Release layer composition for part transfer

Abstract

Release layers comprising oligomeric components containing units of formula (I) are useful for releasably transferring components from one surface to another during the manufacture of microelectronic devices.

Description

[Technical field]

[0001] Incorporation by reference of any priority application Any application for which a foreign or domestic priority claim is identified in the Application Data Sheet filed with this application is incorporated herein by reference under 37 CFR 1.57 and Rules 4.18 and 20.6. U.S. Provisional Application No. 63 / 234,406, filed August 18, 2021, is incorporated herein by reference in its entirety.

[0002] background Field The present disclosure relates to release layers used for releasably transferring components from one surface to another during the manufacture of microelectronic devices. [Background technology]

[0003] 2. Description of Related Art The transfer of microelectronic objects from one surface to another is a pervasive process in the assembly and packaging of functional products, whether they are purely electronic (as in computer motherboards), optoelectronic (as in displays), sensors, or actuators. The physics of the patterning system limit the size of the systems that can be fabricated in one integrated parallel process, and the compatibility of the process limits the type of materials. Useful systems therefore require integration at the packaging level.

[0004] Integrated circuits, where various components (e.g. passive components) can be fabricated with the same technology as transistors, have made it possible to create entire functional circuits in parallel, i.e., by processing areas rather than devices at the same time. Today, much of the innovation in microelectronics revolves around packaging, specifically heterogeneous packaging. This means that many different types of integration technologies (silicon ICs (digital or analog), compound semiconductor ICs and optical emitters and receivers, microelectromechanical sensors, and other devices and systems) are integrated in novel ways that achieve better performance.

[0005] Many techniques have been used in recent years for processing and packaging, such as serial pick and place, laser ablation, stamps and adhesives, but there is still a need for further development in the field. Summary of the Invention [Problem to be solved by the invention]

[0006] For purposes of summarizing the disclosure and the advantages achieved over the prior art, certain objects and advantages of the disclosure are described herein. Not all such objects or advantages may be achieved in any particular embodiment. Thus, for example, one skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages taught herein without necessarily achieving other objects or advantages, as may be taught or suggested herein. [Means for solving the problem]

[0007] Various embodiments include compounds of formula (I) and / or formula (II): [ka] (In the formula, each * represents a chiral carbon; n and m are independently integers ranging from 1 to 15; Each A and E is independently -O-, -NH-, [ka] [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] or optionally substituted [ka] and; 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 or C 1~3 is alkyl; wherein each s and t is independently an integer in the range of 1 to 10.

[0008] Various embodiments include compounds of formula (I) and / or formula (II): [ka] (In the formula, each * represents a chiral carbon; n and m are independently integers ranging from 1 to 15; Each A and E is independently -O-, -NH-, [ka] [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] or optionally substituted [ka] and; 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 is alkynyl; wherein each of ss, tt, s and t is independently an integer in the range of 1 to 10.

[0009] In some embodiments, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is hydrogen. In some embodiments, the release layer composition further comprises a polymeric component mixed with the oligomeric component. In some embodiments, the oligomeric component is present in the release layer composition in an amount greater than the amount of the polymeric component by weight.

[0010] In some embodiments, the polymer component comprises Formula (III) and / or Formula (IV): [ka] (In the formula, each * represents a chiral carbon; q and r are independently an integer in the range of 16 to 200; Each G and J is independently -O-, -NH-, [ka] [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] or optionally substituted [ka] and; 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, C1~10 Alkyl, C 2~10 Alkenyl or C 2~10 is alkynyl; Each uu, vv, u and v is independently an integer in the range of 1 to 10).

[0011] In some embodiments, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 is hydrogen. In some embodiments, the chiral carbons in Formula (I) and Formula (II) are selected such that the oligomeric component has a cis:trans ratio in the range of about 20:80 to about 80:20. In some embodiments, the oligomeric component comprises a number average molecular weight (Mn) of about 1000 to 5000 g / mol. In some embodiments, the oligomeric component comprises a weight average molecular weight (Mn) of about 2000 to 7000 g / mol. In some embodiments, the oligomeric component has a Mw:Mn ratio of about 1:1 to 4:1. In some embodiments, the oligomeric component has a glass transition temperature (T g ).

[0012] In some embodiments, the release layer composition further comprises an amount of a catalyst effective to catalyze the decomposition of the oligomeric component in the presence of radiation. In some embodiments, the catalyst comprises an acid catalyst, a base catalyst, or a combination thereof. In some embodiments, the acid catalyst is a photoacid generator (PAG). In some embodiments, the release layer formulation comprises about 1-20 wt % of a catalyst.

[0013] In some embodiments, the release layer composition further comprises an amount of a thermal sensitizer effective to increase the rate of decomposition of the oligomeric component in the presence of radiation, hi some embodiments, the release layer composition further comprises an amount of a low molecular weight additive that vaporizes under conditions where the oligomeric component decomposes in the presence of radiation.

[0014] Various embodiments provide a release layer that includes a release layer formulation.

[0015] Various embodiments provide an assembly that includes a release layer disposed over the donor plate. In some embodiments, the assembly further includes a plurality of components in contact with the release layer.

[0016] Various embodiments provide a method of forming a transfer assembly, comprising: A release layer is disposed over the donor plate, the release layer comprising a compound represented by Formula (I) and / or Formula (II): [ka] (In the formula, each * represents a chiral carbon; n and m are independently integers ranging from 1 to 15; Each A and E is independently -O-, -NH-, [ka] [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] or optionally substituted [ka] and; 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 C2~10 is alkynyl; each ss, tt, s and t is independently an integer in the range of 1 to 10; and contacting the release layer with a plurality of parts to form the transfer assembly; The present invention provides a method comprising:

[0017] Various embodiments provide a method for transferring multiple parts, comprising: A transfer assembly is disposed over a receiving substrate, the transfer assembly including a donor plate, a release layer disposed over the donor plate, and a plurality of components in contact with the release layer, the release layer comprising a compound represented by Formula (I) and / or Formula (II): [ka] (In the formula, each * represents a chiral carbon; n and m are independently integers ranging from 1 to 15; Each A and E is independently -O-, -NH-, [ka] [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] or optionally substituted [ka] and; 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 is alkynyl; each ss, tt, s and t is independently an integer in the range of 1 to 10; exposing portions of the release layer in contact with the plurality of components to a radiation source; heating the release layer; and decomposing portions of the release layer in contact with the plurality of components, thereby transferring the plurality of components to the receiving substrate; The present invention provides a method comprising:

[0018] These and other embodiments are described in more detail below.

[0019] These and other features, aspects, and advantages of the present disclosure will be described with reference to drawings of specific embodiments, which are illustrative of specific embodiments and are not intended to limit the invention. [Brief description of the drawings]

[0020] [Figure 1] FIG. 1 shows an embodiment of a process flow in which a release layer composition (B) is used to transfer a part (C) from a light-transmissive donor plate (A) to a target substrate (D).

[0021] [Diagram 2] FIG. 2 shows an example of an embodiment of a monomer carbonate taut structure.

[0022] [Diagram 3] FIG. 3 shows examples of dimer, trimer, oligomer and polymer carbonate structures.

[0023] [Figure 4] FIG. 4 shows an example of an oligomeric or polymeric component as a block-co-oligomer / polymer.

[0024] [Diagram 5] FIG. 5 depicts the 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).

[0025] [Figure 6] FIG. 6 depicts gel permeation chromatography traces with UV and refractive index detectors used to determine the molecular weight distribution of a synthetic polymer, according to some embodiments.

[0026] [Figure 7] FIG. 7 depicts the H-NMR spectrum and proton assignments for a polymer according to some embodiments.

[0027] [Figure 8] FIG. 8 depicts a graph showing film thickness of polymer coated at variable spin speeds, according to some embodiments.

[0028] [Figure 9] FIG. 9 depicts an image of a polymer film coated on a fused silica substrate according to some embodiments.

[0029] [Figure 10] FIG. 10 depicts thermogravimetric curves for the decomposition of a release layer formulation before and after UV irradiation, according to some embodiments.

[0030] [Figure 11] FIG. 11 depicts gas chromatography (GC) retention curves of decomposition products of release layer formulations according to some embodiments.

[0031] [Figure 12A] FIG. 12A depicts pyrolysis-GC-FTIR of the decomposition products of a release layer formulation at an early time according to some embodiments.

[0032] [Figure 12B] FIG. 12B depicts pyrolysis-GC-FTIR of the decomposition products of the release layer formulation at a later time, according to some embodiments.

[0033] [Figure 13A]FIG. 13A depicts an image of a 3D height data profile of a crater obtained by laser profilometry of an irradiated and heated exfoliation layer according to some embodiments.

[0034] [Figure 13B] FIG. 13B depicts an image of a 3D height data profile of a crater obtained by laser profilometry of an irradiated and heated exfoliation layer according to some embodiments.

[0035] [Figure 13C] FIG. 13C depicts an image of a 3D height data profile of a crater obtained by laser profilometry of an irradiated and heated exfoliation layer according to some embodiments.

[0036] [Figure 14A] FIG. 14A depicts an image of a 3D height data profile of a crater obtained by laser profilometry of a release layer heated during irradiation, according to some embodiments.

[0037] [Figure 14B] FIG. 14B depicts an image of a 3D height data profile of a crater obtained by laser profilometry of a heated exfoliation layer during irradiation, according to some embodiments.

[0038] [Figure 15] FIG. 15 depicts an image of a silicon chip component attached to a release layer according to some embodiments.

[0039] [Figure 16A] FIG. 16A depicts an image of a micro LED component disposed on top of a donor plate with a release layer after laser-induced forward transfer according to some embodiments.

[0040] [Figure 16B]FIG. 16B depicts an image of a micro LED component disposed on a target substrate after laser-induced forward transfer from the donor plate shown in FIG. 16A, according to some embodiments.

[0041] [Figure 17A] FIG. 17A depicts an image of a silicon die component transferred onto a target substrate from a donor plate including a release layer, according to some embodiments.

[0042] [Figure 17B] FIG. 17B depicts an image of a silicon die component transferred onto a target substrate from a donor plate including a release layer, enlarged from the image shown in FIG. 17A, according to some embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0043] Detailed Description In various embodiments, the release layer compositions described herein may be used in processes for transferring and / or packaging semiconductor components. The release layer compositions may allow for as many components as desired to be placed simultaneously on a surface, limited only by how large a mechanical fixture one wishes to create for the substrate. These components may range in size from microns (such as micro LEDs) to centimeters (such as large ICs).

[0044] The use of the release layer compositions described herein in a transfer process 100 is illustrated in FIG. 1. In the process flow shown, a light-transmitting donor plate (A) is provided 102 and coated 104 (e.g., solvent coated) with a film of a release layer composition (B) to form a coated donor plate 106. The desired component (C) to be transferred and the release layer (B) of the coated donor plate 106 are then contacted with applied pressure and / or heat to adhere the component (C) to the release layer (B) 108 to form a component-loaded donor plate 110. In some embodiments, the component is attached to a carrier substrate (e.g., tape) before being loaded onto the release layer. In some embodiments, a uniform pressure may be applied to the carrier substrate and / or donor plate. In some embodiments, a pressure of about, at most, or at most about 500 N / cm 2 , 1000N / cm 2 , 1500N / cm 2 , 2000N / cm 2 , 2250N / cm 2 , 2500N / cm 2 , 2750N / cm 2 , 3000N / cm 2 , 3250N / cm 2 , 3350N / cm 2 , 3750N / cm 2 or 4000N / cm 2, or any range of values ​​therebetween, is applied to the carrier substrate and / or donor plate. In some embodiments, the pressure may be applied for, for example, about, at least, or at least about 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 1.5 hours, or 2 hours, or any range of values ​​therebetween. In some embodiments, while the release layer and the component are in contact for loading, the release layer may be heated to a temperature of about, at most, or 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. In some embodiments, the release layer is allowed to cool to room temperature before the pressure is removed. In some embodiments, once the components are attached to the release layer, the carrier substrate may be removed (e.g., peeled off) to provide a component-loaded donor plate 110. The component-loaded donor plate 110 is then aligned 112 with a target substrate (D) surface prior to illumination 114 of the release layer (B) through the donor plate (A) with a light source. Irradiation 118 induces photochemical reactions in the release layer (B) that catalyze the decomposition of the material into low molecular weight species that are then vaporized 120 by heat provided from the irradiation to form a component (C) that is released from the donor plate (A). The vaporization generates a force 122 that pushes the component (C) to land on the target substrate (D) where it adheres to the surface to form a component-loaded substrate 124.

[0045] The process depicted in Figure 1 relies on a release layer that delaminates in the presence of light of a specific wavelength and energy (X-ray, UV, VIS, IR) and maintains good adhesion in the absence of such light. In various embodiments, the release layer composition is also chemically homogeneous, amorphous, and / or light-transmitting to promote homogeneous decomposition reactions and homogeneous vapor formation in the area of ​​irradiation.

[0046] In some embodiments, the release layer is exposed to radiation having a wavelength of about, at most, or 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 purposes of activation and / or decomposition. In some embodiments, the release layer is heated to a temperature of about, at most, or 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 purposes of activation and / or decomposition.

[0047] In some embodiments, the features retained and / or transferred by the release layer comprise a longest dimension (e.g., diameter, length, width, thickness) of about, at least, or at least about 10 nm, 25 nm, 50 nm, 75 nm, 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 0.9 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 15 μm, 20 μm, 30 μm, 50 μm, 60 μm, 80 μm, 100 μm, 150 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1 mm, 2 mm, 3 mm, or 5 mm, or any range of values ​​therebetween.

[0048] definition Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. All patents, applications, issued applications and other publications referenced herein are incorporated by reference in their entirety unless otherwise stated. In the event that there are a plurality of definitions for terms within this specification, the definition in this paragraph prevails unless otherwise stated.

[0049] Whenever a group is described as "optionally substituted," the group may be unsubstituted or substituted with one or more of the indicated substituents. Similarly, when a group is described as "unsubstituted" or "substituted," if substituted, the substituent(s) may be selected from one or more of the indicated substituents. If no substituents are indicated, the indicated "optionally substituted" or "substituted" group includes any of the following: 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 It means that it is optionally substituted with one or more group(s) individually and independently selected from 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, C-carboxy, O-carboxy, sulfenyl, sulfinyl, sulfonyl, haloalkoxy, amino, monosubstituted amine groups, and disubstituted amine groups.

[0050] As used herein, "C a ~C b (where "a" and "b" are integers) refer to the number of carbon atoms in the group. The designated group can contain from "a" to "b" carbon atoms inclusive. Thus, for example, a "C1-C4 alkyl" group refers to all alkyl groups having 1 through 4 carbons, i.e., CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2-, CH3CH2CH(CH3)-, and (CH3)3C-. When "a" and "b" are not specified, the maximum ranges set forth in those definitions must be assumed.

[0051] The term "alkyl" as used herein refers to a fully saturated aliphatic hydrocarbon group. The alkyl moiety may be branched or straight chain. Examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, t-butyl, and the like. Examples of 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 (wherever an alkyl group appears herein, a numerical range such as "1 to 30" refers to each integer within 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, and so on, up to 30 carbon atoms, but the definition of the present invention also covers the occurrence of the term "alkyl" where no numerical range is specified). The alkyl group may also be a medium alkyl having 1 to 12 carbon atoms. The alkyl group may also be a lower alkyl having 1 to 6 carbon atoms. The alkyl group can be substituted or unsubstituted.

[0052] The term "alkenyl" as used herein refers to a monovalent straight or branched chain radical of 2 to 30 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. Alkenyl groups can be unsubstituted or substituted.

[0053] The term "alkynyl" as used herein refers to a monovalent straight or branched chain radical of 2 to 30 carbon atoms containing a carbon triple bond(s), including, but not limited to, 1-propynyl, 1-butynyl, 2-butynyl, and the like. Alkynyl groups can be unsubstituted or substituted.

[0054] As used herein, the term "hydroxy" refers to an --OH group.

[0055] The terms "halogen atom" or "halogen" as used herein refer to any one of the radioactive stable atoms in column 7 of the periodic table of the elements, such as fluorine, chlorine, bromine and iodine.

[0056] Where the number of substituents is not specified (e.g., haloalkyl), one or more substituents may be present. For example, "haloalkyl" may include one or more of the same or different halogens. As another example, "C1-C3 alkoxyphenyl" may include one or more of the same or different alkoxy groups containing 1, 2 or 3 atoms.

[0057] As used herein, radical refers to a species that has one unpaired electron, so that the species containing the radical can be covalently bonded to another species. Thus, in this context, a radical is not necessarily a free radical. Rather, a radical refers to a specific portion of a larger molecule. The term "radical" can be used interchangeably with the term "group."

[0058] In any compound described herein having one or more chiral centers, unless the absolute stereochemistry is explicitly indicated, it is understood that each center may be independently R or S configuration, or a mixture thereof. Thus, the compounds provided herein may be enantiomerically pure, enantiomerically enriched, racemic mixture, diastereomerically pure, diastereomerically enriched, or a stereoisomeric mixture. In addition, in any compound described herein having one or more double bond(s) that generate geometric isomers that can be defined as E or Z, it is understood that each double bond may be independently E or Z, or a mixture thereof.

[0059] In some embodiments, all tautomeric forms of any of the compounds described are Also included are compounds such as, but not limited to, the compounds: [ka] The reference is for the tautomers: [ka] may be interpreted as including.

[0060] It should be understood that where the compounds disclosed herein have unfilled valencies, the valence bands will be filled with hydrogen or its isotopes, e.g., hydrogen-1 (protium) and hydrogen-2 (deuterium).

[0061] It is understood that the compounds described herein may be isotopically labeled. Substitution with an isotope such as deuterium may provide certain therapeutic advantages resulting from greater metabolic stability, such as, for example, increased in vivo half-life or reduced administration requirements. Each chemical element as depicted in a compound structure may include any isotope of said element. For example, in a compound structure, a hydrogen atom may be expressly disclosed or understood to be present in the compound. A hydrogen atom may be present at any position of the compound, and the hydrogen atom may be any isotope of hydrogen, including, but not limited to, hydrogen-1 (protium) and hydrogen-2 (deuterium). Thus, reference to a compound herein includes all possible isotopic forms, unless expressly indicated otherwise.

[0062] When a range of values ​​is provided, it is understood that the upper and lower limits of the range, and each intervening value between the upper and lower limits of the range, are encompassed within an embodiment.

[0063] Unless expressly stated otherwise, the terms and phrases used in this application, and variations thereof, particularly in the appended claims, should be construed as open ended as opposed to limiting. As examples of the foregoing, the term "including" should be read to mean "including without limitation," "including, but not limited to," or the like; the term "including" as used herein is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended and does not exclude additional unrecited elements or method steps; the term "having" should be interpreted as "having at least;" the term "including" should be interpreted as "including, but not limited to;" the term "examples" is used to provide exemplary examples of the items being discussed, not an exclusive or exclusive listing thereof; and the use of terms such as "preferably," "preferred," "desired," or "desired" and language of similar import should not be understood to suggest that a particular feature is critical, essential, or important to structure or function, but instead should be understood to merely highlight alternative or additional features that may or may not be used in a particular embodiment. Additionally, the term "including" should be interpreted synonymously with the phrases "having at least" or "including at least." The term "comprising" when used in the context of a process means that the process includes at least the recited steps, but may include additional steps. The term "comprising" when used in the context of a compound, composition, or device means that the compound, composition, or device includes at least the recited features or ingredients, but may include additional features or ingredients.

[0064] With respect to the use of virtually any plural and / or singular terminology herein, one of ordinary skill in the art may convert from plural to singular and / or from singular to plural as appropriate to the context and / or application. Various singular / plural permutations may be expressly indicated herein for clarity. The indefinite article "a" or "an" does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be advantageously used. Any reference signs in the claims should not be construed as limiting the scope.

[0065] Release layers, compositions and compounds The composition of the release layer may include an oligomeric and / or polymeric composition. The oligomeric and / or polymeric composition may include an oligomeric and / or polymeric component that is a unit containing a tetralin or cyclohexene core and a bond. For example, in one embodiment, the oligomeric component is represented by Formula (I) and / or Formula (II): [ka] Includes units of.

[0066] In some embodiments, each *represents a chiral carbon in the cyclohexyl ring. In some embodiments, the chiral carbons are configured such that the cyclohexene ring is in a cis orientation. In some embodiments, the chiral carbons are configured such that the cyclohexene ring is in a trans orientation. In some embodiments, the polymer component has a cis:trans ratio of about, at least about, at least about, at most about, or 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. In some embodiments, 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. In some embodiments, 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. For example, in some embodiments, m is in the range of 1 to 15. In some embodiments, bond A is independently -O-, -NH-, [ka] [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] or optionally substituted [ka] In some embodiments, the bond E is independently -O-, -NH-, [ka] [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] or optionally substituted [ka] In some embodiments, each R 1 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 2 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10In some embodiments, each R 3 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 4 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 5 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 6 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 7 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 8 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 9 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 10 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3Alkyl), C 2~10 Alkenyl or C 2~10 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. 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 polymeric material. In some embodiments, the release layer composition includes a polymer component mixed with an oligomeric component. In some embodiments, the polymer component forms a homogeneous film with the oligomeric component. In some embodiments, the polymer component includes a plurality of polymers. In some embodiments, the polymer component may be used in an amount effective to adjust the material properties and / or release properties of the release layer film. In some embodiments, the polymer component may include linear homopolymers, block copolymers, polymer networks, and the like. In some embodiments, the polymer component acts as a matrix supporting the oligomeric component and influences the physical and / or optical properties of the release layer. It may be advantageous to tailor the material properties of the release layer by modifying the polymer component, since the properties of the release layer may be altered from application to application without the need to redesign the oligomeric raw material. Furthermore, different polymers may alter the processing conditions for adhering the component to the release layer. In addition, the network polymer may help trap non-volatile residues so that they are not transferred during gassing. In some embodiments, the polymer component is photochemically inert. In some embodiments, the polymer component is photochemically active. Examples of potential polymer components include polymer components containing tetralin or cyclohexene cores and bonds, polypropylene, poly(propyl carbonate), polyurethane, ABS block copolymers, polyester, polyvinyl chloride, polystyrene, copolymers thereof, and combinations thereof. An example of a network polymer can be a polyethylene glycol polymer crosslinked by thiol-ene photochemical properties after coating on a donor substrate. As another example, in one embodiment, the polymer component is represented by Formula (III) and / or Formula (IV): [ka] Includes units of.

[0068] In some embodiments, each of Formula (III) and / or Formula (IV) *represents a chiral carbon in the cyclohexene ring. In some embodiments, the chiral carbons are configured such that the cyclohexene ring is in a cis orientation. In some embodiments, the chiral carbons are configured such that the cyclohexyl ring is in a trans orientation. In some embodiments, the polymer component has a cis:trans ratio of about, at least about, at least about, at most, or 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. In some embodiments, 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. For example, in some embodiments, q is in the range of 16-50 or 16-200. In some embodiments, 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. For example, in some embodiments, r is in the range of 16-50 or 16-200. In some embodiments, the bond G is independently -O-, -NH-, [ka] [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] or optionally substituted [ka] In some embodiments, the bond J is independently -O-, -NH-, [ka] [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] Possibly replaced [ka] or optionally substituted [ka] In some embodiments, each R 11 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 12 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 13 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 14 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 15 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 16 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 17 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 18are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 19 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C 2~10 Alkenyl or C 2~10 In some embodiments, each R 20 are independently hydrogen, halogen, C 1~10 Alkyl (e.g., C 1~3 Alkyl), C2 ~10 Alkenyl or C 2~10 In some embodiments, each uu is independently an integer in the range of 1 to 10. In some embodiments, each vv is independently an integer in the range of 1 to 10. In some embodiments, each u is independently an integer in the range of 1 to 10. In some embodiments, each v is independently an integer in the range of 1 to 10.

[0069] When irradiated, the bonds (e.g., bonds A, E, G, and / or J) are either cleaved through heat alone, generated by photothermal heating, or generated through heat and nucleophilic acid and / or base catalysis. Bond cleavage converts the residue of the bond into a relatively volatile unreacted small molecule. The gaseous by-products generate a force through volume expansion that pushes the bonded part against the target substrate. The tetralin core is an aromatic chromophore that facilitates film heating with irradiation (e.g., by a laser) at wavelengths in the range of approximately 240-300 nm. The cyclohexene core may be heated indirectly through irradiation of a compound within the film that acts as a chromophore. The ability to undergo effective heating allows for decomposition reaction kinetics on the microsecond timescale, which facilitates homogeneous transfer forces.

[0070] The efficiency of the process illustrated in Figure 1 depends on the core structure of the oligomeric and / or polymeric component (in embodiments where the polymeric component contains a photochemically active component). In some embodiments, the oligomeric or polymeric component contains units of a tetralin (i.e., bicyclic tetrahydronaphthalene) or cyclohexene core linked to a carbonate linkage. As long as the component contains the core and linkages described herein, the structure can be a monomer, such as the example shown in Figure 2, or a dimer, trimer, oligomer, or polymer, as shown in Figure 3. Figure 4 shows examples of oligomeric or polymeric components as diblock, triblock, or multiblock co-oligomers / polymers.

[0071] In various embodiments, the aromatic portion of tetralin (i.e., tetrahydronaphthalene) or another compound acts as a chromophore for UV radiation, which acts to convert light to heat for decomposition and vaporization of decomposition products and / or volatile additives. In some embodiments, the decomposed core may be converted to unreacted and volatile products. For example, in a carbonate bond attached to a benzylic site of tetralin (i.e., tetrahydronaphthalene), when the carbonate is cleaved, the tetrahydronaphthalene core is converted to naphthalene, which is unreacted and volatile. This also completes the decomposition reaction by forming an aromatic system. As another example, benzylic carbonates (e.g., oligomeric or polymeric components having tetralin (i.e., tetrahydronaphthalene) units and carbonate bonds) may be advantageous because the benzylic functionality may stabilize the cationic intermediate of carbonate cleavage, resulting in a much faster and lower energy fragmentation reaction. As a further example, a biscarbonate core (i.e., an oligomeric or polymeric moiety having a tetralin (i.e., tetrahydronaphthalene) or cyclohexene linked to two carbonate bonds) may be advantageous because cleavage of the two carbonates results in the formation of two C=C bonds, thereby resulting in an all-aromatic structure. The formation of the aromatic structure may help drive rapid bond cleavage and gas formation.

[0072] Examples of cores and linkages for oligomeric and polymeric components are shown in Table 1 below. [Table 1-1] [Table 1-2]

[0073] In some embodiments, the polymeric and / or oligomeric components have a molecular weight of about, at least, or 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, 450 g / mol, 4600 g / mol, 4700 g / mol, 4800 g / mol, 4900 g / mol, 5000 g / mol, 5100 g / mol, 5200 g / mol, 5300 g / mol, 5400 g / mol, 5500 g / mol, 5600 g / mol, 5700 g / mol, 5800 g / mol, 5900 g / mol, 6000 g / mol, 6100 g / mol, 6200 g / mol, 6300 g / mol, 6400 g / mol, 6500 g / mol, 6600 g / mol, 6700 g / mol, 6800 g / mol, 6900 g / mol, 7000 g / mol, 7100 g / mol, 7200 g / mol, 7300 g / mol, 7400 g / mol, 7500 g / mol, 7600 g / mol, 7700 g / mol, 7800 g / mol, 7900 g / mol, 8000 g / mol, 8100 g / mol The polymer has a number average molecular weight (Mn) of 0 g / mol, 5000 g / mol, 6000 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, 1000000 g / mol or 1500000 g / mol, or any range of values ​​therebetween. In some embodiments, the polymeric and / or oligomeric components have a molecular weight of about, at least, or 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, 1000000 g / mol, 1500000 g / mol or 2000000 g / mol, or any range of values ​​therebetween. In some embodiments, the polymeric and / or oligomeric components have a Mw:Mn ratio of about, at least, or 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.

[0074] In some embodiments, the polymeric and / or oligomeric components have a glass transition temperature (T) of about, at most about, at least, or 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., −50° C., or −60° C., or any range of values ​​therebetween. g ).

[0075] In some embodiments, the blend comprises a cis isomer of the polymeric and / or oligomeric component. In some embodiments, the blend comprises a trans isomer of the polymeric and / or oligomeric component. In some embodiments, the blend comprises both cis and trans isomers of the polymeric and / or oligomeric component. In some embodiments, the mixture of 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 decomposition material (e.g., oligomeric component) is the majority ingredient of the release layer formulation (i.e., the ingredient that constitutes the largest wt% or mass%). In embodiments of the release layer compositions described herein, the decomposition material (e.g., oligomeric component) is the minor ingredient of the release layer formulation. For example, in one embodiment, the polymeric component can be the primary ingredient of the release layer, and the oligomeric component is the minor ingredient. In some embodiments, the release layer composition comprises about, at least, at least about, at most, or 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% oligomeric component, or any range of values ​​therebetween. In some embodiments, the release layer composition comprises about, at least, at least about, at most, or 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 polymer component, or any range of values ​​therebetween.

[0077] In various embodiments, the release layer composition includes an (optional) thermal sensitizing agent in the form of one or more additives that absorb light and convert it to heat. Thermal sensitizing agents may have high photon absorption quantum yield, low fluorescence / phosphorescence quantum yield, and / or short excited state lifetimes that decay through non-irradiation pathways. They may be used in an amount effective to assist the heating rate during irradiation, thereby increasing the rate of bond decomposition and gas formation. These agents may also facilitate heating with lower power and longer wavelength lasers. In some embodiments, 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. In some embodiments, the thermal sensitizing agent will form an opaque film with the release layer formulation. Examples of 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 metal-based agents. In some embodiments, the organic thermal sensible agent comprises one or more of the following structural features: aromaticity, fused polycyclic ring systems, S- or N-containing heterocyclic compounds, polycyclic ring systems, and / or polyaromatic systems. Examples of organic thermal sensible agents include melanin, eumelanin, indole, pyrrole, quinoline, purine, triphenylmethyl compounds (e.g., (methoxymethanetriyl)tribenzene), fused aromatic compounds (e.g., anthracene and pyrene), dibenzothiophene, thiophene, and derivatives thereof.

[0078] In various embodiments, an (optional) acid or base additive is included in the release layer composition in an amount effective to catalyze oligomer and / or polymer decomposition. In some embodiments, the acid additive is selected from sulfonic acids (e.g., p-toluenesulfonic acid, methanesulfonic acid, heptadecafluorooctane sulfonic acid), benzoic acids (e.g., benzoic acid, salicylic acid, nonyloxybenzoic acid, oxybis(benzoic acid)), monocarboxylic acids (e.g., butyric acid, perfluorooctanoic acid), polyfunctional carboxylic acids (e.g., citric acid, malic acid, fumaric acid), derivatives thereof (e.g., butene-1,2-diol (p-toluenesulfonate), and combinations thereof. In some embodiments, the base additive is selected from ammonium hydroxide (e.g., tetrabutylammonium hydroxide), tertiary amines (e.g., N,N-diisopropylethylamine), amino bases (e.g., 1,4-diazabicyclo[2.2.2]octane, bis[2-(N,N-dimethylamino)ethyl]ether, pentamethyldiethylenetriamine, 1,8 ... cyclo[5.4.0]undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene), pyridine bases (e.g., 4-(dimethylamino)pyridine), derivatives thereof, and combinations thereof. In some embodiments, the acid additive is a photoacid generator (PAG). In some embodiments, the PAG comprises a chromophore unit and an acid precursor unit. In some embodiments, the chromophore unit is selected from diphenyliodonium, triphenylsulfonium, and combinations thereof. In some embodiments, the acid precursor unit is selected from trifluoromethanesulfonate (i.e., triflate), hexafluorophosphate, nitrate, p-toluenesulfonate, perfluoro-1-butanesulfonate, and combinations thereof. In some embodiments, the PAG is an ionic PAG or a non-ionic PAG.In some embodiments, 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. In some embodiments, 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-thyrazine, and combinations thereof. In some embodiments, the PAG is (4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate. In some embodiments, the acid or base additive is included in the release layer composition in an amount of about, at most, or 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.

[0079] In various embodiments, the release layer composition includes an optional low molecular weight additive that vaporizes under the conditions of transfer. One or more such additives may affect the generation of forces during irradiation. The low molecular weight additive may be used in an amount effective to enhance, thereby aiding in lifting or peeling of the part from the release layer. In some embodiments, the low molecular weight additive may also aid in modifying the viscoelastic properties of the release layer, thereby facilitating rapid bonding at lower temperatures.

[0080] In another embodiment, additives that absorb light and convert it into heat can be the main raw material of the release layer. They may be used in an effective amount to assist the heating rate during irradiation, thereby increasing the rate of oligomer and / or polymer decomposition and gas formation. These agents may also facilitate heating with lower power and longer wavelength lasers. Examples of additives include colloidal metals, Si, SiO2, TiO2, SnO2, anthracene, naphthalene, dimethoxybenzene, tetrahydronaphthalene, diphenyl ether, phenylcyclohexane, tert-butylphenol, acetoxy-tetrahydronaphthalene, and derivatives thereof. In some embodiments, the additive is configured to absorb at a wavelength of about, at most, at most about, at least, or 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.

[0081] In another embodiment, the additive that vaporizes under the conditions of transfer can be the main raw material of the release layer. The additive can be used in an amount effective to enhance the force generation during irradiation. In some embodiments, the additive can be any organic molecule that does not contain heteroatoms other than oxygen. The additive can be used to adjust the physical properties for processing the release layer in solid film state by lowering the Tg of the film, allowing the reduction of the temperature and pressure used in attaching the transferred part. In some embodiments, the additive can be vaporized when irradiated.

[0082] In some embodiments, the additive has a molecular weight of about, at most, or 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. In some embodiments, the additive has a boiling point of about, at most, or 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. In some embodiments, the additive has a flash point of about, at least, or 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. In some embodiments, the additive has a melting point of about, at most, or 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. In some embodiments, the additive has a room temperature vapor pressure of about, at most, or at most about 0.8 Torr, 0.7 Torr, 0.6 Torr, 0.5 Torr, 0.4 Torr, 0.3 Torr, 0.2 Torr, 0.1 Torr, 0.08 Torr, 0.06 Torr, about 0.04 Torr, 0.02 Torr, or 0.01 Torr, or any range of values ​​therebetween.

[0083] In some embodiments, the oligomeric and / or polymeric composition comprises a plurality of oligomers. In some embodiments, the at least two oligomeric and / or polymeric components are different. In some embodiments, the release layer comprises a plurality of release layer portion layers. In some embodiments, the release layer has a thickness of about, at most, or at most about 0.1 μm, 0.5 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.8 μm, 2 μm, 2.2 μm, 2.5 μm, 3 μm, 3.5 μm, or 4 μm, 5 μm, 7 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 120 μm, 150 μm, or 200 μm, or any range of values ​​therebetween. EXAMPLES

[0084] The synthesis of oligomeric components and intermediates is described in the following examples. Examples 12-14 describe the formulation and coating of release layers.

[0085] 1 1 H NMR analyses were performed on a 500 MHz Bruker Avance Neo instrument.

[0086] Example 1 Scheme 1 illustrates the one-step synthesis of (A) 1,1'-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)di-1H-imidazole-1-carboxylate. [ka]

[0087] (A) 1,1'-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)di-1H-imidazole-1-carboxylate: A solution of 1,1'-carbonyldiimidazole (34.5 g, 212.8 mmol) in dichloromethane (265 mL) was added dropwise via an addition funnel to a solution of 1,4-dihydroxy-1,2,3,4-tetrahydronaphthalene (17.4 g, 106.3 mmol) in pyridine (15.8 mL, 195.7 mmol) and dichloromethane (160 mL) in a 1 L round-bottom flask. The mixture was stirred gently for 16 hours at room temperature. At this point, additional dichloromethane (265 ml) was added and the mixture was stirred for an additional 6 hours. The mixture was then quenched with deionized water (160 mL). The reaction mixture was transferred to a separatory funnel and the lower organic phase was removed. The aqueous phase was extracted with dichloromethane (200 mL x 2) and all dichloromethane extracts were combined. The solution was washed with deionized water (150 mL x 2), a 1.0% solution of acetic acid (150 mL x 3), deionized water again (150 mL x 3), dried over anhydrous MgSO4 and filtered. The solvent was then removed on a rotary evaporator. The crude product was dried in vacuum at room temperature overnight to give a beige solid (31.6 g, 84%). Yield based on 1,4-dihydroxy-1,2,3,4-tetrahydronaphthalene. δH (300 MHz, CDCl3): 8.16, 8.08 (2 × 2H, s, CHim), 7.49-7.37 (12H, br.m, CHim and CHAr), 7.07, 7.04 (2 × 2H, s, CHim), 6.28, 6.18 (2 × 2H, m, CH-O), 2.49-2.26 (8H, br.m, CH2-CH2). Figure 5 shows the 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).

[0088] Example 2 Scheme 2 shows a one-step synthesis of (B) 1,1'-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)di-tert-butyl carbonate. [ka]

[0089] (B) 1,1'-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)di-tert-butyl carbonate: To a solution of triethylamine (0.263 ml, 1.87 mmol) and 4-(dimethylamino)pyridine (5.2 mg, 0.043 mmol) in anhydrous dichloromethane (5 ml), 1,4-dihydroxy-1,2,3,4-tetrahydronaphthalene (140 mg, 0.852 mmol) is added and the clear solution is stirred for 15 min. Di-tert-butyl dicarbonate (560 mg, 2.56 mmol) is added and the solution is stirred for an additional 2 h, at which time the solution turns clear and pale yellow. The product is extracted with ethyl acetate, washed three times with 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.

[0090] Example 3 Scheme 3 shows a two-step synthesis of (C) 1-(1-imidazolylcarbonyloxy)-1,2,3,4-tetrahydronaphthalene and (D) 1,1′-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)di-1-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)carbonate. [ka]

[0091] (C) 1-(1-Imidazolylcarbonyloxy)-1,2,3,4-tetrahydronaphthalene: Carbonyl-N,N'-diimidazole (1.46 g, 9.0 mmol) is slowly added to a solution of 1.0 g (6.7 mmol) of 1,2,3,4-tetrahydronaphthalen-1-ol in 8 ml of chloroform. Heat is generated by the highly exothermic reaction, which is completed after 30 min of stirring. The reaction solution is extracted twice with 10 ml of water. The organic phase is dried over Na2SO4. The solvent is removed under reduced pressure and the crude product is purified by crystallization from n-hexane / ethyl acetate.

[0092] (D) 1,1'-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)di-1-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)carbonate: In an ampoule with a PTFE stopcock, 1,4-dihydroxy-1,2,3,4-tetrahydronaphthalene (12.9 g, 78.6 mmol), (C) 1-(1-imidazolylcarbonyloxy)-1,2,3,4-tetrahydronaphthalene (3,880 g, 160.0 mmol), 18-crown-6 (4.3 g, 16.0 mmol) and anhydrous potassium carbonate (56.9 g, 412 mmol) are combined. The ampoule is connected to a high vacuum pump and the introduced material is dried for another 24 hours. Anhydrous CHCl (430 mL) is added. The sealed ampoule is magnetically stirred and heated in a 45° C. oil bath under nitrogen for 5 days. At the end of the reaction, additional CH2Cl2 (250 mL) and saturated solution of sodium bicarbonate (250 mL) are added to the ampoule. 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×2) and the CH2Cl2 extracts are combined. The dichloromethane solution is then washed with deionized water (150 mL×2), saturated solution of sodium bicarbonate (150 mL×3), again with deionized water (150 mL×3), and dried over anhydrous MgSO4. After filtration, the solution is concentrated on a rotary evaporator and the polymer is precipitated with methanol (600 mL). The polymer is collected as a beige powder by filtration, washed with MeOH (100 mL), and dried in vacuum at room temperature for 24 h.

[0093] Example 4 Scheme 4 shows a one-step synthesis of (E) 1,4-di-tert-butoxy-1,2,3,4-tetrahydronaphthalene. [ka]

[0094] (E) 1,4-di-tert-butoxy-1,2,3,4-tetrahydronaphthalene: Sulfuric acid (20 mmol) is added very slowly to a stirred solution of 1,4-dihydroxy-1,2,3,4-tetrahydronaphthalene (1.6 g, 10 mmol), 2 g molecular sieves, and 20 ml of methyl tert-butyl ether in a round bottom flask. The reaction is stirred at room temperature for 7 hours and then slowly quenched by the addition of 20 ml of saturated aqueous sodium bicarbonate over 2 hours. The organic layer is then separated and then washed with water (2×20 ml) before being dried over anhydrous sodium sulfate. The purified product is then obtained via flash chromatography using hexane and diethyl ether (10:1) as eluents.

[0095] Example 5 Scheme 5 shows a two-step synthesis of (F) 1-acetoxy-1,2,3,4-tetrahydronaphthalene and (G) 1-acetoxy-4-trifluoroacetoxy-1,2,3,4-tetrahydronaphthalene. [ka]

[0096] (F) 1-Acetoxy-1,2,3,4-tetrahydronaphthalene: Excess acetic anhydride ( 144 mL, 1.51 mol) in pyridine (200 mL) To a solution of hydronaphthalen-1-ol (51.2 g, 345.5 mmol) was added. The mixture was stirred at room temperature for 2 days. The volatile components were removed under reduced pressure, diethyl ether (1 L) was added, and the solution was transferred to a separatory funnel. The ethereal solution was washed with dilute aqueous hydrochloric acid (1%, 500 mL) and then saturated aqueous NaCl solution (500 mL). The extract was dried (MgSO4) and then concentrated under reduced pressure to yield the crude acetate salt. Distillation under reduced pressure yielded 60.0 g, 92% yield based on 1,2,3,4-tetrahydronaphthalen-1-ol (bp 84°C / 0.4 mmHg). δH(300MHz,CDCl3)1.78-2.06(4H,m,3-H,3'-H,2-H,2'-H),2.06(3H,s,OCOCH3),2.73-2.88(2H,m,4-H,4'-H),5.98(1H,t,1-H) and 7.09-7.26(4H,m,Ar-H).

[0097] (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. in a heating mantle. N-bromosuccinimide (30.9 g, 173.6 mmol) and a catalytic amount of azoisobutyronitrile (approximately 0.040 g) were added and the solution was heated to reflux for 2 hours. The solution was cooled, filtered (filter paper), and concentrated under reduced pressure to yield a mixture of cis- and trans-1-acetoxy-4-bromo-1,2,3,4-tetrahydronaphthalene as a yellowish oil, which was then dissolved in 1.3 L of ice-cold toluene. A suspension of silver trifluoroacetate (87 g, 394 mmol) in toluene (600 mL) was added to the cooled solution. The reaction was stirred at room temperature for 5 h, after which the silver bromide precipitate was filtered. The organic filtrate was concentrated under reduced pressure to yield (G) 1-acetoxy-4-trifluoroacetoxy-1,2,3,4-tetrahydronaphthalene as a brown oil. 1H NMR analysis confirmed the quantitative formation of trifluoroacetoxy derivatives based on (F)1-acetoxy-1,2,3,4-tetrahydronaphthalene. δH (300 MHz, CDCl3) 2.07 (3H, s, OCOMeA), 2.13 (3H, s, OCOMeB), 2.09-2.39 (8H, m, 2-HA, 2'-HA, 2-HB, 2'-HB, 3-HA, 3'-HA, 3-HB, 3'-HB), 5.97-6.20 (4H, m, 1-HA, 1-HB, 4-HA, 4-HB), 7.29-7.48 (8H, m, Ar-H).

[0098] Example 6 Scheme 6 shows a one-step synthesis of (H) 1,2,3,4-tetrahydronaphthalene, 1,1'-bis(tetrahydropyranyl ether)-. [ka]

[0099] (H) 1,2,3,4-tetrahydronaphthalene, 1,1'-bis(tetrahydropyranyl ether)-: 1,4-dihydroxy-1,2,3,4-tetrahydronaphthalene ( To a mixture of 1,4-dihydroxy-1,2,3,4-tetrahydronaphthalene (1.67 mmol) and dihydro-4H-pyran (10 mmol), NaHSO4 on silica (3 mg, 3 mmol NaHSO4 / g) is added and the mixture is stirred at room temperature for 16 h or until thin layer chromatography analysis indicates complete disappearance of 1,4-dihydroxy-1,2,3,4-tetrahydronaphthalene. After completion of the reaction, the mixture is directly loaded onto silica gel for flash chromatography purification using 1:9 ethyl acetate-hexane eluent. The pure product is obtained as a white powder.

[0100] Example 7 Scheme 7 illustrates the one-step synthesis of (I) 1,2,3,4-tetrahydronaphthalene, 1,1'-bis(methoxymethoxy)-. [ka]

[0101] (I) 1,2,3,4-Tetrahydronaphthalene, 1,1'-bis(methoxymethoxy)-: A solution of 1,4-dihydroxy-1,2,3,4-tetrahydronaphthalene (3.0 g, 18.3 mmol) in dichloromethane (36 ml) is cooled to 0°C. Ethyldiisopropylamine (10 ml) and chloromethyl methyl ether (4.2 ml, 55 mmol) are then slowly added to the solution. The reaction solution is allowed to slowly warm to room temperature overnight with continuous stirring. After stirring for at least 14 hours, the resulting yellow solution is poured into an aqueous solution of ammonium chloride (50% saturated, 60 ml). The resulting mixture is extracted with dichloromethane (2 x 20 ml) and the organic phase is then collected and dried over Na2SO4. The organic phase is then passed through a short silica plug to remove trace impurities with diethyl ether to elute the absorbed product. The colorless solution is then concentrated in vacuo to give the pure compound.

[0102] Example 8 Scheme 8 shows the one-step synthesis of (J) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol carbonate) through reaction with (A) 1,1′-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)di-1H-imidazole-1-carboxylate. [ka]

[0103] (J) Poly(1,2,3,4-tetrahydronaphthalene-1,4-diol carbonate): 1,4-dihydroxy-1,2,3,4 in an ampoule with a PTFE stopcock. -tetrahydronaphthalene (12.9 g, 78.6 mmol), (A) 1,2,3,4-tetrahydronaphthalene-1,4-diylbis(1H-imidazole-1-carboxylate) (27.7 g, 78.6 mmol), 18-crown-6 (4.3 g, 16.0 mmol) and anhydrous potassium carbonate (56.9 g, 412 mmol) were combined. The ampoule was connected to a high vacuum pump and the introduced material was dried for another 24 hours. Anhydrous CHCl (430 mL) was added. The sealed ampoule was magnetically stirred and heated under nitrogen in a 45° C. oil bath for 5 days. At the end of the reaction, additional CHCl (250 mL) and a saturated solution of sodium bicarbonate (250 mL) were added to the ampoule. The reaction mixture was transferred to a separatory funnel and the lower organic phase was removed. The aqueous phase was extracted with CHCl (200 mL×2) and the CHCl extracts were combined. The dichloromethane solution was then washed with deionized water (150 mL×2), saturated solution of sodium bicarbonate (150 mL×3), deionized water again (150 mL×3), and dried over anhydrous MgSO. After filtration, the solution was concentrated on a rotary evaporator and the polymer was precipitated with methanol (600 mL). The polymer was recovered as a beige powder by filtration, washed with MeOH (100 mL), collected and dried in vacuum at room temperature for 24 hours, giving a yield of 79% based on 1,4-dihydroxy-1,2,3,4-tetrahydronaphthalene and (A) 1,2,3,4-tetrahydronaphthalene-1,4-diylbis(1H-imidazole-1-carboxylate).

[0104] Table 2 shows the number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (Mw / Mn) of the synthesized polymers. [Table 2]

[0105] FIG. 6 shows the gel permeation chromatography traces with UV and refractive index detectors used to determine the molecular weight distribution of the polymer 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 chromatographic traces using polystyrene as the reference standard, and the chromatography was performed using THF as the mobile phase. [Table 3]

[0106] Example 9 Scheme 9 shows the one-step synthesis of (K) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol formal). [ka]

[0107] (K) Poly(1,2,3,4-tetrahydronaphthalene-1,4-diol formal): In a 250 mL round bottom flask, 1,4-dihydroxy-1,2,3,4-tetrahydronaphthalene (1.64 g, 10.0 mmol), tetrabutylammonium bromide (0.52 g, 1.6 mmol) and dibromomethane (2.2 mL, 31.6 mmol) are added. Then, aqueous KOH solution (20 mL, 60 wt%) is added. The reaction mixture is magnetically stirred and vigorously stirred at room temperature for 24 hours. At the end of the reaction, 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 of the dichloromethane solution is combined. They are then washed with deionized water (30 mL x 3) and then dried over anhydrous MgSO4. After filtration, the solvent is removed by rotary evaporation. The product white powder is air-dried overnight in a fume hood and then dried in a vacuum oven at room temperature for 24 hours.

[0108] Example 10 Scheme 10 shows the one-step synthesis of (L) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol-alt-α,α′-dibromo-p-xylene). [ka]

[0109] (L) Poly(1,2,3,4-tetrahydronaphthalene-1,4-diol-alt-α,α'-dibromo-p-xylene): α,α'-dibromo-o-xylene (2.64 g, 10 mmol) and 1,4-dihydroxy-1,2,3,4-tetrahydronaphthalene (1.64 g, 10 mmol) are dissolved in anhydrous THF (125 mL). This solution is added dropwise to a suspension of NaH (1.5 g) in anhydrous 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, sufficient water (150 mL) is added dropwise to consume excess NaH and dissolve the resulting NaBr and NaOH. The THF-water mixture is extracted with ethyl ether (4 x 100 mL) and the combined organic extracts are washed with 100 mL of saturated NaHCO3 solution, 100 mL of saturated NaCl solution, and finally with 100 mL of water. The organic layer is dried over anhydrous Na2SO4 and filtered. The solution is concentrated and then the polymer is precipitated by dropwise addition into ice-cold methanol to give the desired polymer. The white-yellow powder is dried in vacuum for 48 hours to give the purified product.

[0110] Example 11 Scheme 11 shows a one-step synthesis of (M) 1,4,9,12-tetraoxadispiro[4.2.4.2]tetradeca-6,13-diene. [ka]

[0111] (R) 1,4,9,12-Tetraoxadispiro[4.2.4.2]tetradeca-6,13-diene: 1000 g (5 mol) of 3,3,6,6-tetramethoxycyclohexa-1,4-dione are suspended in 2000 ml of 1,2-ethanediol. At 5° C., 0.6 g of p-toluenesulfonic acid are added and the suspension is stirred at the same temperature for 2 hours. The reaction is followed by gas chromatography. To complete the precipitation, the reaction mixture is cooled to 0° C. The solid is filtered off, washed with 1000 ml of cold water and dried under vacuum at room temperature to give the pure product.

[0112] Example 12 A release layer formulation comprising (J) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol carbonate), diphenyl ether, quinoline, and a photoacid generator (PAG) (4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, as shown in Scheme 12, is prepared and a release layer is coated. [ka]

[0113] Solutions of each component are 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. The solutions are then mixed and diluted with filtered PGMEA to make a solution of 10 wt% (J) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol carbonate), 0.3 wt% diphenyl ether, 0.3 wt% quinoline, and 0.5 wt% PAG. 100 μl of the combined solution is then dynamically spin-coated onto a 51 mm (2 inch) diameter fumed silica disk at a rotation speed of 2000 rpm for 60 seconds. The release layer coated disk is then soft-baked at 150° C. for 120 seconds, then cooled to room temperature before being attached to a miniature part for transfer.

[0114] Example 13 A release layer formulation comprising (L) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol-alt-α,α'-dibromo-p-xylene), (B) 1,1'-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)di-tert-butyl carbonate, dibenzothiophene, and PAG(4-phenylthiophenyl)disulfenylsulfonium trifluoromethanesulfonate, as shown in Scheme 13, is prepared and a release layer is coated. [ka]

[0115] Solutions of each component were prepared by dissolving 1.0 g in 3.33 g PGMEA and then filtering each solution through a 450 nm PTFE syringe filter. The solutions were then mixed and diluted with filtered PGMEA to obtain 5 wt% (J) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol carbonate) and 10 wt% (B) 1,1'-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)di-tert-butyl ether. A solution of ethyl carbonate, 0.3 wt% dibenzothiophene, and 0.5 wt% PAG is prepared. 100 μl of the formulated solution is then dynamically spin-coated onto a 51 mm (2 inch) diameter fumed silica disk at a spin speed of 2000 rpm for 60 seconds. The release layer coated disk is then soft-baked at 150° C. for 120 seconds, then cooled to room temperature before being attached to a miniature part for transfer.

[0116] Example 14A As shown in Scheme 14, (H) 1,2,3,4-tetrahydronaphthalene, 1,1'-bis(tetrahydropyranyl ether)- and poly(bisphenol A carbonate) (M n = 50,000 g / mol) and p-toluenesulfonic acid was prepared and the release layer was coated. [ka]

[0117] Solutions of each component are prepared by dissolving 1.0 g in 3.33 g of (PGMEA) and then filtering each solution through a 450 nm PTFE syringe filter. The solutions are then mixed and diluted with filtered PGMEA to give 5 wt % (H) 1,2,3,4-tetrahydronaphthalene poly(bisphenol A carbonate) (M n = 50,000 g / mol) and 0.02 wt% p-toluenesulfonic acid. 100 μl of the formulated solution is then dynamically spin-coated onto a 51 mm (2 inch) diameter fumed silica disk at a spin speed of 2000 rpm for 60 seconds. The release layer-coated disk is then soft-baked at 150 °C for 120 seconds, then cooled to room temperature and attached to a miniature part for transfer.

[0118] Example 14B As shown in Scheme 14, (H) 1,2,3,4-tetrahydronaphthalene, 1,1'-bis(tetrahydropyranyl ether)- and poly(bisphenol A carbonate) (M n = 50,000 g / mol) and a PAG was prepared and the release layer was coated. [ka]

[0119] Solutions of each component are prepared by dissolving 1.0 g in 3.33 g of (PGMEA) and then filtering each solution through a 450 nm PTFE syringe filter. The solutions are then mixed and diluted with filtered PGMEA to give 5 wt % (H) 1,2,3,4-tetrahydronaphthalene poly(bisphenol A carbonate) (M n= 50,000 g / mol) and 0.5 wt% PAG. 100 μl of the formulated solution is then dynamically spin-coated onto a 51 mm (2 inch) diameter fumed silica disk at a spin speed of 2000 rpm for 60 seconds. The release layer-coated disk is then soft-baked at 150 °C for 120 seconds, then cooled to room temperature and attached to a miniature part for transfer.

[0120] Example 15 A release layer formulation comprising (J) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol carbonate) and a photoacid generator (PAG) (4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, as shown in Scheme 15, was prepared and coated as a release layer. For characterization and experimental purposes, the data included are n 2700g / mol and M w A batch of (J) was obtained that was 4,100 g / mol. [ka]

[0121] 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. The solutions were then mixed and diluted with filtered PGMEA to make solutions of 10, 20, and 30 wt% (J) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol carbonate) with varying amounts of PAG depending on the desired concentration of catalyst to polymer. 100 μl of the blended solutions were then spin-coated onto a 51 mm (2 in) x 51 mm (2 in) diameter fumed silica plate for 60 seconds at a spin speed between 1000 and 6000 rpm depending on the desired thickness, and the thickness vs spin speed results are presented in Figure 8.

[0122] Films containing 1, 2, 3, 3.5, 5, 10, and 19 wt% PAG were prepared and tested for their ability to form stable release layer coatings and transfer parts, and were tested using a 266 nm YAG laser to perform laser transfer. The release layer coated plates were then soft baked at 150° C. for 120 seconds, then cooled to room temperature and attached to miniature parts for transfer. Figure 9 shows an example of a fused silica donor plate coated with 1.6 μm such a release layer film containing 3 wt% PAG, demonstrating the optical transparency and uniformity of the thin film coating.

[0123] A decomposition analysis of Example 15 release layer formulation with active ingredients of Mn 2500 g / mol and Mw 3370 g / mol, incorporating 3.5 wt% PAG, has been performed and demonstrates that the material decomposes into volatile small molecules as specified when activated by UV light. Figure 10 shows the decomposition temperature of the material before and after exposure to 311 nm light. When heated at a constant rate of 10°C / min prior to activation of the photoacid generator, decomposition occurs at 179°C and is complete at approximately 250°C. After UV exposure, the material begins to decompose at 61°C and reaches maximum decomposition around 131°C. This demonstrates the ability to completely decompose the photoactivated areas at temperatures below the decomposition temperature of the non-photoactivated areas of the film.

[0124] 11, 12A, and 12B show the results of an analysis of the vapor decomposition products of the activated release layer when heated to 150° C. The analysis confirms that the primary products of decomposition are water, carbon dioxide, and naphthalene, as predicted by the putative decomposition mechanism of the material when catalyzed by a photoacid generator.

[0125] 13A-14B demonstrate the decomposition behavior of the material under part transfer relevant conditions when irradiated with a 266 nm UV laser. Laser profilometry analysis of the craters shows that the 5 wt% P It is shown that when formulated with AG, craters are generated to a depth that spans the entire film thickness while being heated to 110°C with an external heat source. It is important to note that successful transfer from a loaded donor plate part does not require complete decomposition of the material in the exposed area. If sufficient force is generated by the vaporous decomposition products when irradiated, transfer can be achieved with less than 1% decomposition of the material.

[0126] The release layer of Example 15 was coated onto a donor plate and used to transfer components from a source carrier to a target substrate, including a die attached to a 0.9 μm release layer, a 5 μm diameter micro LED attached to a 0.23 μm release layer, and a 50 μm×60 μm silicon chip attached to a 1 μm film as shown in FIG 15. Components may be loaded from a carrier substrate onto a donor plate containing a release layer and released onto a target substrate as described in connection with FIG 1.

[0127] 16A-17B depict multiple size scale parts transferred to a target substrate using a donor plate containing the release layer of Example 15. FIGS. 16A and 16B show the result of transfer of 5 μm diameter micro LEDs from a coated donor plate to a pressure sensitive adhesive (PSA). Transfer was performed by irradiating individual micro LED locations with a single 266 nm laser pulse with a total fluence of 500 mJ / cm2. FIGS. 17A and 17B show the result of transfer of a 50 μm×60 μm silicon die from the coated donor plate to a PSA coated target substrate using a single 266 nm laser pulse with a total fluence of 30 mJ / cm2.

[0128] Example 16 A release layer formulation comprising (D) 1,1′-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)di-1-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)carbonate, poly(propylene carbonate) (Mn=50,000 g / mol), and PAG(4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, as shown in Scheme 16, is prepared and a release layer is coated. [ka]

[0129] 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. The solutions were then mixed and diluted with filtered PGMEA to give 10 wt% poly(propylene carbonate) and 1 wt% (D) 1,1'-(1, A solution of 2,3,4-tetrahydro-1,4-naphthalenediyl)di-1-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)carbonate and 0.5 wt% PAG was prepared. 100 μl of the formulated solution was then dynamically spin-coated onto a 51 mm (2 inch) diameter fumed silica disk at a spin speed of 2000 rpm for 60 seconds. The release layer coated disk was then soft-baked at 150° C. for 120 seconds, then cooled to room temperature and attached to a miniature part for transfer.

[0130] Example 17 A release layer formulation comprising (I) 1,2,3,4-tetrahydronaphthalene, 1,1′-bis(methoxymethoxy)-, poly(propylene carbonate) (Mn=50,000 g / mol), and PAG (4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, as shown in Scheme 17, is prepared and coated as a release layer. [ka]

[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. The solutions were then mixed and diluted with the filtered PGMEA to make 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 μl of the blended solution was then dynamically spin-coated onto a 51 mm (2 inch) diameter fumed silica disk at a spin speed of 2000 rpm for 60 seconds. The release layer-coated disk was then soft-baked at 150° C. for 120 seconds and then cooled to room temperature before being attached to a miniature part for transfer.

[0132] Example 18 A release layer formulation comprising (J) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol carbonate)-, poly(propylene carbonate) (Mn=50,000 g / mol) and PAG(4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, as shown in Scheme 18, is prepared and coated as a release layer. [ka]

[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. The solutions were then mixed and diluted with filtered PGMEA to make 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 μl of the blended solution was then dynamically spin-coated onto a 51 mm (2 inch) diameter fumed silica disk at a spin speed of 2000 rpm for 60 seconds. The release layer-coated disk was then soft-baked at 150° C. for 120 seconds, then cooled to room temperature, and attached to a miniature part for transfer.

[0134] Example 19 A release layer formulation comprising (E) naphthalene, di-1,1'-(1,1-dimethoxyethoxy)-1,2,3,4-tetrahydro-, poly(n-butyl acrylate) (Mn=20,000 g / mol), and PAG (4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, as shown in Scheme 19, was prepared and coated as a release layer. [ka]

[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. The solutions were then mixed and diluted with the filtered PGMEA to make a solution of 10 wt% poly(butyl acrylate), 1 wt% (E)naphthalene di-1,1'-(1,1-dimethylethoxy)-1,2,3,4-tetrahydro-, and 0.5 wt% PAG. 100 μl of the combined solution was then dynamically spin-coated onto a 51 mm (2 inch) diameter fumed silica disk at a spin speed of 2000 rpm for 60 seconds. The release layer coated disk was then soft-baked at 150° C. for 120 seconds, then cooled to room temperature, and attached to a miniature part for transfer.

[0136] Example 20 A release layer formulation comprising (M) 1,4,9,12-tetraoxadispiro[4.2.4.2]tetradeca-6,13-diene, poly(n-butyl acrylate) (Mn=20,000 g / mol), and PAG(4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, as shown in Scheme 20, is prepared and a release layer is coated. [ka]

[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. The solutions were then mixed and diluted with the filtered PGMEA to make a solution of 10 wt% poly(butyl acrylate), 1 wt% (M) 1,4,9,12-tetraoxadispiro[4.2.4.2]tetradeca-6,13-diene, and 0.5 wt% PAG. 100 μl of the combined solution was then dynamically spin-coated onto a 51 mm (2 inch) diameter fumed silica disk at a spin speed of 2000 rpm for 60 seconds. The release layer-coated disk was then soft-baked at 150° C. for 120 seconds, then cooled to room temperature, and attached to a miniature part for transfer.

[0138] Example 21 A release layer formulation comprising (K) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol formal), dibenzothiophene, and PAG(4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, as shown in Scheme 21, is prepared and a release layer is coated. [ka]

[0139] Solutions of each component were prepared by dissolving 1.0 g in 3.33 g PGMEA and then filtering each solution through a 450 nm PTFE syringe filter. The solutions were then mixed and diluted with filtered PGMEA to make a solution of 10 wt% (K) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol formal), 0.3 wt% dibenzothiophene, and 0.5 wt% PAG. 100 μl of the combined solution was then dynamically spin-coated onto a 51 mm (2 inch) diameter fumed silica disk at a rotation speed of 2000 rpm for 60 seconds. The release layer-coated disk was then soft-baked at 150° C. for 120 seconds, then cooled to room temperature, and attached to a miniature part for transfer.

[0140] Example 22 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 PAG(4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, as shown in Scheme 22, is prepared and a release layer is coated. [ka]

[0141] 1.0 g was dissolved in 3.33 g of PGMEA, and then each solution was applied to a 450 nm PTFE sieve. Solutions of each component were prepared by filtering through a ring filter. The solutions were then mixed and diluted with filtered PGMEA to produce a solution of 10 wt% (J) poly(1,2,3,4-tetrahydronaphthalene-1,4-diol carbonate), 1 wt% (A) 1,1'-(1,2,3,4-tetrahydro-1,4-naphthalenediyl)di-1H-imidazole-1-carboxylate, and 0.5 wt% PAG. 100 μl of the combined solution was then dynamically spin-coated onto a 51 mm (2 inch) diameter fumed silica disk at a spin speed of 2000 rpm for 60 seconds. The release layer-coated disk was then soft-baked at 150° C. for 120 seconds, and then cooled to room temperature before being attached to a miniature part for transfer.

[0142] Although the foregoing has been described in some detail by way of illustration and example for purposes of clarity and understanding, it will be understood by those skilled in the art that numerous and various modifications may be made thereto without departing from the spirit of the present disclosure. It should therefore be expressly understood that the forms disclosed herein are illustrative only and are not intended to limit the scope of the present disclosure, but rather to cover all modifications and alternatives which fall within the true scope and spirit of the present invention.

[0143] It should be understood that a feature, material, characteristic, or group described in conjunction with a particular aspect, embodiment, or example may be applied to any other aspect, embodiment, or example described in this paragraph or elsewhere in this specification, unless incompatible. All of the features disclosed in this specification (including any attached claims, abstract, and drawings), and / or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations in which at least some of such features and / or steps are mutually exclusive. This protection is not limited to the details of any of the foregoing embodiments. This protection extends to any novel one or any novel combination of the features disclosed in this specification (including any attached claims, abstract, and drawings), or any novel one or any novel combination of the steps of any method or process so disclosed.

[0144] Moreover, certain features described in this disclosure in the context of separate implementations may also be implemented in combination in a single implementation. Conversely, various features described in the context of a single implementation may also be implemented in multiple implementations separately or in any suitable subcombination. Moreover, although features may have been previously described as working in a particular combination, one or more features from a claimed combination may in some instances be cut out of the combination and the combination may be claimed as a subcombination or a variation of the subcombination.

[0145] Moreover, although operations may be depicted in the figures or described herein in a particular order, such operations need not be performed in the particular order or sequential order shown, or all operations need not be performed, to achieve the desired results. Other operations not depicted or described may be incorporated into the example methods and steps. For example, one or more additional operations may be performed before, after, simultaneously with, or between any of the described operations. Furthermore, operations may be rearranged or resequenced in other implementations. Those skilled in the art will recognize that in some embodiments, the actual steps performed in the illustrated and / or disclosed steps may differ from those shown in the figures. Depending on the embodiment, certain of the steps described above may be removed and other steps may be added. Furthermore, features and attributes of the specific embodiments disclosed above may be combined in different ways to form further embodiments, all of which are within the scope of the present disclosure. Likewise, the separation of various system components in the implementations described above should not be understood to require such separation in all implementations, and it should be understood that the components and systems described may generally be integrated together in one product or packaged into multiple products. For example, any of the components for an energy storage system described herein may be integrated together to form an energy storage system. The components may be provided separately or may be integrated together (eg, packaged together or attached together) to provide a single integrated solution.

[0146] For purposes of this disclosure, certain aspects, advantages, and novel features are described herein. Not necessarily all such advantages may be achieved in accordance with any particular embodiment. Thus, for example, one skilled in the art will recognize that the disclosure may be embodied or carried out in a manner that achieves one advantage or group of advantages taught herein without necessarily achieving other advantages, as may be taught or suggested herein.

[0147] Conditional language such as "can," "could," "could have," or "may," unless specifically stated otherwise or otherwise understood within the context in which it is used, is intended to generally convey that certain embodiments include certain features, elements, and / or steps, but other embodiments do not. Thus, such conditional language does not generally imply that the features, elements, and / or steps are required for one or more embodiments, or that one or more embodiments necessarily include logic for determining, with or without user input or prompting, whether those features, elements, and / or steps are included in or will be performed in any particular embodiment.

[0148] Unless specifically stated otherwise, it is understood by the context that conjugations such as the phrase "at least one of X, Y, and Z" are otherwise generally used to convey that an item, term, etc. can be either X, Y, or Z. Thus, such conjugations generally do not imply that a particular embodiment requires the presence of at least one of X, at least one of Y, and at least one of Z.

[0149] As used herein, language of degree, such as the terms "approximately," "about," "generally," and "substantially," refers to a value, amount, or characteristic that is close to a stated value, amount, or characteristic that performs a desired function or achieves a desired result. For example, the terms "approximately," "about," "generally," and "substantially" can refer to an amount that is within less than 10%, less than 5%, less than 1%, less than 0.1%, and less than 0.01% of the stated amount, depending on the desired function or result.

[0150] The scope of the present disclosure is not intended to be limited to the specific disclosure of preferred embodiments in this paragraph or elsewhere herein, but may be defined by the claims set forth in this paragraph or elsewhere herein, or hereafter set forth, which claim language shall be construed broadly based on the language used in the claims, and not limited to the examples described herein or during prosecution of a patent application, which examples shall be construed as non-exclusive.

[0151] The headings provided herein, if any, are present for convenience only and do not necessarily affect the scope or meaning of the devices and methods disclosed herein.

Claims

1. Formula (I) and / or Formula (II): 【Chemical 1】 (In the formula, each ＊ represents a chiral carbon; n and m are independently integers ranging from 1 to 15; Each A and E is independently —O—, —NH—, 【Chemistry 2】 【Chemistry 3】 Possibly replaced 【Chemistry 4】 Possibly replaced 【Chemistry 5】 Possibly replaced 【Chemistry 6】 Possibly replaced 【Chemistry 7】 Possibly replaced 【Chemistry 8】 Possibly replaced 【Chemistry 9】 Possibly replaced 【Chemistry 10】 Possibly replaced 【Chemistry 11】 Possibly replaced 【Chemistry 12】 Possibly replaced 【Chemistry 13】 or possibly substituted 【Chemistry 14】 and 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 is alkynyl; wherein each of ss, tt, s, and t is independently an integer in the range of 1 to 10.

2. R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ and R １０ The release layer composition of claim 1 , wherein is hydrogen.

3. The release layer composition of claim 1 further comprising a polymeric component intermixed with the oligomeric component.

4. The release layer composition of claim 3 , wherein the oligomeric component is present in the release layer composition in an amount, by weight, that is greater than the amount of the polymeric component.

5. The polymer component has formula (III) and / or formula (IV): 【Chemistry 15】 (In the formula, each ＊ represents a chiral carbon; q and r are independently integers in the range of 16 to 200; Each G and J is independently —O—, —NH—, 【Chemistry 16】 【Chemistry 17】 Possibly replaced 【Chemistry 18】 Possibly replaced 【Chemistry 19】 Possibly replaced 【Chemistry 20】 Possibly replaced 【Chemical 21】 Possibly replaced 【Chemical 22】 Possibly replaced 【Chemical 23】 Possibly replaced 【Chemistry 24】 Possibly replaced 【Chemistry 25】 Possibly replaced 【Chemical 26】 Possibly replaced 【Chemical 27】 or possibly substituted 【Chemical 28】 and 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 is alkynyl; 4. The release layer composition of claim 3, comprising units of the formula: wherein each uu, vv, u and v is independently an integer in the range of 1 to 10.

6. R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ , R １８ , R １９ and R ２０ The release layer composition of claim 5 wherein is hydrogen.

7. 7. The release layer composition of claim 1, wherein the chiral carbons in formula (I) and formula (II) are selected so that the oligomeric components have a cis:trans ratio in the range of 20:80 to 80:

20.

8. The oligomeric component comprises a number average molecular weight (Mn) of 1000 to 5000 g / mol. The release layer composition according to any one of claims 1 to 6.

9. The release layer composition of any one of claims 1 to 6, wherein the oligomeric component comprises a weight average molecular weight (Mw) of 2000 to 7000 g / mol.

10. 10. The release layer composition of claim 9, wherein the oligomeric component has a Mw:Mn ratio of 1:1 to 4:

1.

11. The oligomer component has a glass transition temperature (T ｇ 7. The release layer composition of claim 1, comprising:

12. 7. The release layer composition of claim 1, further comprising a catalyst for catalyzing the decomposition of the oligomeric component in the presence of radiation, wherein the release layer composition comprises 1 to 20 wt % of the catalyst.

13. The release layer composition of claim 12 , wherein the catalyst comprises an acid catalyst, a base catalyst, or a combination thereof.

14. The release layer composition of claim 13, wherein the acid catalyst is a photoacid generator (PAG).

15. The release layer composition of any one of claims 1 to 6, further comprising a thermal sensitizer for increasing the rate of decomposition of the oligomeric component in the presence of radiation.

16. The release layer composition of any one of claims 1 to 6, further comprising a low molecular weight additive that vaporizes under conditions that cause the oligomeric component to decompose in the presence of radiation.

17. A release layer comprising the release layer composition of any one of claims 1 to 6.

18. 20. An assembly comprising the release layer of claim 17 disposed over a donor plate.

19. 20. The assembly of claim 18, further comprising a plurality of components in contact with the release layer.

20. 1. A method of forming a transfer assembly, comprising: A release layer is disposed on the donor plate, the release layer comprising a compound represented by Formula (I) and / or Formula (II): 【Chemical formula 29】 (In the formula, each ＊ represents a chiral carbon; n and m are independently integers ranging from 1 to 15; Each A and E is independently —O—, —NH—, 【Chemistry 30】 【Chemical 31】 Possibly replaced 【Chemical 32】 Possibly replaced 【Chemical Formula 33】 Possibly replaced 【Chemical 34】 Possibly replaced 【Chemistry 35】 Possibly replaced 【Chemical 36】 Possibly replaced 【Chemical 37】 Possibly replaced 【Chemical 38】 Possibly replaced 【Chemical 39】 Possibly replaced 【Chemistry 40】 Possibly replaced 【Chemistry 41】 or possibly substituted 【Chemistry 42】 and 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 is alkynyl; each ss, tt, s, and t is independently an integer in the range of 1 to 10; and contacting the release layer with a plurality of parts to form the transfer assembly; A method comprising:

21. 1. A method for transferring multiple parts, comprising: a transfer assembly disposed over a receiving substrate, the transfer assembly including a donor plate, a release layer disposed over the donor plate, and a plurality of components in contact with the release layer, the release layer comprising a compound represented by Formula (I) and / or Formula (II): 【Chemistry 43】 (In the formula, each ＊ represents a chiral carbon; n and m are independently integers ranging from 1 to 15; Each A and E is independently —O—, —NH—, 【Chemical 44】 【Chemistry 45】 Possibly replaced 【Chemistry 46】 Possibly replaced 【Chemistry 47】 Possibly replaced 【Chemistry 48】 Possibly replaced 【Chemistry 49】 Possibly replaced 【Chemistry 50】 Possibly replaced 【Chemistry 51】 Possibly replaced 【Chemistry 52】 Possibly replaced 【Chemistry 53】 Possibly replaced 【Chemical 54】 Possibly replaced 【Chemistry 55】 or possibly substituted 【Chemical Formula 56】 and 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 is alkynyl; each ss, tt, s, and t is independently an integer in the range of 1 to 10; exposing portions of the release layer in contact with the plurality of components to a radiation source; heating the release layer; and decomposing the portions of the release layer in contact with the plurality of components, thereby transferring the plurality of components to the receiving substrate; A method comprising:

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