and/or polymeric components are different components.
• the release layer comprises a plurality of release layer sublayers.
• the release layer has a thickness of, of about, of at most, or of at most about, 0.1 ⁇ m, 0.5 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, 1 ⁇ m, 1.1 ⁇ m, 1.2 ⁇ m, 1.3 ⁇ m, 1.4 ⁇ m, 1.5 ⁇ m, 1.6 ⁇ m, 1.8 ⁇ m, 2 ⁇ m, 2.2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m or 4 ⁇ m, 5 ⁇ m, 7 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 100 ⁇ m, 120 ⁇ m, 150 ⁇ m or 200 ⁇ m, or any range of values therebetween.
• Di-tert- butyl dicarbonate (560 mg, 2.56 mmol) is added, and the solution is allowed to stir for a further 2 h, in which time it develops a light clear yellow color.
• the product is extracted from ethyl acetate and is washed with 3 brine and dried over MgSO4. Further purification is performed using silica gel chromatography (EtOAc:n-hexane, 1:4). The solvent is removed And the product is isolated.
• This ampule is connected to a high vacuum pump and the materials engaged are further dried for 24 h. Dry CH2Cl2 (430 mL) is added. The sealed ampule is stirred magnetically and heated in an oil bath at 45°C for 5 days under nitrogen. At the end of the reaction, more CH2Cl2 (250 mL) and a saturated solution of sodium bicarbonate (250 mL) are added to the ampule. The reaction mixture is transferred to a separatory funnel and the lower organic phase is removed. The aqueous phase is extracted with CH2Cl2 (200 mL x 2) and the CH2Cl2 extracts are combined.
• (G) 1-acetoxy-4-trifluoroacetoxy-1,2,3,4- tetrahydronaphthalene A solution of (F) 1-acetoxy-1,2,3,4-tetrahydronaphthalene (30.0 g, 157.8 mmol) in cyclohexane (1 L) was heated to 50°C with a heating mantel. N-Bromosuccinimide (30.9 g, 173.6 mmol) and a catalytic amount of azoisobutyronitrile (ca. 0.040 g) were added and the solution was heated to the reflux for 2 h.
• the resulting yellow solution is poured into an aqueous solution of ammonium chloride (50% saturated, 60 ml).
• the resulting mixture is extracted with dichloromethane (2x20 ml) and then the organic phase is collected and dried with Na 2 SO 4 .
• the organic phase is then passed through a short silica plug to remove trace impurities using diethyl ether to elute the absorbed product.
• the colorless solution is then concentrated under vacuum to afford the pure compound.
• This ampule was connected to a high vacuum pump and the materials engaged were further dried for 24 h. Dry CH2Cl2 (430 mL) was added. The sealed ampule was stirred magnetically and heated in an oil bath at 45°C for 5 days under nitrogen. At the end of the reaction, more CH2Cl2 (250 mL) and a saturated solution of sodium bicarbonate (250 mL) were added to the ampule. The reaction mixture was transferred to a separatory funnel and the lower organic phase was removed. The aqueous phase was extracted with CH2Cl2 (200 mL x 2) and the CH2Cl2 extracts were combined.
• the dichloromethane solution was then washed with deionized water (150 mL x 2), a saturated solution of sodium bicarbonate (150 mL x 3), again with deionized water (150 mL x 3) and dried over anhydrous MgSO4. After filtration, the solution was concentrated on a rotary evaporator and the polymer was precipitated in methanol (600 mL).
• Example 6 depicts a gel permeation chromatography trace with a UV and refractive index detector used for determination of molecular weight distribution of polymers synthesized by the method of Example 8, and Table 3 shows the calculated molecular weight (Mn and Mw) and molecular weight distribution values based on the chromatography trace using polystyrene as a reference standard, where chromatography was performed using THF as the mobile phase.
• dichloromethane (30 mL) is added to the reaction flask.
• the reaction mixture is transferred to a separatory funnel (250 mL) and the lower organic phase is removed.
• the aqueous phase is washed with dichloromethane (30 mL x 2) and all the dichloromethane solutions are combined. These are then washed with deionized water (30 mL x 3) and then are dried over anhydrous MgSO 4 . After filtration, the solvent is removed by rotary evaporation.
• the product a white powder, is dried in air overnight in a fume hood and then in a vacuum oven for 24 hours at room temperature.
• This solution is added dropwise to a suspension of NaH (1.5 g) in dry THF (300 mL) under an inert atmosphere. The mixture is stirred under reflux for 24 hours and then allowed to cool at room temperature. To this solution enough water (150 mL) is added dropwise to consume the excess NaH and dissolve the resulting NaBr and NaOH.
• THF-water mixture is extracted with ethyl ether (4 x 100 mL), and the combined organic extracts are washed with 100 mL saturated NaHCO 3 solution, with 100 mL saturated NaCl solution, and finally with 100 mL water. The organic layer is dried over anhydrous Na 2 SO 4 and filtered.
• a release layer formulation comprising (J) Poly(1,2,3,4- tetrahydronaphthalene-1,4-diol carbonate), diphenyl ether, quinoline, and the photoacid generator (PAG) (4-Phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, shown in Scheme 12, are prepared and a release layer is deposited.
• PAG photoacid generator
• a release layer formulation comprising (L) Poly(1,2,3,4- tetrahydronaphthalene-1,4-diol-alt- ⁇ , ⁇ ’-dibromo-p-xylene), (B) 1,1'-(1,2,3,4-Tetrahydro-1,4- naphthalenediyl) di-tert-butyl carbonate, dibenzothiophene, and the PAG (4- Phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, shown in Scheme 13, are prepared and a release layer is deposited.
• Example 15 A release layer formulation comprising (J) Poly(1,2,3,4- tetrahydronaphthalene-1,4-diol carbonate) and the photoacid generator (PAG) (4- Phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, shown in Scheme 15, were prepared and release layer was deposited.
• PAG photoacid generator
• FIG. 9 shows an example of a fused silica donor plate coated with a 1.6 ⁇ m of such a release layer film containing 3 wt% PAG, and demonstrates the optical transparency and homogeneity of the thin film coating.
• Example 15 release layer formulation with an active ingredient with an Mn of 2500 g/mol and Mw of 3370 g/mol, combined with 3.5 wt% PAG was carried out and demonstrate that the material decomposes into volatile small molecules as designed when activated by UV light.
• FIG. 10 shows the decomposition temperature of the material before and after exposure to 311 nm light. Prior to activation of the photoacid generator, decomposition occurs at 179 °C when heated at a steady rate of 10 °C per minute with decomposition completing at ⁇ 250 °C. After UV exposure, the material begins decomposing at 61 °C and reaches the maximum decomposition around 131 °C.
• FIGS. 11, 12A and 12B show the results of analyzing the vaporous decomposition products of the activated release layer when heated at 150 °C. The analysis confirms that the primary products of the decomposition are water, carbon dioxide, and naphthalene, as predicted by the materials hypothesized decomposition mechanism when catalyzed by the photoacid generator.
• FIGS. 13A-14B demonstrate the decomposition behavior of the material under component transfer relevant conditions when irradiated with a 266 nm UV laser.
• Example 15 The release layer of Example 15 was coated onto a donor plate and utilized to transfer components from their source carriers to a target substrate, including die attached to a 0.9 ⁇ m release layer, 5 ⁇ m diameter microLEDs attached to a 0.23 ⁇ m release layer, and 50 ⁇ m by 60 ⁇ m silicon chips attached to a 1 ⁇ m film as shown in FIG. 15. Components may be loaded from carrier substrates onto a donor plate comprising the release layer, and released onto a target substrate as described with regard to FIG. 1. [0127] FIGS. 16A-17B depict components of multiple size scales that have been transferred to target substrates using donor plates comprising the release layer of Example 15.
• FIGS. 16A and 16B show the transfer results of 5 ⁇ m diameter microLEDs from a coated donor plate to a pressure sensitive adhesive (PSA). Transfers were conducted by irradiating individual microLED locations with a single 266 nm laser pulse with a total fluence of 500 mJ/cm2.
• FIGS. 17A and 17B show the transfer of results of 50 ⁇ m by 60 ⁇ m silicon die from a coated donor plate to a target substrate coated with a PSA with a single 266 nm laser pulse with a total fluence of 30 mJ/cm2.
• 100 ⁇ l of the formulated solution was then dynamically spin-coated onto a 2-inch diameter fused silica disk with a spin rate of 2000 rpm for 60s.
• the release layer coated disk was then soft-baked for 120 seconds at 150 °C and then cooled to room temperature prior to attaching small-components for transfer.
• Scheme 17 [0131] Solutions of each component were prepared by dissolving 1.0 g in 3.33 g of propylene glycol monomethyl ether (PGMEA) and then filtering each solution through a 450 nm PTFE syringe filter.
• PMEA propylene glycol monomethyl ether
• Solutions were then mixed and diluted with filtered PGMEA to create a solution of 10 wt% poly(propylene carbonate), 1 wt% (I) 1,2,3,4-tetrahydronaphthalene, 1,1’- bis(methoxymethoxy)-, and 0.5 wt% PAG.
• 100 ⁇ l of the formulated solution was then dynamically spin-coated onto a 2-inch diameter fused silica disk with a spin rate of 2000 rpm for 60s.
• the release layer coated disk was then soft-baked for 120 seconds at 150 °C and then cooled to room temperature prior to attaching small-components for transfer.
• Scheme 18 [0133] Solutions of each component were prepared by dissolving 1.0 g in 3.33 g of propylene glycol monomethyl ether (PGMEA) and then filtering each solution through a 450 nm PTFE syringe filter.
• PMEA propylene glycol monomethyl ether
• Solutions were then mixed and diluted with filtered PGMEA to create a solution of 10 wt% poly(propylene carbonate), 5 wt% (J) poly(1,2,3,4- tetrahydronaphthalene-1,4-diol carbonate)-, and 0.5 wt% PAG.
• 100 ⁇ l of the formulated solution was then dynamically spin-coated onto a 2-inch diameter fused silica disk with a spin rate of 2000 rpm for 60s.
• the release layer coated disk was then soft-baked for 120 seconds at 150 °C and then cooled to room temperature prior to attaching small-components for transfer.
• Scheme 19 [0135] Solutions of each component were prepared by dissolving 1.0 g in 3.33 g of propylene glycol monomethyl ether (PGMEA) and then filtering each solution through a 450 nm PTFE syringe filter.
• PMEA propylene glycol monomethyl ether
• Scheme 20 [0137] Solutions of each component were prepared by dissolving 1.0 g in 3.33 g of propylene glycol monomethyl ether (PGMEA) and then filtering each solution through a 450 nm PTFE syringe filter.
• PMEA propylene glycol monomethyl ether
• Example 21 A release layer formulation comprising (K) poly(1,2,3,4- tetrahydronaphthalene-1,4-diol formal), dibenzothiophene, and the PAG (4- Phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, shown in Scheme 21, is prepared and a release layer is deposited.
• Scheme 21 Solutions of each component were prepared by dissolving 1.0 g in 3.33 g of PGMEA and then filtering each solution through a 450 nm PTFE syringe filter.
• a release layer formulation comprising (J) poly(1,2,3,4- tetrahydronaphthalene-1,4-diol carbonate), (A) 1,1'-(1,2,3,4-Tetrahydro-1,4-naphthalenediyl) di-1H-imidazole-1-carboxylate, and the PAG (4-Phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, shown in Scheme 22, is prepared and a release layer is deposited.

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