CURABLE COMPOSITIONS FOR NANOFABRICATION - Patent application

Abstract

To provide a curable composition for nano-fabrication for providing better process control than the prior art and / or improving the throughput.SOLUTION: A curable composition comprises expanding monomers of at least 10 wt.% based on the total weight of the curable composition, acrylate monomers of at least 25 wt.% based on the total weight of the curable composition, a photoinitiator, and a photosensitizer. The acrylate monomers have molecular weight of 500 or less. The curable composition has a viscosity of 10 cP or less. The total amount of the expanding monomers and the acrylate monomers are at least 90 wt.% based on the total weight of the curable composition.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present disclosure relates to curable compositions for nanofabrication. [Background technology]

[0002] Nanofabrication involves the creation of very small structures, with features on the order of 100 nanometers or less. One application in which nanofabrication has had a significant impact is the creation of integrated circuits. The semiconductor processing industry continues to strive for greater production yields while increasing the circuits per unit area formed on a substrate. Improvements in nanofabrication include providing greater process control and / or increasing throughput while continually decreasing the dimensions of the smallest features of the structures being formed.

[0003] One nanofabrication technique currently in use is commonly referred to as nanoimprint lithography. Nanoimprint lithography is useful in a variety of applications including, for example, fabricating one or more layers of integrated devices by molding a film on a substrate. Examples of integrated devices include, but are not limited to, CMOS logic, microprocessors, NAND flash memory, NOR flash memory, DRAM memory, MRAM, 3D cross-point memory, Re-RAM, Fe-RAM, STT-RAM, MEMS, and the like. Exemplary nanoimprint lithography systems and methods are described in detail in numerous publications, such as U.S. Pat. No. 6,393,633, U.S. Pat. No. 6,493,351, all of which are incorporated herein by reference.

[0004] The nanoimprint lithography techniques disclosed in each of the above patents describe molding a coating on a substrate by forming a relief pattern in a (polymerizable) layer of a formable material, the topography of which can then be used to transfer a pattern corresponding to the relief pattern into and / or onto the underlying substrate.

[0005] The patterning process uses a template spaced apart from a substrate and a liquid containing a formable material (the formable liquid) is applied between the template and the substrate. The template is contacted with the formable material, causing the formable material to spread and fill the space between the template and the substrate. The formable liquid is solidified to form a coating having a shape (pattern) that matches the shape of the surface of the template in contact with the formable liquid. After solidification, the template is separated from the solidified layer to space the template from the substrate.

[0006] The substrate and solidified layer can then be subjected to additional processes, such as an etching process, to transfer an image to the substrate that corresponds to the pattern in one or both of the solidified layer and / or the patterned layer immediately beneath the solidified layer. The patterned substrate can be subjected to further known steps and processes for device (article) fabrication including, for example, curing, oxidation, layering, deposition, doping, planarization, etching, removal of formable material, dicing, bonding, packaging, and the like. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] U.S. Patent No. 8,349,241 [Patent Document 2] U.S. Patent No. 8,066,930 [Patent Document 3] U.S. Patent No. 6,936,194 [Non-patent literature]

[0008] [Non-Patent Document 1] Moeck et al., "Shrinkage of UV Oligomers and Monomers," UV & EB Technical Conference Proceedings (2014) Summary of the Invention [Problem to be solved by the invention]

[0009] When performing imprinting or planarization as part of nanofabrication, after spraying the curable composition, the curable composition is cured, such as by exposure to ultraviolet (UV) light, as discussed in more detail below. However, known curable compositions, particularly compositions based on acrylate monomers, undergo volumetric shrinkage during curing. The volumetric shrinkage of compositions based on acrylate monomers can be, for example, 4% to 20%. The volumetric shrinkage is primarily a result of relatively long-distance van der Waals bonds being replaced by much shorter covalent bonds during curing. For example, van der Waals bonds are typically 3 angstroms to 5 angstroms, whereas covalent bonds are typically 1 angstrom to 2 angstroms. Volumetric shrinkage in the range of 4% to 20% adversely affects imprinting and planarization. See, for example, Non-Patent Document 1. Volumetric shrinkage is particularly detrimental to planarization, since it results in a non-flat surface. Disclosed herein is a curable composition that minimizes the above shrinkage. [Means for solving the problem]

[0010] The curable composition includes at least 10% by weight of an expandable monomer, based on the total weight of the curable composition, at least 25% by weight of an acrylate monomer, based on the total weight of the curable composition, a photoinitiator, and a photosensitizer. The acrylate monomer has a molecular weight of 500 or less. The curable composition has a viscosity of 10 cP or less. The total amount of the expandable monomer and the acrylate monomer is at least 90% by weight, based on the total weight of the curable composition.

[0011] The dispensing system includes a first chuck configured to grip a template or superstrate, a second chuck configured to grip a substrate, a dispensing system configured to dispense a curable composition onto the substrate, a positioning system configured to contact the template or superstrate with the curable composition on the substrate, and a radiation source configured to cure the curable composition by exposing the curable composition to radiation. The curable composition includes at least 10% by weight of an expandable monomer based on the total weight of the curable composition, at least 25% by weight of an acrylate monomer based on the total weight of the curable composition, a photoinitiator, and a photosensitizer. The acrylate monomer has a molecular weight of 500 or less. The curable composition has a viscosity of 10 cP or less. The total amount of the expandable monomer and the acrylate monomer is at least 90% by weight based on the total weight of the curable composition.

[0012] A method of making an article includes contacting a curable composition on a substrate with a template or superstrate, curing the curable composition by exposing the curable composition to radiation to form a cured composition, separating the template or superstrate from the cured composition, and treating the substrate with the cured composition to produce the article. The curable composition includes at least 10% by weight of an expandable monomer based on the total weight of the curable composition, at least 25% by weight of an acrylate monomer based on the total weight of the curable composition, a photoinitiator, and a photosensitizer. The acrylate monomer has a molecular weight of 500 or less. The curable composition has a viscosity of 10 cP or less. The total amount of the expandable monomer and the acrylate monomer is at least 90% by weight based on the total weight of the curable composition.

[0013] These and other objects, features and advantages of the present disclosure will become apparent from the following detailed description of illustrative embodiments of the present disclosure, taken in conjunction with the accompanying drawings and the appended claims.

[0014] In order that the features and advantages of the present invention may be understood in detail, a more particular description of the embodiments of the present invention may be made by referring to the embodiments shown in the accompanying drawings. It should be noted, however, that the accompanying drawings merely illustrate typical embodiments of the present invention and therefore should not be considered as limiting the scope of the present invention, which may embrace other equally effective embodiments for the present invention. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 illustrates an exemplary nanoimprint lithography system having a template with a mesa spaced apart from a substrate, in accordance with an exemplary embodiment. [Diagram 2] FIG. 1 is a diagram of an exemplary template according to an exemplary embodiment. [Diagram 3] 4 is a flow chart illustrating an exemplary imprinting method in accordance with an exemplary embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Throughout the drawings, the same reference numerals and characters are used to denote like features, elements, components or portions of the illustrated embodiments, unless otherwise stated. Moreover, while the present subject disclosure will be described in detail with reference to the figures, it is done so in connection with the illustrative exemplary embodiments. It is intended that changes and modifications can be made in the exemplary embodiments described without departing from the true scope and spirit of the present subject disclosure, as defined by the appended claims.

[0017] Throughout this disclosure, reference is made to nanoimprint lithography using the patterned template described above to impart a pattern to a formable liquid. However, as described below, in alternative embodiments, the template may be featureless, in which case a flat surface may be formed on the substrate. In such embodiments where a flat surface is formed, the forming process is referred to as planarization. Thus, throughout this disclosure, whenever nanoimprint lithography is mentioned, it should be understood that the same methods are applicable to planarization. In cases where the template is featureless, the term superstrate is used instead of the term template. Additionally, it should be understood that the term "formable liquid" is used interchangeably with "curable composition."

[0018] Nanoimprint system (molding system) 1 is a diagram of a nanoimprint lithography system 100 in which an embodiment may be implemented. The nanoimprint lithography system 100 is used to form a film on a substrate 102. The substrate 102 may be gripped by a substrate chuck 104. The substrate chuck 104 may be, but is not limited to, a vacuum chuck, a pin-type chuck, a groove-type chuck, an electrostatic chuck, an electromagnetic chuck, and / or the like.

[0019] The substrate 102 and substrate chuck 104 may be further supported by a substrate positioning stage 106. The substrate positioning stage 106 may provide translational and / or rotational motion along one or more of the x-, y-, z-, θ-, ψ-, and φ-axes. The substrate positioning stage 106, substrate 102, and substrate chuck 104 may also be disposed on a stage (not shown). The substrate positioning stage may be part of a positioning system.

[0020] The template 108 is spaced apart from the substrate 102. The template 108 may include a body having a mesa (also called a mold) 110 extending towards the substrate 102 on a front side of the template 108. The mesa 110 may have a patterned surface 112 thereon, also on the front side of the template 108. Alternatively, the template 108 may be formed without the mesa 110, in which case the surface of the template facing the substrate 102 corresponds to the mold 110 and the patterned surface 112 is that surface of the template 108 facing the substrate 102.

[0021] The template 108 may be formed from materials including, but not limited to, fused silica, quartz, silicon, organic polymers, siloxane polymers, borosilicate glass, fluorocarbon polymers, metals, reinforced sapphire, and / or the like. The patterned surface 112 may have features defined by a plurality of spaced apart template recesses 114 and / or template protrusions 116. The patterned surface 112 defines the underlying pattern of the pattern to be formed on the substrate 102. In an alternative embodiment, the patterned surface 112 is featureless, in which case a flat surface is formed on the substrate. In an alternative embodiment, the patterned surface 112 is featureless and is the same size as the substrate, in which case a flat surface is formed across the substrate. In such an embodiment in which a flat surface is formed, the formation process may instead be referred to as planarization, and the featureless template may instead be referred to as a superstrate.

[0022] The template 108 may be gripped by a template chuck 118. The template chuck 118 may be, but is not limited to, a vacuum chuck, a pin-type chuck, a groove-type chuck, an electrostatic chuck, an electromagnetic chuck, and / or other similar chuck types. The template chuck 118 may be configured to apply different stresses, pressures, and / or strains to the template 108 through the template 108. The template chuck 118 may comprise piezoelectric actuators that can clamp and / or stretch different portions of the template 108. The template chuck 118 may comprise a zone-based vacuum chuck, an actuator array, a pressure bladder, or other system that can apply a pressure differential to the back side of the template to cause bending and deformation in the template.

[0023] The template chuck 118 may be grasped by an imprint head 120 that is part of the positioning system. The imprint head may be movably coupled to the bridge. The imprint head may include one or more actuators, such as a voice coil motor, a piezoelectric motor, a linear motor, a nut and screw motor, etc., configured to move the template chuck 118 relative to the substrate in at least the z-axis direction, and possibly other directions (e.g., the x-axis, the y-axis, the θ-axis, the ψ-axis, and the φ-axis).

[0024] The nanoimprint lithography system 100 may further include a fluid dispenser 122. The fluid dispenser 122 may also be movably coupled to the bridge. In one embodiment, the fluid dispenser 122 and the imprint head 120 share one or more or all positioning components. In an alternative embodiment, the fluid dispenser 122 and the imprint head 120 move independently of one another. The fluid dispenser 122 may be used to deposit a liquid formable material 124 (e.g., a polymerizable material) in a pattern onto the substrate 102. Additional formable material 124 may also be added to the substrate 102 prior to depositing the formable material 124 onto the substrate 102 using techniques such as drop spraying, spin coating, dip coating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thin film deposition, thick film deposition, and / or the like. Depending on design considerations, the formable material 124 can be dispensed onto the substrate 102 before and / or after a desired volume is defined between the mold 110 and the substrate 102. The formable material 124 can include mixtures including monomers as described in U.S. Patent Nos. 7,157,036 and 8,076,386, both of which are incorporated herein by reference.

[0025] Different fluid dispensers 122 may use different technologies for dispensing the formable material 124. If the formable material 124 is jettable, an inkjet-type dispenser may be used to dispense the formable material. For example, thermal inkjet, microelectromechanical system (MEMS)-based inkjet, bubble jet, and piezoelectric inkjet are common technologies for dispensing jettable liquids.

[0026] The nanoimprint lithography system 100 may further include a radiation source 126 that directs actinic energy radiation along an exposure path 128. The imprint head 120 and the substrate positioning stage 106 may be configured to position the template 108 and the substrate 102 in superposition with the exposure path 128. After the template 108 contacts the formable material 124, the actinic energy radiation is sent along the exposure path 128 by the radiation source 126. Although FIG. 1 illustrates the exposure path 128 when the template 108 is not in contact with the formable material 124, this is done for illustrative purposes so that the relative positions of the individual components can be easily identified. One skilled in the art will appreciate that the exposure path 128 does not substantially change when the template 108 contacts the formable material 124.

[0027] The nanoimprint lithography system 100 may further include a field camera 136 positioned to view the spreading of the formable material 124 after the template 108 contacts the formable material 124. FIG. 1 shows the optical axis of the imaging field of the field camera 136 with a dashed line. As shown in FIG. 1, the nanoimprint lithography system 100 may include one or more optical components (dichroic mirrors, beam combiners, prisms, lenses, mirrors, etc.) that combine the actinic energy radiation with the light detected by the field camera 136. The field camera 136 may be configured to inspect the spreading of the formable material under the template 108. The optical axis of the field camera 136 as shown in FIG. 1 is a straight line, but may be bent by one or more optical components. The field camera 136 may comprise one or more of a CCD, a sensor array, a line camera, and a photodetector configured to collect light having wavelengths that exhibit contrast between areas under the template 108 in contact with the formable material and areas under the template 108 that are not in contact with the formable material 124. The field camera 136 may be configured to collect a monochromatic image of visible light. The field camera 136 may be configured to provide images of the spreading of the formable material 124 under the template 108, images of the separation of the template 108 from the hardened formable material, and may be used to track progress during the imprinting process.

[0028] The nanoimprint lithography system 100 may further include a drop inspection system 138 separate from the field camera 136. The drop inspection system 138 may include one or more of a CCD, a camera, a line camera, and a photodetector. The drop inspection system 138 may include one or more optical components, such as lenses, mirrors, apertures, filters, prisms, polarizers, windows, adaptive optics, and / or a light source. The drop inspection system 138 may be positioned to inspect the drops before the patterning surface 112 contacts the formable material 124 on the substrate 102.

[0029] The nanoimprint lithography system 100 may further comprise a thermal radiation source 134 that may be configured to provide a spatial distribution of thermal radiation to one or both of the template 108 and the substrate 102. The thermal radiation source 134 may comprise one or more thermal electromagnetic radiation sources that heat one or both of the substrate 102 and the template 108 without solidifying the formable material 124. The thermal radiation source 134 may comprise a spatial light modulator, such as a digital micromirror device (DMD), liquid crystal on silicon (LCoS), liquid crystal device (LCD), etc., to modulate the spatiotemporal distribution of the thermal radiation. The nanoimprint lithography system may further comprise one or more optical components used to combine the actinic radiation, thermal radiation, and radiation collected by the field camera 136 into a single optical path that intersects the imprint field when the template 108 contacts the formable material 124 on the substrate 102. After the template 108 contacts the formable material 124, the thermal radiation source 134 can send thermal radiation along a thermal radiation path (shown as two thick dark lines in FIG. 1). Although FIG. 1 shows the thermal radiation path when the template 108 is not in contact with the formable material 124, this is done for illustrative purposes so that the relative positions of the individual components can be easily identified. Those skilled in the art will appreciate that the thermal radiation path does not substantially change when the template 108 contacts the formable material 124. Although in FIG. 1 the thermal radiation path is shown terminating at the template 108, it can also terminate at the substrate 102. In an alternative embodiment, the thermal radiation source 134 is directly beneath the substrate 102 and the thermal radiation path is not coupled to the actinic radiation and visible light.

[0030] The substrate coating 132 may be applied to the substrate 102 before the formable material 124 is dispensed onto the substrate. In one embodiment, the substrate coating 132 may be an adhesion layer. In one embodiment, the substrate coating 132 may be applied to the substrate 102 before the substrate is loaded onto the substrate chuck 104. In an alternative embodiment, the substrate coating 132 may be applied to the substrate 102 while the substrate 102 is on the substrate chuck 104. In one embodiment, the substrate coating 132 may be applied by spin coating, dip coating, or the like. In one embodiment, the substrate 102 may be a semiconductor wafer. In another embodiment, the substrate 102 may be a blank template (replica blank) that may be imprinted and then used to create a daughter template.

[0031] The nanoimprint lithography system 100 may be regulated, controlled and / or directed by one or more processors 140 (controllers) in communication with one or more components and / or subsystems, such as the substrate chuck 104, the substrate positioning stage 106, the template chuck 118, the imprint head 120, the fluid dispenser 122, the radiation source 126, the thermal radiation source 134, the field camera 136 and / or the drop inspection system 138. The processor 140 may operate based on instructions in a computer readable program stored in a non-transitory computer readable memory 142. The processor 140 may be or include one or more of a CPU, MPU, GPU, ASIC, FPGA, DSP and a general purpose computer. The processor 140 may be a dedicated controller or may be a general purpose computing element adapted to be a controller. Examples of non-transitory computer readable memory include, but are not limited to, RAM, ROM, CDs, DVDs, Blu-ray, hard drives, network attached storage (NAS), intranet connected non-transitory computer readable storage devices, and internet connected non-transitory computer readable storage devices.

[0032] Either the imprint head 120, the substrate positioning stage 106, or both vary the distance between the mold 110 and the substrate 102 to define a desired volume (a three-dimensional bounded physical area) to be filled with the formable material 124. For example, the imprint head 120 can apply a force to the template 108 to bring the mold 110 into contact with the formable material 124. After the desired volume is filled with the formable material 124, the radiation source 126 generates actinic energy radiation (e.g., UV, 248 nm, 280 nm, 350 nm, 365 nm, 395 nm, 400 nm, 405 nm, 435 nm, etc.) to cure, solidify, and / or crosslink the formable material 124 in conformity with the substrate surface 130 and the patterning surface 112 that defines the patterned layer on the substrate 102. The formable material 124 is hardened while the template 108 is in contact with the formable material 124, thus forming a patterned layer on the substrate 102. Thus, the nanoimprint lithography system 100 uses an imprinting process to form a patterned layer having recesses and protrusions that are the inverse of the pattern of the patterned surface 112. In an alternative embodiment, the nanoimprint lithography system 100 uses an imprinting process to form a flat layer with the patterned surface 112 lacking features.

[0033] The imprinting process can be repeated in multiple imprint fields that span the entire substrate surface 130. Each imprint field can be the same size as a mesa 110 or just a pattern area of ​​the mesa 110. The pattern area of ​​the mesa 110 is the area of ​​the patterned surface 112 that is used to imprint a pattern on the substrate 102 that is a device feature or that is then used to form the device feature in a subsequent process. The pattern area of ​​the mesa 110 may or may not include a mass velocity variation mechanism that is used to prevent overprinting. In an alternative embodiment, the substrate 102 has only one imprint field that is the same size as the substrate 102 or the area of ​​the substrate 102 that is to be patterned on the mesa 110. In an alternative embodiment, the imprint fields overlap. Some of the imprint fields can be partial imprint fields that intersect the boundaries of the substrate 102.

[0034] The patterned layer may be formed to have a residual layer with a residual layer thickness (RLT) that is the minimum thickness of formable material 124 between the substrate surface 130 and the patterning surface 112 in each imprint field. The patterned layer may also include one or more features, such as protrusions that extend above the residual layer having a thickness. These protrusions coincide with the recesses 114 in the mesas 110.

[0035] Template / Super Straight 2 is a diagram of a template 108 that may be used in one embodiment. The patterned surface 112 may be on a mesa 110 (identified by a dashed box in FIG. 2). The mesa 110 is surrounded by a recessed surface 244 on the front side of the template. A mesa sidewall 246 connects the recessed surface 244 to the patterned surface 112 of the mesa 110. The mesa sidewall 246 surrounds the mesa 110. In embodiments where the mesa is circular or has rounded corners, the mesa sidewall 246 refers to a single mesa sidewall that is a continuous wall with no corners.

[0036] In another embodiment, an alternative template, referred to herein as a superstrate, can be used. In the case of a superstrate, there may be no mesas and the patterned surface 112 is featureless. That is, in one embodiment, there is no pattern on the surface 112. A superstrate without a pattern is used in the planarization process. Thus, when a planarization process is used, a superstrate is used in place of the template shown in FIG.

[0037] Imprinting / Planarization Process 3 is a flow chart of an imprinting process 300 by the nanoimprint lithography system 100 that can be used to form a pattern in a formable material 124 on one or more imprint fields (also called pattern areas or shot areas). The imprinting process 300 may be performed repeatedly on multiple substrates 102 by the nanoimprint lithography system 100. A processor 140 may be used to control the imprinting process 300.

[0038] In alternative embodiments, a similar process can be performed to planarize the substrate 102. In the case of planarization, substantially the same steps are performed as discussed herein with respect to FIG. 3, but the substrate may or may not have a pattern, while an unpatterned superstrate is used instead of a template. Thus, it should be understood that the following description is also applicable to the planarization method. When used as a superstrate, the superstrate may be the same size or larger than the substrate 102, and may be of similar size to the area to be planarized.

[0039] The start of the imprinting process 300 may include a template loading step in which a template transport mechanism loads the template 108 onto the template chuck 118. The imprinting process may also include a substrate loading step in which the processor 140 may cause the substrate transport mechanism to load the substrate 102 onto the substrate chuck 104. The substrate may have one or more coatings and / or structures. The order in which the template 108 and substrate 102 are loaded onto the nanoimprint lithography system 100 is not particularly limited, and the template 108 and substrate 102 may be loaded sequentially or simultaneously.

[0040] In the positioning step, the processor 140 can cause one or both of the substrate positioning stage 106 and / or the dispenser positioning stage to move imprint field i (index i may be initially set to 1) of the substrate 102 to a fluid dispensing position beneath the fluid dispenser 122. The substrate 102 can be divided into N imprint fields, where each imprint field is identified by an index i, {N∈Z, where N is a real integer such as 1, 10, 75, etc. +}. In the dispensing step S302, the processor 140 can cause the fluid dispenser 122 to dispense the formable material onto the imprint field i. In one embodiment, the fluid dispenser 122 dispenses the formable material 124 as multiple droplets. The fluid dispenser 122 can include one nozzle or multiple nozzles. The fluid dispenser 122 can eject the formable material 124 from one or more nozzles simultaneously. The imprint field i can be moved relative to the fluid dispenser 122 while the fluid dispenser is ejecting the formable material 124. Thus, the time at which some droplets land on the substrate can vary across the imprint field i. In one embodiment, during the dispensing step S302, the formable material 124 can be dispensed onto the substrate according to a droplet pattern. The droplet pattern can include information such as one or more locations for depositing droplets of the formable material, a volume of the droplets of the formable material, a type of the formable material, shape parameters of the droplets of the formable material, etc.

[0041] After the droplets have been dispensed, a contact step S304 can begin, in which the processor 140 can cause one or both of the substrate positioning stage 106 and the template positioning stage to contact the patterned surface 112 of the template 108 with the formable material 124 within the imprint field i.

[0042] During a spreading step S306, the formable material 124 then spreads towards the edges of the imprint field i and the sidewalls 246 of the mesa. The edges of the imprint field may be defined by the sidewalls 246 of the mesa. How the formable material 124 spreads to fill the trenches of the pattern can be observed via the field camera 136 and used to track the progress of the fluid front of the formable material. A curing step S308 can be performed after all gaps between the template and the substrate are filled.

[0043] In a curing step S308, the processor 140 may send instructions to the radiation source 126 to send a curing radiation pattern of active energy radiation through the template 108, the mesas 110, and the patterning surface 112. The curing radiation pattern provides sufficient energy to cure (polymerize) the formable material 124 beneath the patterning surface 112.

[0044] In a separation step S310, the processor 140 uses one or more of the substrate chuck 104, the substrate positioning stage 106, the template chuck 118, and the imprint head 120 to separate the patterned surface 112 of the template 108 from the hardened formable material on the substrate 102.

[0045] If there are additional imprint fields to be imprinted, the process returns to step S302. In one embodiment, additional processing is performed on the substrate 102 in processing step S312 to create a product (e.g., a semiconductor device). In one embodiment, each imprint field includes multiple devices.

[0046] Further processing in processing step S312 may include an etching process to transfer a relief image corresponding to the pattern in the patterned layer or the inverse of the pattern into the substrate. Further processing in processing step S312 may also include known steps and processes for fabricating articles including, for example, curing, oxidation, layering, deposition, doping, planarizing, etching, removal of formable material, dicing, bonding, packaging, etc. The substrate 102 may be processed to produce a number of articles (devices).

[0047] Droplet pattern fabrication It is useful to deposit multiple droplets of formable material 124 on substrate 102 and then imprint / planarize them. The imprint / planarization can be done field by field or over the entire wafer. The droplets of formable material 124 can also be deposited field by field or over the entire substrate. Even if droplets are deposited over the entire substrate, the creation of the droplet pattern is preferably done field by field.

[0048] Creating the droplet patterns for the entire field can include a processor 140 receiving a substrate pattern for the representative substrate 102 and a template pattern for the representative template 108 .

[0049] The substrate pattern may include information about the substrate topography of a representative substrate, a field of a representative substrate, and / or an entire field of a representative substrate. The substrate topography may be measured, created based on a previous manufacturing process, and / or created based on design data. In alternative embodiments, the substrate pattern is featureless, either because there is no previous manufacturing process or the substrate was previously planarized to reduce the topography. The substrate topography may include information about the shape of the edge bevel, radius, etc. of the representative substrate. The substrate topography may include information about the shape and location of one or more flats or notches that identify the orientation of the substrate. The substrate topography may include information about the shape and location of a reference edge that surrounds the area of ​​the substrate where the pattern is to be formed.

[0050] The template pattern may include information regarding the topography of the patterned surface 112 of a representative template. The topography of the patterned surface 112 may be measured and / or created based on design data. In another embodiment, the template pattern of the representative embodiment is featureless and may be used for planarization of the substrate 102. The patterned surface 112 may be the same size as an individual full field, multiple fields, an entire substrate, or larger than the substrate.

[0051] Upon receiving the substrate pattern and the template pattern, the processor 140 may calculate a distribution of the formable material 124 that results in a coating that fills a volume between the substrate and the patterned surface when the substrate and the patterned surface are separated by a gap during imprinting. The distribution of the formable material on the substrate may take the form of an areal density of the formable material, a position of a droplet of the formable material, and / or a volume of a droplet of the formable material. The calculation of the distribution of the formable material may take into account one or more of the material properties of the formable material, the material properties of the patterned surface, the material properties of the substrate surface, spatial variations in the volume between the patterned surface and the substrate surface, fluid flow, evaporation, etc.

[0052] curable composition The formable material is a curable composition. To make the curable composition usable in the context of nanoimprinting and planarization, the curable composition contains an acrylate monomer, where the acrylate monomer has a relatively small size and viscosity. For example, for a curable composition based on an acrylate monomer, the curable composition may include at least 25% by weight of the acrylate monomer based on the total weight of the curable composition. In some exemplary embodiments, the amount of the acrylate monomer may be at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 87% by weight, at least 89% by weight, at least 89.5% by weight, at least 89.9% by weight, or at least 90% by weight based on the total weight of the curable composition. In some exemplary embodiments, the amount of acrylate monomer can be 25% to 90%, 35% to 89.9%, 50% to 89.5%, 60% to 89%, 70% to 87%, or 75% to 85% by weight based on the total weight of the curable composition, i.e., the acrylate monomer can be a major component of the curable composition.

[0053] For the relatively small size, the acrylate monomer may have a molecular weight of 500 or less. In other exemplary embodiments, the molecular weight of the acrylate monomer may be 450 or less, 400 or less, 350 or less, 300 or less, 250 or less, 200 or less, or 150 or less. It should be understood that "or less" with respect to the molecular weight does not include 0, i.e., does not include the case where the acrylate monomer has no weight, since in such a case there is no acrylate. Thus, the value "or less" stated with respect to the molecular weight should be understood to mean the indicated value and values ​​less than it, so long as the amount is greater than 0. In some exemplary embodiments, the molecular weight of the acrylate monomer may be 120-500, 150-450, 200-400, or 250-300. By having an acrylate monomer with a relatively small size as the main component, the curable composition is suitable for nanoimprinting and planarization processes. The acrylate monomer may be monofunctional, difunctional, or multifunctional.

[0054] Examples of suitable monofunctional acrylates include isobornyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 4-cyanobenzyl acrylate, pentafluorobenzyl acrylate, 2-phenylethyl acrylate, phenyl acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl acrylate, n-hexyl acrylate, 4-tert-butylcyclohexyl acrylate, methoxypolyethylene glycol (350) monoacrylate, benzyl methacrylate, 2-methoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, and lauryl acrylate.

[0055] Examples of suitable diacrylates include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,2-propanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 2-butene-1,4-diacrylate, 1,3-butylene glycol diacrylate, 3-methyl-1,3-butanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,3-cyclohexanedimethanol diacrylate, tricyclodecane dimethanol diacrylate, 1,6-hexanediol diacrylate, 1H,1H,6H,6H-perfluoro-1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, acrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol diacrylate, neopentyl glycol diacrylate, cyclohexanedimethanol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, m-xylylene diacrylate, ethoxylated (3) bisphenol A diacrylate, ethoxylated (4) bisphenol A diacrylate, ethoxylated (10) bisphenol A diacrylate, dicyclopentanyl diacrylate, 1,2-adamantanediol diacrylate, 2,4-diethylpentane-1,5-diol diacrylate, poly(ethylene glycol) (400) diacrylate, poly(ethylene glycol) (300) diacrylate, 1,6-hexanediol (EO) 2 diacrylate, 1,6-hexanediol (EO) 5 diacrylate, and alkoxylated aliphatic diacrylate esters.

[0056] Examples of suitable polyfunctional acrylates include trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate (e.g., propoxylated (3) trimethylolpropane triacrylate, propoxylated (6) trimethylolpropane triacrylate), trimethylolpropane ethoxylate triacrylate (e.g., n≈1.3, 3, 5), di(trimethylolpropane)tetraacrylate, propoxylated glyceryl triacrylate (e.g., propoxylated (3) glyceryl triacrylate), propoxylated (4) glyceryl triacrylate, propoxylated (5) glyceryl triacrylate, propoxylated (6) glyceryl triacrylate, propoxylated (7) glyceryl triacrylate, propoxylated (8) glyceryl triacrylate, propoxylated (9) glyceryl triacrylate, propoxylated (10) glyceryl triacrylate, propoxylated (11) glyceryl triacrylate, propoxylated (12) glyceryl triacrylate, propoxylated (13) glyceryl triacrylate, propoxylated (14) glyceryl triacrylate, propoxylated (15) glyceryl triacrylate, propoxylated (16) glyceryl triacrylate, propoxylated (17) glyceryl triacrylate, propoxylated (18) glyceryl triacrylate, propoxylated (19 ... tris(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, tripentaerythritol octaacrylate, trimethylolpropane (PO)n triacrylate (n is 1, 2, 3, etc.), trimethylolpropane (EO)n triacrylate (n is 1, 2, 3, etc.).

[0057] Preferably, the acrylate monomer may be selected from the group consisting of isobornyl acrylate, neopentyl glycol diacrylate, benzyl acrylate, benzyl methacrylate, m-xylylene diacrylate, tricyclodecane dimethanol diacrylate, 1,6-hexanediol diacrylate, dicyclopentenyloxyethyl acrylate, 1,4-butanediol diacrylate, 1,10-decanediol diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, and derivatives thereof.

[0058] The acrylate monomer may further be selected based on the Ohnishi parameter. It is known that the smaller the value of N / (Nc-No) (N: total number of atoms in the monomer unit, Nc: number of carbon atoms in the monomer unit, No: number of oxygen atoms in the monomer unit) of the monomer unit, the lower the dry etching rate (Journal of Electrochemical Society, 130, 143 (1983)). The value of N / (Nc-No) is generally called the "Ohnishi parameter." The Ohnishi parameter of the acrylate monomer is preferably 4.5 or less, 4.0 or less, 3.5 or less, 3.0 or less, 2.5 or less, 2.0 or less, or 1.5 or less. That is, the Ohnishi parameter of the acrylate monomer may be preferably 1.5 to 4.5.

[0059] The curable composition further comprises an expanding monomer. The expanding monomer provides the advantage of a relatively small shrinkage after curing compared to a similar acrylate monomer-based curable composition without the expanding monomer. In other words, if a comparative curable composition is prepared that does not include the expanding monomer but is otherwise substantially the same as the curable composition described herein, the comparative curable composition will shrink much more after curing compared to the amount of shrinkage that occurs when the curable composition described herein is cured. In one exemplary embodiment, the amount of shrinkage of the cured composition calculated by comparing the volume of the cured composition to the volume of the curable composition (i.e., comparing the volume after curing to the volume before curing) is 3.5% or less, 3.0% or less, 2.5% or less, 2.0% or less, 1.5% or less, 1.0% or less, 0.5% or less, 0.25% or less, 0.1% or less, or 0.01% or less. Other examples include shrinkage of 0.1% to 3.5%, 0.25% to 3.0%, 0.5% to 2.5%, or 1.0% to 2.0%. For each of these percentages, it should be understood that the volume of the cured composition is less than the original volume before curing by the indicated percentage. For example, if the volume of the curable composition is "100", then when the shrinkage is 3.0%, the volume of the cured composition is "97". Since the shrinkage is specified as a percentage change in volume, the specific volume units are not relevant. Furthermore, it should be understood that "less than" with respect to the change in volume can include 0, since there may be no change in volume. In one exemplary embodiment, linear shrinkage, i.e., shrinkage in one direction, can be used to represent the overall volumetric shrinkage. For example, linear shrinkage representing the overall volumetric shrinkage can be measured in the height direction, i.e., the thickness direction of the sprayed composition.

[0060] The amount of the expanding monomer in the curable composition can be selected to achieve the volumetric shrinkage amount described above. For example, the curable composition can include at least 10 wt% of the expanding monomer based on the total weight of the curable composition. In some exemplary embodiments, the amount of the expanding monomer can be at least 15 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, or at least 70 wt% based on the total weight of the curable composition. In some exemplary embodiments, the amount of the expanding monomer can be 10 wt% to 70 wt%, 15 wt% to 60 wt%, 20 wt% to 50 wt%, or 30 wt% to 40 wt% based on the total weight of the curable composition. That is, the expanding monomer can be the most or second most abundant component of the curable composition.

[0061] The total amount of the expanding monomer and the acrylate monomer can be at least 85% by weight based on the total weight of the curable composition. In some exemplary embodiments, the total amount of the expanding monomer and the acrylate monomer can be at least 87%, at least 90%, at least 93%, at least 95%, at least 97%, at least 98%, or at least 99% by weight based on the total weight of the curable composition. In some exemplary embodiments, the total amount of the expanding monomer and the acrylate monomer can be 85% to 99%, 87% to 98%, 90% to 97%, or 93% to 97% by weight based on the total weight of the curable composition. That is, any amount of acrylate monomer selected within the previously disclosed ranges of acrylate monomer, and any amount of expanding monomer selected within the previously disclosed ranges of expanding monomer, the combination of these two amounts will fall within the entire previously disclosed ranges of monomer.

[0062] Preferably, the components of the curable composition and the relative amounts of the components are selected such that the Ohnishi parameter of the overall composition is 4.0 or less, 3.5 or less, 3.0 or less, 2.5 or less, 2.0 or less, 1.8 or less, i.e., the Ohnishi parameter of the overall curable composition may preferably be 1.8 to 4.0.

[0063] The expanding monomer may be cationically, anionically and / or free radically polymerizable. The expanding monomer may contain one or more 3-membered rings, one or more 4-membered rings, one or more 5-membered rings, one or more 6-membered rings, one or more 7-membered rings. The expanding monomer may contain one or more rings greater than 7 members. The expanding monomer may have a single ring, a double ring, or a twisted ring.

[0064] Expanding monomers can be classified as bicyclic orthoesters (BOEs, cationically polymerizable), cyclic carbonates (cationically or anionically polymerizable), spiro orthocarbonates (SOCs, cationically polymerizable), spiro orthoesters (SOEs, cationically polymerizable), bicyclic monolactones (cationically or anionically polymerizable), and bicyclic bislactones (cationically or anionically polymerizable). Some of these contain carbon-carbon double bonds in the ortho position to form unsaturated SOEs (free radically polymerizable), unsaturated SOCs (free radically polymerizable). These unsaturated SOEs and SOCs can also be polymerized by free radicals. Epoxides are three-membered monocyclic compounds. Epoxides can contain two or more epoxy groups. In general, epoxides are considered to be expanding monomers because monofunctional epoxides show some shrinkage during polymerization. However, the shrinkage is much smaller compared to non-ring-opening polymerization such as acrylates. In some cases, multifunctional epoxides exhibit near zero shrinkage. Thus, multifunctional epoxides are included within the meaning of expanding monomers as used herein. Polymerization of epoxides can be initiated cationically or by free radicals.

[0065] Examples of suitable expanding monomers include: 3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (EHEHC): [ka] 1,4-Cyclohexanedione bis(ethylene ketal) (CHDB): [ka] Octahydro-spiro[1,3-benzodioxole-2,2'(3'H)-furan] (SBOF): [ka] 3,9-Bis(phenylmethyl)-1,5,7,11-tetraoxaspiro[5.5]undecane (SDPHU): [ka] 2-Methylene-4-phenyl-1,3-dioxolane (MPDO): [ka] 2-Methylene-1,4,6-trioxaspiro[4.4]nonane (MTS): [ka]

[0066] Other examples of SOC include 3,9-di(5-norbornen-2-yl)-1,5,7,11-tetraoxaspiro[5.5]undecane (NSOC) (DER332), 3,9-dimethylene-1,5,7,11-tetraoxaspiro[5.5]undecane (DMSOC), tetramethylspiroorthocarbonate (TMSOC) (EPON 815), dicyclohexene spiroorthocarbonate (DCHeSOC), dicyclohexane spiroorthocarbonate (DCHaSOC), and epoxidized NSOC.

[0067] Examples of SOEs (both saturated and unsaturated) include 1,4,6-trioxaspiro[4.4]nonane (TON), 2-methylene-1,4,6-trioxaspiro[4.4]nonane (MTON), 2-methylene-1,4,6-trioxaspiro[4.6]decane, 2-methylene-1,4,6-trioxaspiro14.61undecane, 2-methyl-7-methylene-1,4,6-trioxaspiro[4.4]nonane, 2-butyl-7-methylene-1,4,6-trioxaspiro[4.4]nonane, 7-bromomethyl spiro-7-oxabicyclo[4.3.0]nonane-8,2'-(1',3')-dioxalane, spiro-7,9-dioxacyclo[4.3.0]nonane-8,2'-1'-oxycyclopentane, spiro-1,3-dioxalane-2,1'-(3H)-isobenzofuran, spiro-7,9-dioxabicyclo[4.3.0]nonane-8,8'-7'-oxabicyclo[4.3.0]nonane, adduct of phenyl diglycidyl ether with gamma-butyrolactone.

[0068] Examples of SOC (saturated and unsaturated) include: 1,4,6,9-tetraoxaspiro[4.4]nonane, 1,5,7,11-tetraoxaspiro[5.5]undecane, 1,6,8,13-tetraoxaspiro[6.6]tridecane, 3-methylene-1,5,7,11-tetraoxaspiro[4.5]decane, 3-methylene-1,5,7,11-tetraoxaspiro[5.6]dodecane, 3-methylene-1,5,7,11-tetraoxaspiro[5.5]undecane, 3,9-dimethylene-1,5,7,11-tetraoxaspiro[5.5] undecane (DMSOC), 3,3-dimethyl-9-methylene-1,5,7,11-tetraoxaspiro[5.5]undecane, 3,9-dicyclohexane-1,5,7,11-tetraoxaspiro[5.5]undecane, 3,9-di(5-norbornen-2-yl)-1,5,7,11-tetraoxaspiro[5.5]undecane (NSOC), epoxidized NSOC, 3,9-di(9,10-dihydro-9,10-ethanoanthracenyl)-1,5,7,11-tetraoxaspiro[5.5]undecane, 2,3,7,8-di(9,10-anthrylene)-1,4,6 ,9-Tetraoxaspiro[4.4]nonane, 2,3,7,8-bis(o-phenylene)1,4,6,9-tetraoxaspiro[4.4]nonane, 3,9-di{benzyl-(1',4'-vinyl)}1,5,7,11-tetraoxaspiro[5.5]undecane, 3,4,10,11-bis{endo-(1',4-butylene)}|1,6,8,13-tetraoxaspiro[6.6]tridecane, 3,4,10,11-bis-(o-phenylene)1,6,8,13-tetraoxaspiro[6.6]tridecane, 3,4,10,11-bis-{endo-(1', 4'-Endomethylene)1',4'-buten-2'-ylidene}1,6,8,13-tetraoxaspiro[6.6]tridecane (DMSOC), 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane (DBSOC), 3,9-dicyclohexene-1,5,7,11-tetraoxaspiro[5.5]undecane (DCHeSOC), 3,3-diethyl-9-methylene-1,5,7,11-tetraoxaspiro[5.5]undecane, 1,4,6,10,12,15,17,19-octaoxatrispiro[4.2 ...2] Nonan.

[0069] Further examples of aromatic SOCs include dispiro[1,3-benzodioxole-2,2'-benzo[1,2-d:4,5-d']bis[1,3]dioxole-6',2''-[1,3]benzodioxole], 5,5''-bi-2,2'-spirobi[1,3-benzodioxole], 2,2'-spirobi[1,3-benzodioxole], 5-(2,2'-spirobi[1,3-benzodioxole]-5'-ylsulfonyl)-, methanone, 2,2'-spirobi[1,3-benzodioxole]-4-yl-2,2'-spirobi[1,3-benzodioxole]-5'-yl-.

[0070] Further examples of unsaturated SOCs include 1,5,7,16-tetraoxadispiro[5.2.5.2]hexadec-11-ene, 3-methylene-, 2-methyl-9-methylidene-1,5,7,11-tetraoxaspiro[5.5]undecane, 2-(propan-2-yl)-1,5,7,11-tetraoxaspiro[5.5]undecane, 8,8-dimethyl-2-methylidene-1,4,6,10-tetraoxaspiro[4.5]decane, 4''-methylidenedispiro[bicyclo[2.2.1]hept-5-ene-2,5'-[1,3]dioxane, 5-methylidene-1,5,7,11-tetraoxaspiro[5.5]undec ... These include 2-methylidene-7-phenyl-1,4,6,9-tetraoxaspiro[4.4]nonane, 5''-methylidenedispiro[bicyclo[2.2.1]hept-5-ene-2,5'-[1,3]dioxane-2',2''-[1,3]dioxane], 3,3-dimethyl-9-methylidene-1,5,7,12-tetraoxaspiro[5.6]dodecane, and 4'-methylidene-1,5-dihydrospiro[[2.4]benzodioxepin-3,2'-[1,3]dioxolane].

[0071] Examples of BOE include: 2,6,7-trioxabicyclo[2.2.2]octane and its derivatives: 1,4-diethyl-2,6,7-trioxabicyclo[2.2.2]octane, 1-ethyl-2,6,7-trioxabicyclo[2.2.2]octane, 4-ethenyl-1-ethyl-2,6,7-trioxabicyclo[2.2.2]octane, 4-ethyl-2,6,7-trioxabicyclo[2 .2.2]octane, 1-ethenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane, 1-[2-bromoethenyl]-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane, 4-ethyl-1-phenyl-2,6,7-trioxabicyclo[2.2.2]octane, 1,4-diphenyl-2,6,7-trioxabicyclo[2.2.2]octane, (1-phenyl-2,6 ,7-trioxabicyclo[2.2.2]octan-4-yl)methyl ethyl carbamate, (1-phenyl-2,6,7-trioxabicyclo[2.2.2]octan-4-yl)methyl methyl carbamate, (1-ethyl-2,6,7-trioxabicyclo[2.2.2]octan-4-yl)methyl ethyl carbamate, (1-butyl-2,6,7-trioxabicyclo[2.2.2]octan-4-yl ) methylethyl carbamate, (1-propyl-2,6,7-trioxabicyclo[2.2.2]octan-4-yl)methylethyl carbamate, 1-methyl-2,6,7-trioxabicyclo[2.2.2]octane, 4-ethyl-1-propyl-2,6,7-trioxabicyclo[2.2.2]octane, (4-ethyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)methanol. Other examples are 2,6,7-trioxabicyclo[3.1.1]heptane, 2,6,7-trioxabicyclo[2.2.1]heptane.

[0072] The curable composition may contain one of the expandable monomers described above or a mixture of two or more of the expandable monomers described above. When a mixture is used, the total amount of expandable monomer in the curable composition is the amount indicated above.

[0073] The ratio of the amount of acrylate monomer to the amount of expanding monomer (X:Y, where X is the amount of acrylate monomer and Y is the amount of expanding monomer) can be 4:1 to 1:3, 2:1 to 4:11, 4:3 to 2:5, or 1:1 to 1:2. Examples include 1:1, 1:1.5, 1:2, 1:2.5, and 1:3.

[0074] The expanding monomer preferably contains a ring having a radically polymerizable functional group. The radically polymerizable functional group can be a carbon-carbon double bond or an epoxide group. Preferably, the radically polymerizable functional group is an acrylate group to enhance compatibility with acrylate monomers.

[0075] The curable composition further comprises a photoinitiator. A photoinitiator is a molecule that generates a reactive species when exposed to radiation, e.g., UV radiation. The curable composition may comprise 5 wt% or less of the photoinitiator, based on the total weight of the curable composition. In some exemplary embodiments, the amount of photoinitiator may be at least 4 wt% or less, 3 wt% or less, 2.5 wt% or less, 2.0 wt% or less, 1.5 wt% or less, 1.0 wt% or less, 0.5 wt% or less, based on the total weight of the curable composition. It should be understood that "or less" with respect to the amount of photoinitiator does not include zero, i.e., does not include the absence of photoinitiator, since, as noted above, the curable composition includes a photoinitiator. Thus, a value "or less" recited with respect to the amount of photoinitiator should be understood to mean less than or equal to the indicated value, so long as the amount is greater than zero. In some exemplary embodiments, the amount of photoinitiator may be 0.5 wt% to 4 wt%, 1.0 wt% to 3 wt%, or 2.0 wt% to 2.5 wt% based on the total weight of the curable composition. That is, the photoinitiator may be a minor component of the hardenable composition.

[0076] The photoinitiator may be a cationic photoinitiator, an anionic photoinitiator, or a free radical photoinitiator. In one exemplary embodiment, the photoinitiator is a cationic photoinitiator. The photoinitiator may be metal-free when the curable composition is used as part of a semiconductor manufacturing process that requires the absence of metal ions. The photoinitiator may be an iodonium, phosphonium, or sulfonium-based photoacid generator, where the counterion may be a halide, triflate, nitrate, sulfonate, phosphate, excluding metals. The photoinitiator may be diphenyliodonium hexafluorophosphate (DPIPF), tetraphenylphosphonium halide, triphenylsulfonium triflate, bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate, bis(4-tert-butylphenyl)iodonium p-toluenesulfonate, diphenyliodonium nitrate, triphenylsulfonium triflate, tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate. A single photoinitiator may be present in the hardenable composition or a combination of photoinitiators may be present in the hardenable composition.

[0077] Examples of photoinitiators include: [ka]

[0078] The curable composition further comprises a photosensitizer. A photosensitizer is a molecule that undergoes a chemical change in another molecule through a photochemical process. The reactive species facilitates the polymerization of the curable composition into a polymerized and hardened composition. Particularly under cationic polymerization conditions, the photosensitizer accelerates the polymerization reaction, so that the cured product can be produced much more quickly. For example, the cationic polymerization reaction of the acrylate monomers and expanding monomers listed above can take minutes or even hours to complete. However, with the appropriate photosensitizer, the polymerization reaction can be completed in a few seconds, i.e., 0.1 to 100 seconds. Fast cure times are particularly desirable for nanoimprinting and planarization processes, which are high throughput operations.

[0079] The curable composition may include 2 wt% or less of photosensitizer based on the total weight of the curable composition. In some exemplary embodiments, the amount of photosensitizer may be 1.75 wt% or less, 1.5 wt% or less, 1.25 wt% or less, 1.0 wt% or less, 0.75 wt% or less, 0.6 wt% or less, 0.5 wt% or less, 0.3 wt% or less, 0.2 wt% or less, or 0.1 wt% or less based on the total weight of the curable composition. It should be understood that "or less" with respect to the amount of photosensitizer does not include 0, i.e., does not include the absence of photosensitizer, because the curable composition includes photosensitizer as described above. Thus, a value "or less" stated with respect to the amount of photosensitizer should be understood to mean the indicated value or less, as long as the amount is greater than 0. In some exemplary embodiments, the amount of photosensitizer can be from 0.1% to 2.0%, 0.2% to 1.75%, 0.3% to 1.5%, 0.5% to 1.25%, or 0.75% to 1.0% by weight based on the total weight of the curable composition, i.e., the photosensitizer can be a minor component of the curable composition.

[0080] The photosensitizer may be benzophenone and its derivatives. The photosensitizer may be 2-isopropylthioxanthone (ITX), benzophenone, phenylbenzophenone, 4,4'-bis(diethylamino)benzophenone, 4-benzoyl 4'-methyldiphenyl sulfide, methyl 2-benzoylbenzoate, 2-isopropylthioxanthone, xanthone, t-butylanthraquinone, phenothiazine, 7-diethylamino-4-methylcoumarin. A single photosensitizer may be present in the curable composition or a combination of photosensitizers may be present in the curable composition.

[0081] The curable composition may further include a surfactant. The surfactant provides the curable composition with a suitable surface tension to allow better separation from the template / superstrate after UV exposure. That is, the curable composition with the surfactant is more easily separated from the template / superstrate than the curable composition without the surfactant. The surfactant acts as a release agent that helps reduce the separation energy when the template is pulled away from the curable composition after curing. The curable composition may include up to 5 wt% of surfactant based on the total weight of the curable composition. It should be understood that "up to" does not include 0 when a surfactant is present. Thus, a value "up to" recited for the amount of surfactant should be understood to mean up to the indicated value as long as the amount is greater than 0. In some exemplary embodiments, the amount of surfactant may be at least 4.0 wt% or less, 3.0 wt% or less, 2.0 wt% or less, 1.0 wt% or less, 0.5 wt% or less, or 0.25 wt% or less based on the total weight of the curable composition. In some exemplary embodiments, the amount of surfactant can be from 0.25% to 5%, from 0.5% to 4.0%, or from 1.0% to 3.0% by weight, based on the total weight of the curable composition, i.e., the surfactant can be a minor component of the curable composition.

[0082] The surfactant may be non-ionic, and in some cases the surfactant may be a fluorinated surfactant. The fluorinated surfactant may comprise one or more poly(oxyalkylenes). Suitable commercially available examples of the included nonionic fluorinated surfactant component include those sold under the product name ZONYL® FSO-100 by DuPont; those sold under the product name FC-4432, FC-4430 by 3M Company; those sold under the product name MASURF FS-2000 by Mason Chemical Company of Arlington Heights; those sold under the product name Lodyne S-222N by Ciba-Geigy Corp; and those sold under the product name MegaFace R-08 by Dainippon Ink & Chemical, Chemguard S554, S550-100 or S550 (Chemguard), S222N (Chemguard), S559-100 or S559 (Chemguard), Capstone® FS-31 (DuPont), Capstone® FS-35 (DuPont (trademark)), Capstone (trademark) FS-34 (DuPont (trademark)), Capstone (trademark) FS-30 (Dupont (trademark)), Capstone (trademark) FS-3100 (Dupont (trademark)), Masurf (trademark) FS-2950 (Mason), Masurf (trademark) FS-3240 (Mason), Masurf (trademark) FS-2900 (Mason), Masurf (trademark) FS-2825 (Mason), Masurf (trademark) FS-1700 (Mason), Masurf (trademark) FS-1800 (Mason), and Megaface 550 (DIC), FTERGENT 222F, FTERGENT 251, FTERGENT 250, DEO-5, DEO-15, and PolyFox PF-656.

[0083] In some other cases, the surfactant may be non-fluorinated. The non-fluorinated surfactant may comprise a poly(oxyalkylene) group. Suitable commercial examples include Pluronic L43, L44, L42, L61, L62, L63, L64, L65, L81, L72, L31, L121, L101, L122, L92; Pluriol A 500 PE; Dow Synalox series including 25-220B, 25-300B, 40-60B, Terigitaol SD, XH; Huntsman JEFFOX WL660, 5000, Croda Atlas G-5000, Claritant Polyglykol B 11-type (B11 / 30, B11 / 50, B11 / 70), Polyglykol D-type (D21 / 100, D21 / 150, D21 / 220), Polyglykol P Includes 41-type (P41 / 200, P41 / 300).

[0084] Other additives may also be included in the curable composition. The additives may be inhibitors, thermal initiators, porogens, etc. Inhibitors are used to stabilize the resist and extend its shelf life. Inhibitors may be hindered phenols, phosphites and thioethers of secondary aromatic amines, benzofuranones, acrylated bisphenols. Examples include 4-methoxyphenol, 2,6-di-tert-butyl-p-cresol, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, C13-15 branched alkyl esters, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 2,2'-methylenebis(6-tert-butyl-4-methylphenol), N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, bis[4-(2-phenyl-2-propyl)phenyl]amine, N-(1,3-dimethylbutyl)-N'-phenyl-1,4 ... Nylenediamine, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 2,2,6,6-tetramethyl-4-piperidinyl stearate, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphate, tris(2,4-di-tert-butylphenyl)phosphite, dioctadecyl 3,3'-thiodipropionate, 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]propane-1,3-diylbis[3-(dodecylthio)propionate].

[0085] Thermal initiators serve to further polymerize the curable composition at elevated temperatures to improve mechanical strength or counter shrinkage and stress induced by the baking process. Some curable components may not cure 100% under exposure to light. Baking the cured resist may further cure some of the uncured monomers or functional groups if properly initiated. Preferably, the thermal initiator is stable at room temperature and decomposes at elevated temperatures, e.g., above 200°C or 250°C or higher, to generate radicals or Lewis acids. Examples include dicyandiamide, cyclohexyl tosylate, tert-butyl hydroperoxide, cumene hydroperoxide, 2,2'-azodi(2-methylbutyronitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, diphenyl(methyl)sulfonium tetrafluoroborate.

[0086] When additives are present, they can make up any amount remaining after selecting the amount of acrylic monomer, expanding monomer, photoinitiator, photosensitizer, and surfactant. For example, the curable composition can include 2 wt% or less of additives based on the total weight of the curable composition. In some exemplary embodiments, the amount of additives can be at least 1.75 wt% or less, 1.5 wt% or less, 1.0 wt% or less, 0.75 wt% or less, 0.5 wt% or less, 0.2 wt% or less, 0.02 wt% or less, or 0.002 wt% or less based on the total weight of the curable composition. When additives are present, "less than" with respect to the amount of additives should be understood to not include 0. Thus, a value "less than" stated with respect to the amount of additives should be understood to mean less than or equal to the indicated value, as long as the amount is greater than 0. In some exemplary embodiments, the amount of additive can be from 0.002 wt % to 2 wt %, from 0.02 wt % to 1.75 wt %, from 0.2 wt % to 1.25 wt %, or from 0.5 wt % to 1.0 wt %, based on the total weight of the curable composition.

[0087] It should be understood that the total amount of all components of the curable composition cannot, by definition, exceed 100% by weight. That is, any amount of acrylate monomer selected within the previously disclosed range of acrylate monomer, any amount of expanding monomer selected within the previously disclosed range of expanding monomer, any amount of photoinitiator selected within the previously disclosed range of photoinitiator, any amount of photosensitizer selected within the previously disclosed range of photosensitizer, and any amount of other components such as surfactants or additives, in combination, is at most 100% by weight. In one exemplary embodiment, the curable composition consists only of acrylate monomer, expanding monomer, photoinitiator, and photosensitizer. In another exemplary embodiment, the curable composition consists only of acrylate monomer, expanding monomer, photoinitiator, photosensitizer, and surfactant. In another exemplary embodiment, the curable composition consists only of acrylate monomer, expanding monomer, photoinitiator, photosensitizer, surfactant, and additive. In such an embodiment, the total amount of these components is, by definition, 100% by weight. In another exemplary embodiment, the curable composition consists essentially of acrylate monomers, expanding monomers, photoinitiators, and photosensitizers, with some amounts of other components that do not significantly affect the use of the curable composition in nanoimprinting / planarization and do not affect the shrinkage benefits described above. In another exemplary embodiment, the curable composition consists essentially of acrylate monomers, expanding monomers, photoinitiators, photosensitizers, and surfactants, with some amounts of other components that do not significantly affect the use of the curable composition in nanoimprinting / planarization and do not affect the shrinkage benefits described above. In another exemplary embodiment, the curable composition consists essentially of acrylate monomers, expanding monomers, photoinitiators, photosensitizers, surfactants, and additives, with some amounts of other components that do not significantly affect the use of the curable composition in nanoimprinting / planarization and do not affect the shrinkage benefits described above.For example, the total amount of acrylate monomer, expanding monomer, photoinitiator, and photosensitizer can be at least 90% by weight, at least 93% by weight, at least 95% by weight, at least 97% by weight, at least 98% by weight, at least 99% by weight, at least 99.5% by weight, at least 99.9% by weight based on the total weight of the curable composition. The remainder can be surfactants and / or additives. In another example, the total amount of acrylate monomer, expanding monomer, photoinitiator, photosensitizer, and surfactant can be at least 95% by weight, at least 96% by weight, at least 97% by weight, at least 98% by weight, at least 99% by weight, at least 99.5% by weight, at least 99.9% by weight based on the total weight of the curable composition. The remainder can be additives.

[0088] For use in nanoimprinting / planarization processes, the viscosity of the curable composition may be 10 cP or less at 25° C. In some exemplary embodiments, the viscosity of the curable composition may be 8 cP or less, 6 cP or less, or 5 cP or less at 25° C. It should be understood that "or less" with respect to viscosity does not include 0, i.e., does not include the case where the viscosity is 0 cP. Thus, a recited value "or less" with respect to viscosity should be understood to mean less than or equal to the indicated value, so long as the amount is greater than 0. In some exemplary embodiments, the viscosity of the curable composition may be 2 cP to 10 cP, 3 cP to 8 cP, or 4 cP to 7 cP at 25° C. That is, the particular components of the curable composition and the relative amounts of each component should be selected such that the combination of the components results in a curable composition having a viscosity in the ranges listed above. If the viscosity of the curable composition is greater than 10 cP at 25° C., the curable composition is not suitable for use in nanoimprinting / planarization. This is because the droplets are not small enough (e.g., not less than 1 picoliter size) when ejected by a fluid dispenser, and the droplets do not spread quickly enough into a continuous shape, adversely affecting throughput. EXAMPLES

[0089] The compositions of the curable compositions of Examples 1 to 3 and Comparative Examples 1 to 4 are as follows.

[0090] Example 1 (EX1): 47 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (EHEHC) (expandable monomer), 50 parts of isobornyl acrylate (IBOA) (monoacrylate monomer), 2.5 parts of diphenyliodonium hexafluorophosphate (DPIPF) (photoinitiator), 0.5 parts of 2-isopropylthioxanthone (ITX) (photosensitizer), and 1 part of surfactant, namely fluorinated surfactant FS2000M1 from Wonda Science, were combined to form a curable composition. Each component was weighed and placed in an opaque bottle. The components in the bottle were then vortex mixed for 1 minute and then placed on a roller mixer for about 8 hours to form a curable composition.

[0091] Example 2 (EX2): 15 parts of 1,4-cyclohexanedione bis(ethylene ketal) (CHDB) (expandable monomer), 85 parts of IBOA, 2.5 parts of DPIPF, 0.5 parts of ITX and 1 part of surfactant were prepared using the same method as in Example 1.

[0092] Example 3 (EX3): 79 parts of octahydro-spiro[1,3-benzodioxole-2,2'(3'H)-furan] (T1, shown below) (expandable monomer), 19 parts of neopentyl glycol diacrylate, 0.9 parts of DPIPF, 0.2 parts of ITX and 1.6 parts of surfactant were prepared using the same method as in Example 1.

[0093] [ka]

[0094] Comparative Example 1 (CE1): 47 parts neopentyl glycol diacrylate (NPGDA) (diacrylate monomer), 50 parts IBOA, 2.5 parts DPIPF, 0.5 parts ITX, and 1 part surfactant were prepared using the same method as in Example 1. It should be noted that there is no expanding monomer present in this curable composition.

[0095] Comparative Example 2 (CE2): 97 parts NPGDA, 2.5 parts DPIPF, 0.5 parts ITX and 1 part surfactant was prepared using the same method as in Example 1. It should be noted that there is no expanding monomer present in this curable composition.

[0096] Comparative Example 3 (CE3): 97 parts EHEHC, 2.5 parts DPIPF, 0.5 parts ITX and 1 part surfactant was prepared using the same method as in Example 1. Note that there is no acrylate monomer present in this curable composition.

[0097] Comparative Example 4 (CE4): 79 parts IBOA (acrylate monomer), 19 parts neopentyl glycol diacrylate, 0.9 parts DPIPF, 0.2 parts ITX and 1.6 parts surfactant were prepared using the same method as in Example 1.

[0098] The curable compositions of the Examples and Comparative Examples were tested for the amount of shrinkage after curing. The shrinkage tests were performed on an Anton Paar MCR-301 rheometer coupled to a UV curing system and heater. 92 mW / cm at 365 nm. 2 ~98mW / cm 2Each curable composition was cured for 25 minutes using a mercury UV lamp equipped with a 340 nm broadband long wave filter with an intensity of 100 nm. The UV intensity was varied and a UV power meter was used to measure the UV light intensity at 365 nm. The total dose can be calculated by intensity x exposure time. The induction time and cure time were recorded along with the storage and loss moduli. The cure time was recorded when the storage modulus reached 10 MPa. The induction period was recorded at the onset of the modulus increase. The volume change was recorded at 10 minutes cure time and / or 20 minutes cure time based on when the volume change stabilized. The results are reported in Table 1 below.

[0099] [Table 1]

[0100] UV irradiation was started at the 50 second mark. The storage modulus of CE1, EX1 and EX2 increased rapidly after initiation and reached its plateau at about 50 seconds. However, for CE3, which only has ring-opening monomers, a very gentle slope was shown with a 10 times longer induction period. Even at the 10 minute mark, CE3 did not finish polymerization. This is likely because CE3 only has a cationic ring-opening mechanism and is slow to react, while all other formulations contained acrylates and both radical and cationic polymerizations occurred. The addition of acrylate monomer dramatically increased the cure speed.

[0101] Table 2 reports the shrinkage for each of the Examples and Comparative Examples as measured by the rheometer at 10 minutes.

[0102] [Table 2]

[0103] For CE1, EX1 and EX2, Table 2 shows how the shrinkage is affected by the amount of expanding monomer. As can be seen in Table 2, by comparing EX1 with CE1, EX1 showed only 0.8% shrinkage with 47 parts of the three-membered expanding monomer EHEHC relative to the diacrylate NPGDA in CE1, almost completely offsetting the shrinkage from the polymerization of the acrylate. Meanwhile, EX2 has a five-membered ring CHDB, which is more expanding compared to the three-membered ring. However, EX2 only had 15 parts CHDB. The final result showed a net reduction of 21% in terms of shrinkage compared to CE1 (from 3.9% to 3.1%). By using EX1, a planarization layer with a thickness of 100 nm can show a shrinkage of less than 1 nm in height, which is acceptable for some manufacturing process specifications. For example, the planarization process, which is a lithography process for manufacturing integrated circuit substrates, can replace the more complicated and expensive chemical mechanical polishing (CMP) process.

[0104] For CE2 and CE3, when the percentage of monomer is increased significantly, the volume shrinkage is reduced to almost zero. This directly affects the height difference across the sprayed layer. When the sprayed layer is 50 nm thick, the height difference across the sprayed layer is only 0.1 nm. When the sprayed layer is 100 nm thick, which is typical in the semiconductor field, the height shrinkage is about 0.2 nm, which is suitable for replacing CMP. For the curable composition of the embodiment, one spray pass is probably sufficient to replace other planarization processes, such as spin-on carbon and CMP processes.

[0105] Although CE3 exhibits very little shrinkage at the 10 minute time point, CE3 is not suitable for spray application in the above-described application system 100. In particular, CE3 has a viscosity of greater than 10 cP at 25° C., which means that CE3 is not sprayable and cannot be used in the above-described system 100.

[0106] CE4 shows that the curable composition without the mixture of expanding monomer and acrylate had poor shrinkage, i.e., greater than 3.0%, at 10 minutes. EX3 shows that the curable composition having a large amount of expanding monomer (wherein the expanding monomer is different from the expanding monomer of the previous example) in combination with a small amount of diacrylate component had good shrinkage at 10 minutes.

[0107] Each of the examples also had a viscosity in the range of 7 cP to 9 cP, i.e., less than 10 cP, at 25° C. Thus, the curable compositions are jettable and can be dispensed by the system 100 described above with sufficient accuracy and throughput.

[0108] Further modifications and alternative embodiments of various aspects will be apparent to those skilled in the art upon consideration of this detailed description. Accordingly, this detailed description should be interpreted as illustrative only. It should be understood that the forms shown and described herein should be interpreted as examples of embodiments. Elements and materials may be substituted for those shown and described herein, components and processes may be reversed, and certain features may be utilized independently, all as would be apparent to one skilled in the art after benefiting from this detailed description. [Explanation of symbols]

[0109] 100 Nanoimprint Lithography System 102 Substrate 104 Substrate chuck 106 Substrate positioning stage 108 Templates 110 Mesa part (mold) 112 Patterned Surfaces 114 Template recess 116 Template convex part 118 Template chuck 120 Imprint Head 122 Fluid Dispenser 124 Formable materials 126 Radiation Source 128 Exposure Path 130 Board surface 132 Substrate Coating 134 Thermal radiation source 136 Field Camera 138 Droplet Inspection System 140 Processor (Controller) 142 Computer-Readable Memory 244 recessed surface (front side of template) 246 Mesa side wall 300 Imprinting Process

Claims

1. A planarizing curable composition comprising: at least 10% by weight, based on the total weight of the curable composition, of a monomer that reduces shrinkage of the curable composition; at least 25 wt. % of an acrylate monomer having a molecular weight of 500 or less, based on the total weight of the curable composition; A photoinitiator; A photosensitizer; Including, The monomer that reduces the shrinkage of the curable composition is a monomer that contains one or more rings having a five-membered or larger ring structure and undergoes polymerization associated with cleavage of the ring, The curable composition has a viscosity of 10 cP or less, A curable composition, wherein the total amount of the shrinkage-reducing monomer and the acrylate monomer is at least 90 wt %, based on the total weight of the curable composition.

2. 10% to 50% by weight, based on the total weight of the curable composition, of a monomer that reduces shrinkage of the curable composition; 50% to 90% by weight of the acrylate monomer, based on the total weight of the curable composition; 2. The curable composition of claim 1, comprising, in total, not more than 100% by weight.

3. 3. The curable composition of claim 1 or 2, wherein the total amount of the shrinkage reducing monomer and the acrylate monomer of the curable composition is at least 95 wt%, based on the total weight of the curable composition.

4. 4. The curable composition of claim 1, wherein the volume of the cured product obtained by curing the curable composition is no more than 3.5% smaller than the volume of the curable composition before curing.

5. 5. The curable composition according to claim 1, wherein the ratio between the amount of the acrylate monomer and the amount of the monomer that reduces shrinkage of the curable composition is from 4:1 to 1:

1.

6. The monomer that reduces shrinkage of the curable composition is 【Chemistry 1】 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 and 【Chemistry 5】 The curable composition according to any one of claims 1 to 5, selected from the group consisting of:

7. The hardenable composition of any one of claims 1 to 6, wherein the hardenable composition shrinkage reducing monomer comprises a mixture of different hardenable composition shrinkage reducing monomers.

8. The acrylate monomer is The curable composition according to any one of claims 1 to 7, wherein the Onishi parameter, which is the value of N / (Nc-No) of the monomer unit, is 4.5 or less. (N: total number of atoms in the monomer unit, Nc: number of carbon atoms in the monomer unit, No: number of oxygen atoms in the monomer unit)

9. The curable composition according to any one of claims 1 to 8, wherein the acrylate monomer is selected from the group consisting of isobornyl acrylate, neopentyl glycol diacrylate, benzyl acrylate, benzyl methacrylate, m-xylylene diacrylate, tricyclodecane dimethanol diacrylate, 1,6-hexanediol diacrylate, dicyclopentenyloxyethyl acrylate, 1,4-butanediol diacrylate, 1,10-decanediol diacrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate, and derivatives thereof.

10. The curable composition of any one of claims 1 to 9, wherein the acrylate monomer comprises a mixture of different acrylate monomers.

11. The curable composition of any one of claims 1 to 10, comprising up to 5 wt% of a photoinitiator, based on the total weight of the curable composition.

12. The curable composition of any one of claims 1 to 11, comprising up to 3 wt% of a photosensitizer, based on the total weight of the curable composition.

13. The curable composition of any one of claims 1 to 12, wherein the photoinitiator is a combination of a metal-free cationic photoinitiator and a radical photoinitiator.

14. 14. The curable composition of claim 1, wherein the total amount of the shrinkage-reducing monomer, the acrylate monomer, the photoinitiator, and the photosensitizer is at least 98% by weight, based on the total weight of the curable composition.

15. The curable composition of any one of claims 1 to 14, further comprising a surfactant.

16. 16. The curable composition according to claim 1, wherein the amounts of the monomer that reduces shrinkage of the curable composition and the monomer that reduces shrinkage of the curable composition, the amounts of the acrylate monomer and the acrylate monomer, and the total amount of the monomer that reduces shrinkage of the curable composition and the acrylate monomer are selected so that a volume of a cured product obtained by curing the curable composition shrinks by 3.0% or less from the volume of the curable composition before curing.

17. a first chuck configured to grip the template or superstrate; a second chuck configured to grip the substrate; A dispensing system configured to dispense the curable composition of any one of claims 1 to 16 onto the substrate; a positioning system configured to bring the template or the superstrate into contact with the curable composition on the substrate; a radiation source configured to cure the curable composition by exposing the curable composition to radiation; and A nanoimprint lithography system comprising:

18. Contacting the curable composition of any one of claims 1 to 16 on a substrate with a template or superstrate; curing the curable composition by exposing the curable composition to radiation to form a cured composition; Separating the template or the superstrate from the hardened composition; and treating the substrate on which the cured composition is formed to produce an article; and A method of making an article comprising:

19. the curable composition has a first volume before curing and the cured composition has a second volume after curing; 20. The method of claim 18, wherein the second volume is no more than 3.5% smaller than the first volume.

20. a first chuck configured to grip the superstrate; a second chuck configured to grip the substrate; A dispensing system configured to dispense the curable composition of any one of claims 1 to 16 onto the substrate; a positioning system configured to bring the superstrate into contact with the curable composition on the substrate; a radiation source configured to cure the curable composition by exposing the curable composition to radiation; and A system for planarization comprising:

21. Contacting the curable composition of any one of claims 1 to 16 on a substrate with a superstrate; curing the curable composition by exposing the curable composition to radiation to form a cured composition; separating the superstrate from the cured composition; and treating the substrate on which the cured composition is formed to produce an article; and A method of making an article comprising:

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