TW201723649A - Substrate pretreatment for reducing fill time in nanoimprint lithography - Google Patents

Abstract

A nanoimprint lithography method includes disposing a pretreatment composition on a substrate to form a pretreatment coating. The pretreatment composition includes a polymerizable component. Discrete imprint resist portions are disposed on the pretreatment coating, with each discrete portion of the imprint resist covering a target area of the substrate. A composite polymerizable coating is formed on the substrate as each discrete portion of the imprint resist spreads beyond its target area. The composite polymerizable coating includes a mixture of the pretreatment composition and the imprint resist. The composite polymerizable coating is contacted with a template, and is polymerized to yield a composite polymeric layer on the substrate. The interfacial surface energy between the pretreatment composition-and air exceeds the interfacial surface energy between the imprint resist and air or between at least a component of the imprint resist and air.

Description

Substrate pretreatment for shortening the filling time in nanoimprint microdisplay [Related application]

This application is related to U.S. Patent Application Serial No. 15/195,789, entitled "SUBSTRATE PRETREATMENT FOR REDUCING FILL TIME IN NANOIMPRINT LITHOGRAPHY", filed on June 28, 2016, which claims to be filed on January 22, 2016 The name of the U.S. Patent Application Serial No. 15/004,679, entitled "SUBSTRATE PRETREATMENT FOR REDUCING FILL TIME IN NANOIMPRINT LITHOGRAPHY", which claims to be "SUBSTRATE PRETREATMENT FOR REDUCING FILL TIME" on September 8, 2015. The priority of U.S. Patent Application Serial No. 62/215,316, the entire disclosure of which is incorporated herein by reference.

SUMMARY OF THE INVENTION The present invention is directed to a technique for improving the yield of nanoimprint lithography by processing a nanoimprint lithography substrate to enhance the spread of the embossed photoresist material on the substrate.

As the semiconductor processing industry strives to increase production per unit of circuit while increasing the number of circuits per unit, attention has been focused on the continued development of reliable high-resolution patterning techniques. One of the techniques used today is commonly referred to as imprint lithography. The embossing lithography process is described in detail in a number of publications, such as U.S. Patent Application Publication No. 2004/0065252, and U.S. Patent No. 6,936,194, the disclosure of which is incorporated herein by reference. . Other areas of development that have used imprint lithography include biotechnology, optical technology, and mechanical systems.

An imprint lithography technique as described in each of the aforementioned patent documents includes forming a relief pattern in an imprint photoresist material and transferring a pattern corresponding to the concavo-convex pattern to a bottom On the substrate. The patterning process uses a template spaced apart from the substrate and a polymerizable component (imprinted photoresist material) between the template and the substrate. In some cases, the embossed photoresist material is disposed on the substrate in the form of separate, spaced apart droplets. The droplets are allowed to expand before the embossed photoresist material contacts the stencil. After the embossed photoresist material contacts the stencil, the photoresist material is allowed to uniformly fill a space between the substrate and the stencil, and then the embossed photoresist material is cured to form a layer having a A pattern that retains the shape of the surface of the template. Between curing, the template is separated from the patterned layer such that the template and the substrate are separated.

The yield of an embossing lithography process is roughly dependent on many factors. When the embossed photoresist material is disposed on the substrate in the form of separate, spaced apart droplets, the yield is dependent at least in part on the efficiency and uniformity of the expansion of the droplets on the substrate. degree. The expansion of the embossed photoresist material can be limited by a number of factors, such as an air gap between the droplets and the substrate and/or the template being wetted by the droplets that are not completed.

In a first aspect, a nanoimprint lithography method includes disposing a pretreatment composition on a substrate to form a pretreatment coating on the substrate, and separating the embossed photoresist A portion of the material is disposed on the pretreatment coating, and each of the separate imprinted photoresist materials partially covers a target region of the substrate. The pretreatment composition comprises a polymerizable component and the imprinted photoresist material is a polymerizable component. A polymerizable coating comprising a composite of the pretreatment composition and the imprinted photoresist material is formed on the substrate as each discrete embossed photoresist material portion extends beyond its target area. The synthetic polymerizable coating is contacted with a nanoimprint lithography template and polymerized to produce a synthetic polymeric layer on the substrate. The interfacial surface energy between the pretreatment composition and the air is greater than the interfacial energy between the imprinted photoresist material and the air or between at least one component of the imprinted photoresist material and the air.

The second aspect includes a nanoimprint lithography stack formed by the method of the first aspect.

The third aspect includes a method of fabricating a device using the first aspect. The device can be a treated substrate, an optical member, or a quartz mold replica.

The fourth aspect includes the device fabricated in the third aspect.

In a fifth aspect, a nanoimprint lithography kit includes a pretreatment composition and an imprint photoresist material. The pretreatment composition comprises a polymerizable component, the imprinted photoresist material is a polymerizable composition, and an interface energy between the pretreatment composition and air is greater than the imprinted photoresist material and air The interfacial energy between at least one component of the imprinted photoresist material and the air.

In a sixth aspect, a method of pretreating a nanoimprint lithography substrate comprises coating the substrate with a pretreatment composition and disposing a separate portion of the imprinted photoresist material in the pretreatment composition on. The pretreatment composition comprises a polymerizable component. The embossed photoresist material disposed within the separate portions of the pretreatment composition expands faster than the embossed photoresist material disposed within the portion of the same substrate that is free of the pretreatment composition. After a defined length of time between the arrangement of the separated portions of the imprinted photoresist material on the pretreatment composition and the contact of the imprinted photoresist material with the nanoimprint lithography template, The embossed photoresist material is in contact with a nano-imprint lithography template. When the embossed photoresist material is in contact with the nanoimprint lithography template, the volume of the gap between the separated portions of the embossed photoresist material disposed on the pretreatment composition is less than The configuration of the separated portions of the imprinted photoresist material in the portion of the substrate that does not have the pretreatment composition has passed the defined length of time The volume of the gap between the same imprinted photoresist material disposed within the portion of the same substrate that does not have the pretreatment composition.

In a seventh aspect, a nanoimprint lithography stack includes a nanoimprint lithography substrate and a synthetic polymeric layer formed on a surface of the nanoimprint lithography substrate. The chemical composition of the synthesized polymeric layer is non-uniform and includes a plurality of central regions separated by boundaries. The chemical composition of the synthesized polymeric layer at the boundary is different from the chemical composition of the synthetic polymeric layer within the central region. In some cases, the nanoimprint lithography substrate includes an adhesive layer, and the resultant polymeric layer is formed on a surface of the adhesive layer. In some cases, the central region and boundaries of the resultant polymeric layer are formed from a heterogeneous mixture of a pretreatment composition and an embossed photoresist material.

Implementations of the above aspects may include one or more of the following features or may be formed by a process or member that includes one or more of the following features.

Disposing the pretreatment composition on the nanoimprint lithography substrate can be accomplished by spin coating the pretreatment composition onto the nanoimprint lithography substrate. In some cases, the nanoimprint lithography substrate comprises an adhesive layer, and disposing the pretreatment composition on the nanoimprint lithography substrate comprises disposing the pretreatment composition on the adhesive On the floor.

Disposing the separate portions of the embossed photoresist material on the pretreatment coating can include dispensing droplets of the embossed photoresist material onto the pretreatment coating. In some cases, a separate portion of the imprinted photoresist material contacts at least one other discrete portion of the imprinted photoresist material that contacts the nanoimprint lithography template at the resultant polymerizable coating. Preform A boundary between two separate parts. When the synthetic polymerizable coating contacts the nanoimprint lithography template, each separate portion of the imprinted photoresist material and at least one other separated portion of the imprinted photoresist material may be subjected to the pre-preparation The treatment composition is separated. In some cases, the synthetic coating is a heterogeneous mixture of the pretreatment composition and the imprinted photoresist material.

Polymerizing the synthetic polymerizable coating to produce the synthetic polymeric layer can include covalently bonding a component of the pretreatment composition to a component of the imprinted photoresist material. The chemical composition of the synthetic polymerizable coating can be non-uniform. The nanoimprint lithography template and the synthetic polymerizable coating can be separated.

In some cases, the difference between the interface energy between the pretreatment composition and air and the interfacial energy between the imprinted photoresist material and air is between 0.5 mN/m and 25 mN/m, 0.5 mN/ m to 15 mN/m, or within the range of 0.5 mN/m to 7 mN/m. In some cases, the interfacial energy between the imprinted photoresist material and air is in the range of 20 mN/m to 60 mN/m, 28 mN/m to 40 mN/m, or 32 mN/m to 35 mN/m. In other cases, the interfacial energy between the pretreatment composition and air is in the range of 30 mN/m to 45 mN/m. The viscosity of the pretreatment composition at 23 ° C is typically in the range of 1 cP to 200 cP, 1 cP to 100 cP, or 1 cP to 50 cP, and the viscosity of the imprinted photoresist material at 23 ° C is typically from 1 cP to 50 cP. , from 1 cP to 25 cP, or from 5 cP to 15 cP.

The pretreatment composition can include a monomer. In some cases, the pretreatment composition comprises a single monomer consisting essentially of a single monomer or a single monomer. In some cases, the pretreatment composition includes two or more monomers (eg, monofunctional, difunctional, or polyfunctional acrylate monomers). The pretreatment composition may include propoxylated (3) trimethylolpropane triacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, trimethylolpropane ethoxy triacrylate, 1,12-dodecanediol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,3-adamantanediol diacrylate, decanediol diacrylate, m-two Toluene diacrylate, tricyclodecane dimethanol diacrylate, or any combination thereof. The pretreatment composition may include 1,12-dodecanediol diacrylate, tricyclodecane dimethanol diacrylate, or a combination thereof; tetraethylene glycol diacrylate, tricyclodecane dimethanol diacrylate Or a combination thereof; 20 wt% to 40 wt% 1,12-dodecanediol diacrylate and 60 wt% to 80 wt% tricyclodecane dimethanol diacrylate; or about 30 wt% 1,12-dodecane di Alcohol diacrylate and about 70% by weight of tricyclodecane dimethanol diacrylate. In some cases, the pretreatment composition is free of a polymerization initiator.

The imprinted photoresist material may comprise from 0 wt% to 80 wt%, from 20 wt% to 80 wt%, or from 40 wt% to 80 wt% of one or more monofunctional acrylates; from 20 wt% to 98 wt% of one or more difunctional groups Or a polyfunctional acrylate; from 1% to 10% by weight of one or more photoinitiators; and from 1% to 10% by weight of one or more surfactants. In some cases, the embossed photoresist material comprises from 90 wt% to 98 wt% of one or more difunctional or polyfunctional acrylates and is substantially free of monofunctional acrylates. in In some cases, the embossed photoresist material comprises one or more monofunctional acrylates and from 20% to 75% by weight of one or more difunctional or polyfunctional acrylates.

The polymerizable component of the pretreatment composition and a polymerizable component of the imprinted photoresist material can react to form a covalent bond during polymerization of the synthetic polymerizable coating. The pretreatment composition and the imprinted photoresist material may each comprise a monomer having a common functional group (eg, an acrylate group).

The details of one or more embodiments of the inventive subject matter described in this specification are presented in conjunction with the drawings and the description below. Other features, aspects, and advantages of the invention will become apparent from the following description, drawings, and claims.

100‧‧‧imprint lithography system

102‧‧‧Substrate

104‧‧‧Substrate chuck

106‧‧‧Table

108‧‧‧ Template

110‧‧‧ platform

112‧‧‧Surface pattern

114‧‧‧ spaced apart depressions

116‧‧‧ bumps

118‧‧‧ chuck

120‧‧ ‧ Imprint head

122‧‧‧ Fluid Dispensing System

124‧‧‧ Imprinted photoresist material

126‧‧‧Energy source

128‧‧‧ Path

130‧‧‧Processor

132‧‧‧ memory

134‧‧‧ surface

200‧‧•Nano imprint lithography stack

202‧‧‧ patterned polymeric layer

204‧‧‧Residual layer

206‧‧‧ bumps

208‧‧‧ dent

T1‧‧‧ thickness

T2‧‧‧ thickness

300‧‧‧First liquid

302‧‧‧Second liquid

304‧‧‧Substrate

306‧‧‧ gas

400‧‧‧Process

402-410‧‧‧ operation

500‧‧‧Base

502‧‧‧Adhesive layer

506‧‧‧Pretreatment coating

504‧‧‧Pretreatment composition

Tp‧‧‧ thickness

600‧‧‧Dropped droplets of liquid photoresist (droplets)

602‧‧‧Target area

604‧‧‧Synthetic coating

606‧‧‧Area

608‧‧‧Area

610‧‧‧ border

900‧‧‧Synthetic coating

902‧‧N. Nanoimprint lithography stack

904‧‧‧Synthesized polymeric layer

1000‧‧‧Synthetic coating

1002‧‧•nano imprint lithography stack

1004‧‧‧polymer layer

1006‧‧‧Area

1008‧‧‧Area

1100‧‧‧ droplets

1102‧‧‧Adhesive layer

1104‧‧‧ Ring

1200‧‧‧ droplets

1202‧‧‧Pretreatment coating

1204‧‧‧Synthetic coating

1206‧‧‧ border

1208‧‧‧Area

1300‧‧‧ droplets

1302‧‧‧Pretreatment coating

1306‧‧‧ border

1400‧‧‧ droplets

1402‧‧‧Pretreatment coating

1404‧‧‧Synthetic coating

1406‧‧‧ border

PC1-PC9‧‧‧Pretreatment composition

Figure 1 shows a simplified side view of a lithography system.

Figure 2 shows a simplified side view of the substrate shown in Figure 1 with a patterned layer formed thereon.

Figures 3A-3D show the extended interaction between droplets of a second liquid on a first liquid layer.

Figure 4 is a flow chart showing a process for promoting the yield of nanoimprint lithography.

Figure 5A shows a substrate. Figure 5B shows a pretreatment coating disposed on the substrate.

Figures 6A-6D show the configuration from a pretreatment coating The droplets of the imprinted photoresist material on the substrate form the formation of a synthetic coating.

Figures 7A-7D show cross-sectional views along the w-w, x-x, y-y, and z-z lines of Figures 6A-6D, respectively.

Figures 8A and 8B show a pretreatment coating displaced by droplets on a substrate.

Figures 9A-9C show cross-sectional views of a template in contact with a homogeneous synthetic coating and the results of the resulting nanoimprint lithography stack.

Figures 10A-10C show cross-sectional views of a template in contact with a heterogeneous synthetic coating and the results of the resulting nanoimprint lithography stack.

Figure 11 is an image of a droplet corresponding to the imprinted photoresist material of Comparative Example 1 after being spread over an adhesive layer of a substrate without a pretreatment coating.

Figure 12 is an image of the droplets of the imprinted photoresist material described in Example 1 after being spread over a pretreatment coating.

Figure 13 is an image of the droplets of the imprinted photoresist material described in Example 2 after being spread over a pretreatment coating.

Figure 14 is an image of the droplets of the imprinted photoresist material described in Example 3 after being spread over a pretreatment coating.

Figure 15 shows the defect density as a function of the pre-expansion time for the imprinted photoresist material and the pre-treatment of Example 2.

Figure 16 shows the droplet diameter vs. the time to extend the pretreatment composition.

Figure 17A shows the viscosity as a function of the fractional fraction of one of the two component pretreatment compositions. Figure 17B The droplet diameter vs. different fractions of the pretreatment composition of the two components are shown. Figure 17C shows the surface tension vs. the fraction of one component of the pretreatment composition of the two components.

FIG. 1 shows an imprint lithography system 100 that is used to form a relief pattern on a substrate 102. The substrate 102 can include a substrate and an adhesive layer adhered to the substrate. Substrate 102 can be coupled to substrate chuck 104. As shown, the substrate chuck 104 is a vacuum chuck. However, the substrate chuck 104 can be, but is not limited to, vacuum, pin, groove, electromagnetic, and/or the like. An exemplary collet is described in U.S. Patent No. 6,873,087, the disclosure of which is incorporated herein by reference. Substrate 102 and substrate chuck 104 can be further supported by table 106. Table 106 can provide motion along the x-axis, y-axis, and z-axis. The table 106, the substrate 102, and the substrate holder 104 can also be disposed on a pedestal.

Separated from the substrate 102 is a template 108. The template 108 generally includes a rectangular or square mesa 110 that projects some distance from the surface of the substrate 102. A surface of the platform 110 can be patterned. In some cases, platform 110 is referred to as mold 110 or mask 110. Template 108, mold 110, or both may include, but are not limited to, fused vermiculite, quartz, tantalum, niobium nitride, organic polymers, siloxane polymers, borosilicate glass, fluorocarbon polymers, metals (eg, Chromium, bismuth), hardened sapphire, and the like, or a combination thereof, are formed. As shown, the pattern 112 of the surface includes a plurality of spaced apart The features defined by the recesses 114 and the projections 116 are not limited to these configurations. The pattern 112 of the surface can define any original pattern that forms the basis of a pattern to be formed on the substrate 102.

The template 108 is coupled to the collet 118. The collet 118 is typically constructed, but not limited to, a vacuum, pin, groove, electromagnetic, or other similar type of collet. An exemplary collet is described in U.S. Patent No. 6,873,087, the disclosure of which is incorporated herein by reference. Additionally, the collet 108 can be coupled to the imprint head 120 such that the collet 118 and/or the imprint head 120 can be constructed to facilitate movement of the template 108.

System 100 can further include a fluid dispensing system 122. The fluid dispensing system 122 can be used to place the imprinted photoresist material 124 on the substrate 102. The imprinted photoresist material 124 can be used, for example, in droplet dispensing, spin coating, immersion coating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thin film deposition, thick film deposition, or the like. Techniques are deposited on the substrate 102. In the droplet dispensing method, the embossed photoresist material 124 is disposed on the substrate 102 in the form of separate, spaced apart droplets, as shown in FIG.

System 100 can further include an energy source 126 coupled to direct energy along path 128. Imprint head 120 and table 106 can be constructed to place the template 108 and the substrate 102 in a manner that overlaps the path 128. The system 100 can be adjusted by a processor 130 that communicates with the table 106, the embossing head 120, the fluid dispensing system 122, and/or the energy source 126, and can be stored in a computer readable program stored in the memory 132. To operate.

The embossing head 120 can apply a force to the stencil 108 such that the mold 110 contacts the embossed photoresist material 124. After the desired space has been filled with the imprinted photoresist material 124, the energy source 126 generates energy (eg, electromagnetic radiant energy or thermal energy), causing the imprinted photoresist material 124 to cure (eg, polymerize and/or crosslink) The shape of the surface 134 of the substrate 102 is followed and the surface 112 is patterned. After the imprinted photoresist material 124 is cured to form a polymeric layer on the substrate 102, the mold 110 and the polymeric layer are separated.

2 shows a nanoimprint lithography stack 200 formed by curing embossed photoresist material 124 to create a patterned polymeric layer 202 on substrate 102. The imprinted photoresist material 124 of the patterned layer 202 can include a residual layer 204 and a plurality of features configured as bumps 206 and recesses 208, wherein the bumps 206 have a thickness t ₁ and the residual layer 204 has a thickness t ₂ . In nanoimprint lithography, one or more of the protrusions 206, recesses 208, or both are parallel to the length of the substrate 102 of less than 100 nm, less than 50 nm, or less than 25 nm. In some cases, the length of one or more of the protrusions 206, recesses 208, or both is between 1 nm and 25 nm, or between 1 nm and 10 nm.

The above described systems and processes can be further implemented in other embossing lithography processes and systems, such as those described in U.S. Patent Nos. 6,932,934, 7,077,992, 7,197,396, and 7,396,475. The contents of these patents are hereby incorporated by reference.

For the imprinted photoresist material 124 disposed on the substrate 102 as a separate portion ("droplet") as shown in Figure 1 For drop-on-demand or droplet dispensing nanoimprint lithography, droplets of the imprinted photoresist material typically extend to the substrate before and after the mold 110 contacts the imprinted photoresist material. On the material 102. If the expansion of the droplets of the imprinted photoresist material 124 is insufficient to cover the substrate 102 or fill the recesses 114 of the mold 110, the polymeric layer 202 may be formed to have defects in the form of voids. Accordingly, the on-demand liquid-implanted nanoimprint lithography process typically includes a movement of the imprinted photoresist material 124 to begin dispensing and the mold 110 begins to move toward the substrate 102 ( And a delay between the subsequent filling of the space between the substrate and the template. Thus, the yield of an automated nanoimprint lithography process is typically limited by the rate of diffusion of the imprinted photoresist material onto the substrate and the fill rate of the stencil. Thus, the yield of on-demand liquid or droplet dispensing nanoimprint lithography can be achieved by shortening the "fill time" (ie, completely filling the space between the template and the substrate). The gap does not exist for the required time) to improve.

One way to reduce the fill time is to increase the rate of expansion of the droplets of the imprinted photoresist material and the coverage of the imprinted photoresist material over the substrate before the movement of the mold toward the substrate is initiated. Increasing the coverage of the substrate reduces the volume of the gap between the droplets of the imprinted photoresist material, thereby reducing the entrapment in the gaps as the imprinted photoresist material contacts the mold The amount of gas reduces the amount and severity of defects in the formed patterned layer. As described herein, the rate of expansion of the imprinted photoresist material and the uniformity of substrate coverage can be improved by pretreating the substrate with a liquid that promotes the pressure during formation of the patterned layer. The separated portion of the printed photoresist material spreads quickly and evenly and the embossed photoresist The material is polymerized such that the amount of gas trapped within the gap and the number and severity of defects within the resulting patterned layer as the embossed photoresist contacts the mold are reduced.

The expansion of the separated portion of a second liquid on a first liquid can be understood by reference to Figures 3A-3D. 3A-3D show the first liquid 300 and the second liquid 302 being in contact with the substrate 304 and with a gas 306 (eg, a combination of air, blunt gas, such as helium or nitrogen, or blunt gas). The first liquid 300 appears on the substrate 304 in the form of a coating or layer (the coatings and layers are used interchangeably herein). In some cases, the first liquid 300 appears as a layer having a thickness of a few nanometers (eg, between 1 nm and 15 nm, or between 5 nm and 10 nm). The second liquid 302 appears as a separate portion ("droplet"). The characteristics of the first liquid 300 and the second liquid 302 may be different with respect to each other. For example, in some cases, the first liquid 300 is more viscous and denser than the second liquid 302.

The interfacial energy, or surface tension, between the second liquid 302 and the first liquid 300 is labeled γ _L1L2 . The interface between the first liquid 300 and the gas 306 can be labeled as γ _L1G . The interface between the second liquid 302 and the gas 306 can be labeled as γ _L2G . The interface between the first liquid 300 and the substrate 304 can be labeled as γ _SL1 . The interface between the second liquid 302 and the substrate 304 can be labeled as γ _SL2 .

FIG. 3A shows the second liquid 302 as a droplet that is dropped on the first liquid 300. The second liquid 302 does not deform the first liquid 300 and does not contact the substrate 304. As shown, the first liquid 300 and the second liquid 302 are not mixed with each other, and the interface between the first liquid and the second liquid is shown to be flat. At equilibrium, the contact angle of the second liquid 302 on the first liquid 300 is θ, which is related to the interfacial energy γ _L1G , γ _L2G and γ _L1L2 by the Young's equation: γ _{L 1 G} = γ _{L 1 L 2} + γ _{L 2 G} . Cos(θ) (1) If, Then θ = 0°, and the second liquid 302 is completely expanded on the first liquid 300. If the first and second liquids are mixed with each other, then after a period of time, γ _{L 1 L 2} =0 (3). In this case, the condition that the second liquid 302 is completely expanded on the first liquid 300 is For the first liquid 300 to be a thin film and the second liquid 302 to be a small liquid droplet, the mixing with each other can be restricted by a diffusion treatment. Therefore, in order to expand the second liquid 302 onto the first liquid 300, when the second liquid 302 is dropped on the first liquid 300 in the form of droplets, the inequality (2) is more suitable for the initial stage of expansion.

FIG. 3B shows the contact angle of the droplets forming the second liquid 302 when the bottom layer of the first liquid 300 is thick. In this example, the droplet does not contact the substrate 304. The droplets of the second liquid 302 and the layers of the first liquid 300 intersect at angles α , β, and θ, where α + β + θ = 2 π (5) There are three conditions for the force balance along each interface: γ _{L 2 G} + γ _{L 1 L 2} . Cos(θ)+ γ _{L 1 G} . Cos( α )=0 (6)

γ _{L 2 G} . Cos(θ)+ γ _{L 1 L 2} + γ _{L 1 G} . Cos(β)=0 (7)

γ _{L 2 G} . Cos( α )+ γ _{L 1 L 2} . Cos(β)+ γ _{L 1 G} =0 (8) If the first liquid 300 and the second liquid 302 are mixed with each other, γ _{L 1 L 2} =0 (9) and the equations (6)-(8) Becomes: γ _{L 2 G +} γ _{L 1 G} . Cos( α )=0 (10)

γ _{L 2 G} . Cos(θ)+ γ _{L 1 G} . Cos(β)=0 (11)

γ _{L 2 G} . Cos( α )+ γ _{L 1 G} =0 (12) Equations (10) and (12) are given And α =0, π (14) when the second liquid 302 wets the first liquid 300, α = π (15)

γ _{L 2 G} = γ _{L 1 G} (16) and equation (11) gives cos(θ) + cos(β) = 0 (17). This result is given in conjunction with equations (5) and (15). =0 (18)

β = π (19) Therefore, equations (15), (18), and (19) give solutions for angles α , β, and θ. when There is no balance between these interfaces. Equation (12) becomes an inequality, even if α = π , and the second liquid 302 continuously expands on the first liquid 300.

3C shows a more complex geometry of a droplet of the second liquid 302 that contacts the substrate 304 while also having an interface with the first liquid 300. An interface region between the first liquid 300, the second liquid 302, and the gas 306 (defined by the angles α , β, θ ₁ ) and the first liquid 300, the second liquid 302, and the substrate 304 The interfacial region (which is defined by the angle θ ₂ ) must be considered to determine the spreading behavior of the second liquid on the first liquid.

The interface region between the first liquid 300, the second liquid 302, and the gas 306 is dominated by equations (6)-(8). Since the first liquid 300 and the second liquid 302 are not mixed with each other, γ _{L 1 L 2} =0 (21) Equation (14) gives the solution of the angle α . In this example, assume that α = 0 (22) and θ ₁ = π (23)

== π (24) At the same time, there is no balance between the droplets of the second liquid 302 and the first liquid 300, and the droplets continuously expand along the interface between the second liquid and the gas until they are otherwise physically restricted (eg, volumetric balance and mutual Mixed) is limited.

Regarding the interface region between the first liquid 300, the second liquid 302, and the substrate 304, an equation similar to the equation (1) should be considered: γ _{SL 1} = γ _{SL 2} + γ _{L 1 L 2} . Cos(θ ₂ ) (26)

The droplet is fully expanded and θ ₂ =0.

Again, for liquids that can be mixed with each other, the second term γ _L1L2 =0, and inequality (27) is reduced to

When energy before and after expansion is considered, the binding condition for droplet expansion is expressed as

This should have a better energy conversion (ie, a conversion that minimizes the energy of the system).

A different relationship between the four terms in inequality (29) will determine the droplet extension feature. If inequality (25) is valid and equation (28) is not valid, the droplets of the second liquid 302 may initially expand along the surface of the first liquid 300. Alternatively, as long as inequality (28) can be maintained and inequality (25) cannot be maintained, the droplets can begin to expand along the liquid-solid interface. Eventually, the first liquid 300 and the second liquid 302 will mix with one another, thus introducing more complexity.

3D shows a pattern of droplets of a second liquid 302 that contacts the substrate 304 while having an interface with the first liquid 300. As shown in Figure 3D, each of the two droplets of the second liquid 302 has two intersecting interface regions. The first interface region is where the first liquid 300, the second liquid 302, and the gas 306 meet, and is indicated by angles α , β, and θ ₁ . The second interface region of the intersection is where the first liquid 300, the second liquid 302, and the substrate 304 meet, which is indicated by the angle θ ₂ . Here, when the surface tension between the interface between the second liquid 302 and the substrate 304 is greater than the surface tension between the first liquid 300 and the substrate (γ _SL2) When γ _SL1 ), θ _{1 is} close to 0° and θ _{2 is} close to 180° as the droplet expands. That is, the droplet of the second liquid 302 expands along the interface between the first liquid 300 and the second liquid and does not spread along the interface between the second liquid and the substrate 304.

Equations (6)-(8) are applicable to the interface between the first liquid 300, the second liquid 302, and the gas 306. The first liquid 300 and the second liquid 302 are not mixed with each other, so γ _{L 1 L 2} =0 (30).

Equation (14) gives the solution of the angle α . For α = π (31), equation (11) gives cos(θ ₁ ) + cos(β) = 0 (32) and θ ₁ = 0 (33)

== π (34) At the same time, there is no balance between the droplets of the second liquid 302 and the first liquid 300, and the droplets continuously expand along the interface between the second liquid and the gas until they are otherwise physically restricted (eg, volumetric balance and mutual Mixed) is limited.

Regarding the interface region between the second liquid 302 and the substrate 304, γ _SL1 = γ _SL2 + γ _L1L2 . Cos(θ ₂ ) (36)

in case And the liquids are not mixed with each other, that is, γ _{L 1 L 2} →0 (39)

Then, the angle θ _{2 is} close to 180° and then becomes undefined. That is, the second liquid 302 has a tendency to shrink along the substrate interface and expand along the interface between the first liquid 300 and the gas 306.

The expansion of the second liquid 302 on the first liquid 300 and the surface energy relationship for full expansion can be summarized into three different situations. In the first case, the droplets of the second liquid 302 are disposed on the layer of the first liquid 300, and the droplets of the second liquid 302 are not in contact with the substrate 304. The layer of the first liquid 300 may be thick or thin, and the first liquid 300 and the second liquid 302 are not miscible with each other. Under ideal conditions, when the surface energy of the first liquid 300 in the gas 306 is greater than or equal to the surface energy of the second liquid 302 in the gas ( γ _{L 1 G} At γ _{L 2 G} ), complete expansion of the droplets of the second liquid 302 can occur on the layers of the first liquid 300. In the second case, droplets of the second liquid 302 are disposed on the layer of the first liquid 300 while contacting the substrate 304 and expanding over the substrate 304 at the same time. The first liquid 300 and the second liquid 302 are not miscible with each other. Under ideal conditions, when: (i) the surface energy of the first liquid 300 in the gas is greater than or equal to the surface energy of the second liquid 302 in the gas ( γ _{L 1 G} γ _{L 2 G} ); and (ii) the surface energy of the interface between the first liquid and the substrate 304 is greater than the surface energy of the interface between the second liquid and the substrate ( γ _{SL 1} When γ _{SL 2} ), a complete extension will occur. In the third case, the droplets of the second liquid 302 are disposed on the layer of the first liquid 300 while contacting the substrate 304. The expansion may occur along the interface between the second liquid 302 and the first liquid 300 or the interface between the second liquid and the substrate 304. The first liquid 300 and the second liquid 302 are not miscible with each other. In an ideal situation, the complete expansion is at (i) the sum of the surface energy of the first liquid 300 in the gas and the surface energy of the interface between the first liquid and the substrate 304 is greater than or equal to the second liquid 302 in the gas The sum of the surface energy in the surface energy and the surface energy between the second liquid and the substrate ( γ _{L 1 G} + γ _{SL 1} γ _{L 2 G} + γ _{SL 2} ), while the surface energy of the first liquid 300 in the gas is greater than or equal to the surface energy of the second liquid 302 in the gas ( γ _{L 1 G} γ _{L 2 G} ), or at (ii) the surface energy of the interface between the first liquid and the substrate 304 is greater than the surface energy of the interface between the second liquid and the substrate ( γ _{SL 1} γ _{SL 2} ) occurs. When the second liquid 302 includes more than one component, the complete expansion is greater than or equal to (i) the sum of the surface energy of the first liquid 300 in the gas and the surface energy of the interface between the first liquid and the substrate 304. Equal to the sum of the surface energy of the second liquid 302 in the gas and the surface energy of the interface between the second liquid and the substrate ( γ _{L 1 G} + γ _{SL 1} γ _{L 2 G} + γ _{SL 2} ) while the surface energy of the first liquid 300 in the gas is greater than or equal to the surface energy of at least one component of the second liquid 302 in the gas, or (ii) between the first liquid Occurs when the surface energy of the interface between the substrate 304 and the substrate is greater than the surface energy of the interface between the component of the second liquid and the substrate.

Pretreating a nanoimprint lithographic substrate by using a selected liquid pretreatment composition for having a surface energy greater than that of the imprinted photoresist material in an ambient atmosphere (eg, air or blunt gas) Surface energy, in an on-demand liquid nanoimprint lithography process, the rate at which the imprinted photoresist material spreads over the substrate can be increased and the imprint is applied before the imprinted photoresist material contacts the template A more uniform thickness of the photoresist material on the substrate can be established to promote the yield of the nanoimprint lithography process. This substrate pretreatment process shortens the dispensing time by improving droplet expansion and reducing the gap volume between the embossed photoresist droplets prior to imprinting. As used herein, "dispensing time" generally refers to the time between the dispensing of a droplet and the contact of a droplet with a template. If the pretreatment composition comprises a polymerizable component capable of being mixed with the imprinted photoresist material, this can make a favorable contribution to the formation of the polymer layer without adding an undesired component, and can be obtained more uniformly. The curing results to provide more uniform mechanical and etch characteristics.

4 is a flow chart showing a process 400 for increasing the yield of a solution-on-demand nanoimprint lithography process. Process 400 includes operations 402-410. In operation 402, a pretreatment composition is disposed on a nanoimprint lithography substrate to form a pretreatment coating on the substrate. In operation 404, separate portions ("droplets") of the imprinted photoresist material are disposed on the pretreatment coating, wherein each droplet covers the A target area of the substrate. The pretreatment composition and the imprinted photoresist material are selected such that an interface energy between the pretreatment composition and the air is higher than an interfacial energy between the imprinted photoresist material and air.

In operation 406, a synthetic polymerizable coating ("synthetic coating") is formed on the substrate as each droplet of the imprinted photoresist material expands beyond its target area. The composite coating comprises a homogenous or heterogeneous mixture of the pretreatment composition and the imprinted photoresist material. In operation 408, the composite coating is in contact with a nanoimprint lithography template ("template") and is allowed to expand and fill the space between the template and the substrate, and in operation 410 The synthetic coating is polymerized to obtain a polymeric layer on the substrate. After polymerization of the resultant coating, the template is separated from the polymeric layer leaving a nanoimprinted lithographic stack. As used herein, "nanoimprint lithography stack" generally refers to the substrate and a polymeric layer adhered to the substrate, either or both of the substrate and the polymeric layer. Includes one or more additional layers (eg, between them). In one example, the substrate includes a base and an adhesive layer adhered to the substrate.

During the expansion of the photoresist material, the surface energy of the imprinted photoresist material plays an important role in the capillary action between the template and the substrate. The pressure difference across the formed capillary meniscus is proportional to the surface energy of the liquid. The higher the surface energy, the greater the driving force for liquid expansion. Therefore, typically, the higher the surface energy, the better the imprinted photoresist material. While interacting with a pretreatment composition, the dynamics of the droplet extension of the photoresist material depends on the viscosity of both the imprinted photoresist material and the pretreatment composition. An imprinted photoresist material or pretreatment composition having a higher viscosity tends to slow the droplet extension power, and thus, for example, slows down the imprint process. The capillary pressure difference is proportional to the interfacial tension ( γ ) and inversely proportional to the effective radius ( γ ) and also depends on the wetting angle θ of the liquid on the surface of the capillary. Imprinted photoresist materials with high surface tension and low contact angle are desirable for fast filling in nanoimprint lithography. The contact angle of the embossed photoresist material on the surface of the surface of the embossed lithography template is typically less than 90°, less than 50°, or less than 30°.

In process 400, the pretreatment composition and the embossed photoresist material are described, for example, in U.S. Patent No. 7,157,036 and U.S. Patent No. 8,076,386, and in Chou et al. 1995, 'Imprint of sub-25 nm vias and trenches in Polymers', Applied Physics Letters 67(21): 3114-3116; Chou et al. 1996, 'Nanoimprint lithography', Journal of Vacuum Science Technology B 14(6): 4129-4133; and Long et al. 2007, 'Materials for step And flash imprint lithography (S-FIL®)', Journal of Materials Chemistry 17: 3575-3580, etc., the contents of which are incorporated herein by reference. Suitable ingredients include polymerizable monomers ("monomers"), crosslinkers, resins, photoinitiators, surfactants, or any combination thereof. The types of monomers include acrylates, methacrylates, vinyl ethers, and epoxides, as well as their polyfunctional derivatives. In some sentiments In this case, the pretreatment composition, the imprinted photoresist material, or both are substantially free of defects. In other cases, the pretreatment composition, the imprinted photoresist material, or both are germanium-containing. The ruthenium-containing monomer includes, for example, a decane and a dioxane. The resin may be a ruthenium-containing resin (for example, a sesquioxane) and a system-free resin (for example, a phenol resin). The pretreatment composition, the imprinted photoresist material, or both may also include one or more polymerization initiators or radical generators. The types of the polymerization initiator include, for example, photoinitiators (for example, samarium, xanthone, and benzophenone), photoacid generators (for example, sulfonates and phosphonium salts), and photobase generation. Agents (for example, ortho-nitrobenzyl carbamates, urethanes, and O-mercaptoquinones).

Suitable monomers include monofunctional, difunctional or polyfunctional acrylates, methacrylates, vinyl ethers, and epoxides, wherein the mono-, di-, and poly- , two and three or more of the indicated functional groups. Some or all of these monomers may be fluorinated (eg, perfluorinated). For example, in the case of an acrylate, the pretreatment composition, the imprinted photoresist material, or both may contain one or more monofunctional acrylates, one or more difunctional acrylates, One or more polyfunctional acrylates or a combination thereof.

Examples of suitable monofunctional acrylates include isobornyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, dicyclopentenyl acrylate, benzyl acrylate, 1-naphthyl acrylate , 4-cyanobenzyl acrylate, pentafluorobenzyl acrylate, 2-phenylethyl acrylate, phenyl acrylate, (2-ethyl-2-methyl-1,3-dioxane-4- Methyl propylene Acid ester, n-hexyl acrylate, 4-tert-butylcyclohexyl acrylate, methoxypolyethylene glycol (350) monoacrylate, and methoxypolyethylene glycol (550) monoacrylate.

Examples of suitable diacrylates include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate (eg, Mn, avg = 575), 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-butanediol diacrylate, 3-methyl-1,3-butanediol diacrylate, 1,5-pentanediol diacrylate 1,6-hexanediol diacrylate, 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-anthracene Diol diacrylate, 1,12-dodecanediol diacrylate, neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A Acrylate, ethoxylated bisphenol A diacrylate, m-xylene diacrylate, ethoxylated (3) bisphenol A diacrylate, ethoxylated (4) bisphenol A diacrylate, Ethoxylated (10) bisphenol A Acrylate, dicyclopentane diacrylate, 1,2-adamantanediol diacrylate, 2,4-diethylpentane-1,5-diol diacrylate, polyethylene glycol (400 Diacrylate, polyethylene glycol (300) diacrylate, 1,6-hexanediol (EO) ₂ diacrylate, 1,6-hexanediol (EO) ₅ diacrylate, and alkoxylated grease Group diacrylate.

Examples of suitable polyfunctional acrylates include trihydroxyl Methylpropane triacrylate, propoxylated trimethylolpropane triacrylate (for example, propoxylated (3) trimethylolpropane triacrylate, propoxylated (6) trimethylolpropane Triacrylate), trimethylolpropane ethoxy triacrylate (eg, n~1.3,3,5), bis(trimethylolpropane)tetraacrylate, propoxylated glyceryl triacrylate ( For example, propoxylated (3) glyceryl triacrylate), tris(2-hydroxyethyl)isocyano uric acid triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate Dipentaerythritol pentaacrylate, tripentaerythritol octaacrylate.

Examples of suitable crosslinking agents include, for example, the difunctional acrylates and polyfunctional acrylates described herein.

The photoinitiator is preferably a free radical generator. Examples of suitable radical generating agents include, but are not limited to, 2,4,5-triarylimidazole dimers optionally having a substituent such as 2-(o-chlorophenyl)-4,5-diphenylimidazole Dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimerization And 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; benzophenone derivatives such as benzophenone, N,N'-tetramethyl- 4,4'-Diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy- 4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-diaminobenzophenone; Amine aromatic ketone derivatives such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(A Thio)phenyl]-2-morpholinyl-propan-1-one; anthraquinones such as 2-ethylhydrazine, phenanthrenequinone, 2-t-butyl Anthraquinone, octamethylguanidine, 1,2-benzopyrene, 2,3-benzopyrene, 2-phenylindole, 2,3-diphenylanthracene, 1-chloroindole, 2-methylindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylhydrazine; benzoin ether derivatives Such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin derivatives such as benzoin, methyl benzoin, ethyl benzoin, and propyl benzoin; benzyl Base derivatives such as benzyl dimethyl ketal; acridine derivatives such as 9-phenyl acridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives For example, N-phenylglycine; acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2 , 2-dimethoxy-2-phenylacetophenone; thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone, a phosphinylphosphine derivative such as oxidized 2,4,6-trimethylbenzhydryldiphenylphosphine, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, and oxidized double (2,6-dimethyl Oxylbenzylidene)-2,4,4-trimethylpentylphosphine; an oxime ester derivative such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O -benzimidyl lipid)], ethyl ketone and 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-B醯 肟 肟); and xanthone, anthrone, benzaldehyde, hydrazine, hydrazine, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1 a ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

Examples of commercially available products of such free radical generators include, but are not limited to, IRGACURE 184, 250, 270, 290, 369, 379, 651,500, 754, 819, 907, 784, 1173, 2022, 2100, 2959, 4265, BP, MBF, OXE01, OXE02, PAG121, PAG203, CGI-1700, -1750, -1850, CG24-61, CG2461, DAROCUR 1116, 1173, LUCIRIN TPO, TPO-L, LR8893, LR8953, LR8728 and LR8970 (manufactured by BASF) ; and EBECRYL P36 produced by UCB.

A sulfonium phosphine-based polymerization initiator or an alkylphenol-based polymerization initiator is preferred. In the examples listed above, the ceramide-based phosphine-based polymerization initiator is a cerium oxide-based phosphine compound such as oxidized 2,4,6-trimethylbenzhydryldiphenylphosphine, oxidized bis (2,4) , 6-trimethylbenzimidyl)phenylphosphine, and bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide. In the examples listed above, the alkylphenol-based polymerization initiator is a benzoinone derivative such as benzoin ketone, benzoin ethyl ether, and benzoin phenyl ether; a benzoin derivative such as a benzophenone Margin, methyl benzoin, ethyl benzoin and propyl benzoin, benzyl derivatives such as benzyl dimethyl ketal; acetophenone derivatives such as acetophenone, 3-methylbenzene Ethyl ketone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone; and α-aminoaromatic ketone derivatives such as 2 -benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-? Orolinyl propan-1-one.

The content of the photoinitiator is 0.1 wt% or more and 50 wt% or less, preferably 0.1 wt% or more and 20 wt% or less, based on the total weight of all components (excluding the components for the solvent). More preferably, it is 1 wt% or more and 20 wt% or less.

When the content of the photoinitiator is the total weight excluding the solvent component When the amount is 1% by weight or more, the curing rate of the curable component is accelerated. Therefore, the reaction efficiency can be improved. When the content of the photoinitiator is 50% by weight or less based on the total weight of the solvent component, the obtained cured product may be a cured product having a certain mechanical strength.

Examples of suitable photoinitiators include IRGACURE 907, IRGACURE 4265, 651, 1173, 819, TPO and TPO-L.

a surfactant can be applied to the patterned surface of an embossed lithography template, can be applied to the embossed lithographic photoresist material, or both to reduce the cured photoresist material and The separation force between the stencils reduces defects in the embossed pattern formed in the embossing lithography process and increases the number of successful embossings that can be fabricated using an embossed lithography template. Factors in selecting a liberating agent for imprinting the photoresist material include, for example, affinity with the surface, desired surface characteristics of the treated surface, and shelf life of the liberating agent within the embossed photoresist material ( Shelf life). While certain liberating agents form covalent bonds with the template, the fluorinated nonionic surfactant interacts with the template through non-covalent bonding interactions (eg, hydrogen bonding and van der Waals interaction).

Examples of suitable surfactants include fluorinated and non-fluorinated surfactants. The fluorinated and non-fluorinated surfactants can be ionic or nonionic surfactants. Suitable nonionic fluorinated surfactants include fluorine-containing aliphatic polymeric esters, perfluoroether surfactants, polyoxyethylene fluorosurfactants, polyalkyl ether fluorosurfactants , fluoroalkyl polyethers and the like. Suitable nonionic non-fluorinated surfactants include ethoxylated alcohols, ethoxylated alkyl phenols, polyethylene oxide-polyoxygenation Propylene block copolymer.

Exemplary commercially available surfactant ingredients include, but are not limited to, ZONYL® FSO and ZONYL® FS-300 manufactured by EI du Pont de Nemours and Company, Wilmington, Delaware, USA; 3M Company, Maplewood, Minnesota Manufactured FC-4432 and FC-4430; MASURF® FS-1700, FS-2000 and FS-2800 manufactured by Pilot Chemical Company, Cincinnati, Ohio; S-107B, manufactured by Chemguard, Inc., Mansfield, Texas; NEOS Chemical Chuo-ku, FTERGENT 222F, FTERGENT 250, FTERGENT 251 manufactured by Kobe-shi; PolyFox PF-656 manufactured by OMNOVA Solutions Inc. of Akron, Ohio; BASF Corporation, located in Florham Park, New Jersey Pluronic L35, L42, L43, L44, L63, L64, etc. manufactured by Brij 35, 58, 78, etc., manufactured by Croda Inc. of Edison, New Jersey.

Further, the pretreatment composition and the imprinted photoresist material may include one or more non-polymerizable components according to different purposes, in addition to the above-described components, without detracting from the effects of the present invention. Examples of such ingredients include sensitizers, hydrogen donors, antioxidants, polymer components, and other additives.

The sensitizer is a compound added for the purpose of accelerating the polymerization reaction or improving the conversion rate of the reaction. Examples of suitable sensitizers include sensitizing dyes.

Sensitizing dyes are stimulated by absorbing light of a specific wavelength Excited as a compound that interacts with the photoinitiator as component (B). As used herein, interaction refers to energy transfer, electron transfer, and the like from the sensitizing dye in an activated state to a photoinitiator as component (B).

Examples of suitable sensitizing dyes include, but are not limited to, anthracene derivatives, anthracene derivatives, anthracene derivatives, anthracene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone Derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, Ketocoyl coumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyrylium salt dyes.

One of these sensitizers may be used alone, or two or more of these sensitizers may be used as a mixture.

The hydrogen donor is a free radical reaction with initiation radicals produced by the photoinitiator as component (B) or with the growth end of the polymer to generate more reactive free radicals. The hydrogen donor is preferably added when component (B) is one or more photoradical generators.

Specific examples of suitable hydrogen donors include, but are not limited to, amine compounds such as n-butylamine, di-n-butylamine, tri-n-butylamine, allylthiourea, s-benzylisothiourea-p -toluenesulfinate, triethylamine, diethylamine ethyl methacrylate, triethyltetramine, 4,4'-bis(dialkylamino)benzophenone, N,N-dimethyl Ethyl benzoate, isoamyl N,N-dimethylaminobenzoate Esters, pentyl-4-dimethylaminobenzoic acid esters, triethanolamine and N-phenylglycine; and mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionate.

One of these hydrogen donors may be used singly or two or more of these hydrogen donor systems may be used as one mixture. Moreover, the hydrogen donors have the same function as the sensitizer.

The content of these components (non-polymerizable components) in the imprinted photoresist material is 0 wt% or more and 50 wt% or less based on the total weight of all components (excluding the components for the solvent). It is preferably 0.1% by weight or more and 50% by weight or less, more preferably 0.1% by weight or more and 20% by mass or less.

Additionally, the embossed photoresist material can include one or more solvents as an additional component. Preferred solvents include, but are not limited to, solvents having a boiling point of 80 ° C or higher and 200 ° C or lower at normal pressure. More preferably, each solvent has at least one of a hydroxyl group, an ether structure, an ester structure or a ketone structure.

Specific examples of suitable solvents include alcohol solvents such as propanol, isopropanol and butanol; ether solvents such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, B Glycol diethyl ether, ethylene glycol monobutyl ether and propylene glycol dimethyl ether; ester solvents such as butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate and propylene glycol Monomethyl ether acetate; and ketone solvents such as methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, γ-butyrolactone, and ethyl lactate. It is preferred to use a single solvent or a mixed solvent selected from such solvents.

In some examples, the pretreatment composition can be combined with one or more solvents. In one example where the pretreatment composition is applied in a spin coating manner, the pretreatment composition is combined with one or more solvents to promote expansion on the substrate, after expansion, substantially all of the solvent It is evaporated to leave the pretreatment composition on the substrate.

Solvents suitable for use in combination with the pretreatment composition generally comprise a solvent as described in relation to the imprinted photoresist material. For the application of the pretreatment composition by spin coating, from the viewpoint of coating characteristics, one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, and 2-heptanone A single solvent or a mixed solvent of γ-butyrolactone and ethyl lactate is particularly suitable.

The content of the solvent component to be combined with the pretreatment composition can be appropriately adjusted by the viscosity of the hardened layer to be formed, the coating property, the film thickness, and the like, and is preferably the pretreatment composition and the solvent. 70 wt% or more, 90 wt% or more, more preferably 95 wt% or more of the total weight. The larger solvent component content allows the film thickness of the pretreatment composition to be thinner. If the content of the solvent component is 70% by weight or less of the solvent/pretreatment composition mixture, appropriate coating characteristics cannot be obtained.

Although these solvents can be used in the imprinted photoresist material, the imprinted photoresist material should preferably contain no solvent. As used herein, the term "substantially free of solvent" refers to other solvents (eg, impurities) contained within the solvent other than the solvent. For example, the solvent content in the imprint photoresist material according to this embodiment is preferably the entire pressure 3 wt% or less, more preferably 1 wt% or less of the photoresist material. As used herein, solvent refers to a solvent that is typically used in a curable composition or in a photoinitiator. In other words, the solvent is not limited to their kind as long as the solvent can dissolve and uniformly disperse the compound used in the present invention and does not react with these compounds.

In some examples, the imprinted photoresist material comprises from 0 wt% to 80 wt% (eg, from 20 wt% to 80 wt% or from 40 wt% to 80 wt%) of one or more monofunctional acrylates; from 90 wt% to 98 wt% of one or more A difunctional or polyfunctional acrylate (eg, the imprinted photoresist material may be substantially free of monofunctional acrylates) or from 20 wt% to 75 wt% of one or more difunctional or polyfunctional acrylates (eg, When one or more monofunctional acrylates are present; 1% to 10% by weight of one or more photoinitiators; and from 1% to 10% by weight of one or more surfactants. In one example, the embossed photoresist material comprises from about 40 wt% to about 50 wt% of one or more monofunctional acrylates, from about 45 wt% to about 55 wt% of one or more difunctional acrylates, and about 4 wt% to About 6 wt% of one or more photoinitiators, and about 3 wt% of surfactant. In another example, the embossed photoresist material comprises about 44% by weight of one or more monofunctional acrylates, about 48% by weight of one or more difunctional acrylates, about 5% by weight of one or more photoinitiators, And about 3 wt% of a surfactant. In yet another example, the embossed photoresist material comprises about 10% by weight of a first monofunctional acrylate (eg, isobornyl acrylate), about 34% by weight of a second monofunctional acrylate (eg, benzyl Base acrylate), about 48% by weight of a difunctional acrylate (eg, neopentyl glycol diacrylate), about 2% by weight of a first photoinitiator (eg, IRGACURE TPO), about 3% by weight of a second photoinitiator An agent (for example, DAROCUR 4265), and about 3 wt% of a surfactant. Examples of suitable surfactants include XR-(OCH ₂ CH ₂ ) _n OH wherein R = alkyl, aryl or poly(propylene glycol), X = H or -(OCH ₂ CH ₂ ) _n OH, and n is An integer (for example, 2 to 20, 5 to 15, or 10-12) (for example, X = -(OCH ₂ CH ₂ ) _n OH, R = poly(propylene glycol), and n = 10-12); a surfactant wherein X = perfluoroalkyl or perfluoroether, or a combination thereof. The viscosity of the embossed photoresist material at 23 ° C is typically in the range of 1 cP to 50 cP, 1 cP to 25 cP, or 5 cP to 15 cP. The interfacial energy between the imprinted photoresist material and air is typically in the range of 20 mN/m to 60 mN/m, 28 mN/m to 40 mN/m, or 32 mN/m to 35 mN/m. Viscosity and interfacial energy are defined as described in the examples herein.

In one example, a pretreatment composition comprises from 0 wt% to 80 wt% (eg, from 20 wt% to 80 wt% or from 40 wt% to 80 wt%) of one or more monofunctional acrylates; from 90 wt% to 100 wt% of one or a plurality of difunctional or polyfunctional acrylates (for example, the pretreatment composition is substantially free of monofunctional acrylates) or from 20% to 75% by weight of one or more difunctional or polyfunctional acrylates (for example, when one or more monofunctional acrylates are present); from 0 wt% to 10 wt% of one or more photoinitiators; and from 0 wt% to 10 wt% of one or more surfactants.

The pretreatment composition is typically miscible with the imprinted photoresist material. The pretreatment composition typically has a low vapor pressure such that it maintains the morphology of a film on the substrate until the resultant coating is polymerized. In one example, the pretreatment composition has a vapor pressure system at 25 ° C of less than 1 x 10 ^-4 mm Hg. The pretreatment composition also typically has a low viscosity to promote rapid expansion of the pretreatment composition on the substrate. In one example, the viscosity of the pretreatment composition at 23 ° C is typically in the range of 1 cP to 200 cP, 1 cP to 100 cP, or 1 cP to 50 cP. The interfacial energy between the pretreatment composition and air is typically between 30 mN/m and 45 mN/m. The pretreatment composition is typically selected to be chemically stable such that decomposition does not occur during use.

The pretreatment composition and the imprinted photoresist material should preferably include impurities at a level as small as possible. As used herein, an impurity refers to anything other than the ingredients mentioned above. Therefore, the pretreatment composition and the imprinted photoresist material are preferably obtained via a purification process. This purification treatment is preferably filtered using a filter or the like. In particular, for filtration using a filter, the ingredients mentioned above and optional additions should preferably be mixed and then passed through a filter (which has a 0.001 micron or greater and 5.0, for example). Filter the size of the pores in microns or smaller). For filtration using a filter, it is more preferred that the filtration be carried out in multiple stages or repeatedly. Moreover, the filtered solution can be filtered again. Multiple filters of different hole sizes can be used in the filter. A filter made of polyethylene resin, polypropylene resin, fluororesin, nylon resin or the like can be used. This filtering, but the filter is not limited to this. Impurities (e.g., particles) mixed in the composition can be removed by this purification treatment. This prevents impurities (such as fine particles) from causing pattern defects to be formed in the cured film because of careless unevenness during curing of the curable composition.

In the example of manufacturing the semiconductor integrated circuit using the pretreatment composition and the imprinted photoresist material, it is preferable to avoid impurities (metal impurities) containing metal atoms from being mixed into the curable composition as much as possible. To prevent the operation of the product from being prohibited. In this case, the concentration of the metal impurities contained in the curable composition is preferably 10 ppm or less, more preferably 100 ppb or less.

The pretreatment composition can be a single polymerizable component (eg, a monomer such as a monofunctional acrylate, a difunctional acrylate or a polyfunctional acrylate), a mixture of two or more polymerizable components (eg, two or a mixture of a plurality of monomers), or a mixture of one or more polymerizable components and one or more other components (eg, a mixture of a plurality of monomers; two or more monomers with a surfactant, a photoinitiator or both) a mixture of people, etc.). In some examples, the pretreatment composition includes trimethylolpropane triacrylate, trimethylolpropane ethoxy triacrylate, 1,12-dodecanediol diacrylate, polyethylene glycol diacrylate Ester, tetraethylene glycol diacrylate, 1,3-adamantanediol diacrylate, decanediol diacrylate, m-xylene diacrylate, dicyclopentyl diacrylate, or any combination thereof.

Mixture of polymerizable ingredients produces complementary effects (synergistic effects), the resulting pretreatment composition has a combination of properties (eg, low viscosity, good etch resistance, and film stability) that are more advantageous than the pretreatment composition having a single polymerizable component. In one example, the pretreatment composition is a mixture of 1,12-dodecanediol diacrylate and tricyclodecane dimethanol diacrylate. In another example, the pretreatment mixture is a mixture of tricyclodecane dimethanol diacrylate and tetraethylene glycol diacrylate. The pretreatment composition is typically selected such that one or more components of the pretreatment composition polymerize with one or more components of the imprinted photoresist material during polymerization of the synthetic polymerizable coating (eg, covalent bonds) Knot). In some cases, the pretreatment composition includes a polymerizable component also within the imprinted photoresist material, or includes a polymerizable component having one and one or more of the imprinted photoresist material A functional group (e.g., an acrylate group) shared by the polymerizable component. Suitable examples of such pretreatment compositions include, for example, the polyfunctional acrylates described herein, including propoxylated (3) trimethylolpropane triacrylate, trimethylolpropane triacrylate, and dipentaerythritol. Pentaacrylate.

The pretreatment composition can be selected such that the etch resistance can be similar to the etch resistance of the embossed photoresist material by increasing the etching uniformity. In some cases, the pretreatment composition is selected such that the interface at the interface between the pretreatment composition and the air is greater than the interfacial energy between the imprinted photoresist material and the pretreatment composition, thereby A rapid expansion of the imprinted photoresist material that promotes the liquid onto the pretreatment composition of the liquid is used to form a uniform synthetic coating on the substrate prior to contacting the composite coating with the template. The interface energy between the pretreatment composition and the air is typically better than The interfacial energy between the imprinted photoresist material and the air or the interface energy between the at least one component of the imprinted photoresist material and the air is 0.5 mN/m to 25 mN/m, 0.5 mN/m to 15 mN. /m, 0.5 mN/m to 7 mN/m, 1 mN/m to 25 mN/m, 1 mN/m to 15 mN/m, or 1 mN/m to 7 mN/m, but these ranges may be based on the pretreatment composition and the pressure The chemical and physical properties of the printed photoresist material and the interaction between the two liquids vary. When the difference between the surface energies is too small, the expansion of the imprinted photoresist material is too small, and the droplets remain in a cap-like shape and remain separated by the pretreatment composition. When the difference between the surface energies is too large, the result of excessive expansion of the imprinted photoresist material is caused, that is, too much imprinted photoresist material moves toward the adjacent droplets to cause the center of the droplet to be vacant, so that the synthesized coating There is a concave area at the center of the droplet. Thus, when the difference between the surface energies is too small or too large, the resulting composite coating is non-uniform with significant depressed or convex regions. When the difference between the surface energies is appropriately selected, the imprinted photoresist material rapidly expands to obtain a substantially uniform synthetic coating. An advantageous choice of the pretreatment composition and the imprinted photoresist material allows the fill time to be reduced by 50-90% so that the fill can be achieved in less than 1 second, and in some cases even less than 0.1 second.

Referring to operation 402 of process 400, FIG. 5A shows a substrate 102 including a substrate 500 and an adhesive layer 502. Substrate 500 is typically a single wafer. Other suitable materials for the substrate 500 include molten vermiculite, quartz, tantalum, gallium arsenide, and indium phosphide. The adhesive layer 502 is used to enhance the adhesion of the polymeric layer to the substrate 500, thereby reducing the synthesis. After the polymerization of the coating, defects are formed in the polymeric layer during separation of the template from the polymeric layer. The thickness of the adhesive layer 502 is typically between 1 nm and 10 nm. Examples of materials suitable for use in the adhesive layer 502 include materials disclosed in U.S. Patent Nos. 7,759,407; 8,361,546; 8,557,351; 8,808,808; and 8,846,195, all of which are incorporated herein by reference. In this article. In one example, an adhesive layer is comprised of ISORAD 501, CYMEL 303ULF, CYCAT 4040 or TAG 2678 (tetra-ammonium block of trifluoromethanesulfonic acid), and PM Acetate (a type of Eastman Chemical Company of Kingsport, Tennessee) A composition comprising a solvent consisting of 2-(1-methoxy)propyl acetate is provided. In some examples, substrate 102 includes one or more additional layers between the substrate 500 and the adhesive layer 502. In some cases, substrate 102 includes one or more additional layers on adhesive layer 502. For simplicity, the substrate 102 is shown to include only the substrate 500 and the adhesive layer 502.

FIG. 5B shows the pretreatment composition after the pretreatment composition 504 has been disposed on the substrate 102 to form the pretreatment coating 506. As shown in FIG. 5B, a pretreatment coating 506 is formed directly on the adhesive layer 502 of the substrate 102. In some cases, the pretreatment coating 506 is formed on another surface of the substrate 102 (eg, formed directly on the substrate 500). The pretreatment coating 506 is formed on the substrate 102 using techniques such as spin coating, dip coating, chemical vapor deposition (CVD), physical vapor deposition (PVD), and the like. For example, in spin coating, dip coating, and the like, the pretreatment composition can be dissolved in one or more solvents (eg, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME) And, for example, for application to the substrate, the solvent is then evaporated to leave the pretreatment coating. The thickness of the pretreatment coating 506 t _p typically between 1 nm and 100 nm (e.g., between 1 nm and 50 nm, between 1 nm and 25 nm, or Between 1 nm and 10 nm).

Referring again to FIG. 4, operation 404 of process 400 includes disposing droplets of imprinted photoresist material onto the pretreatment composition such that droplets of each imprinted photoresist material cover a target area of the substrate. The volume of droplets of the embossed photoresist material is typically between 0.6 pL and 30 pL, and the distance between the centers of the droplets is typically between 35 microns and 350 microns. In some examples, the volume ratio between the imprinted photoresist material and the pretreatment composition is between 1:1 and 15:1. In operation 406, a synthetic coating is formed on the substrate as the droplets of each of the imprinted photoresist material expand beyond their target regions to form a composite coating. As used herein, "pre-expanded" means that the droplets of the imprinted photoresist material contact the pre-treatment coating at the beginning and expand beyond its target area and the template contacts the composite coating. Spontaneous expansion between the two.

6A-6D show top views of the droplets of the imprinted photoresist material on the pretreatment coating as the droplets of imprinted photoresist material are disposed onto the target area, and the composite coating is before, during, and during droplet expansion. And the top view at the end. Although the droplets are shown as a square grid, the droplet pattern is not limited to a square or geometric pattern.

Figure 6A shows that the droplet is initially configured to the pretreatment coating On top of the layer, a top view of the droplets 600 on the pretreatment coating 506 is such that the droplets cover the target area 602 but do not extend beyond the target area. After the droplets 600 are disposed to the pretreatment coating 506, the droplets spontaneously expand to cover a surface area of the substrate that is larger than the target area, thereby forming a composite coating on the substrate. . 6B shows the composite coating 604 during pre-expansion (after the portion of the droplet 600 has expanded beyond the target region 602) and typically after partial mixing between the imprinted photoresist material and the pre-treatment composition. Top view. As shown, the composite coating 604 is a mixture of the liquid pretreatment composition and the liquid imprinted photoresist material, wherein the region 606 contains a majority of the imprinted photoresist material ("rich" embossing). The photoresist material, and region 608, contains most of the pretreatment composition ("rich" pretreatment composition). As the pre-expansion progresses, the resultant coating 604 can form a more uniform mixture of the pre-treatment composition and the imprinted photoresist material.

The expansion may proceed until one or more regions 606 contact one or more adjacent regions 606. Figures 6C and 6D show the composite coating 604 at the end of the expansion. As shown in FIG. 6C, each region 606 has been expanded to contact each adjacent region 606 at boundary 610, wherein region 608 is reduced to a separate (discontinuous) portion between regions 606. In other cases, as shown in Figure 6D, region 606 expands to form a continuous layer such that region 608 becomes indistinguishable. In Figure 6D, the composite coating 604 can be a homogeneous mixture of the pretreatment composition and the imprinted photoresist material.

7A-7D are w-w, x-x, respectively, along Figs. 6A-6D, A cross-sectional view of the y-y and z-z lines. 7A is a cross-sectional view taken along line w-w of FIG. 6A showing droplets 600 of the imprinted photoresist material overlying a surface area of the substrate 102 corresponding to the target region 602. Each target area (and each initially configured drop) has a center indicated by a c-c line, and the b-b line indicates an equidistant position between the centers of the two target areas 602. For the sake of simplicity, the droplets 600 are shown as contacting the adhesive layer 502 of the substrate 102, and the imprinted photoresist material and the pre-treatment composition are shown not to be mixed with each other. 7B is a cross-sectional view taken along line x-x of FIG. 6B showing the composite coating 604 exposed between regions 606 after region 606 has expanded beyond target region 602. Figure 7C is a cross-sectional view along the y-y line of Figure 6C at the end of the pre-expansion, showing the composite coating 604 as a homogeneous mixture of the pre-treatment composition and the imprinted photoresist material. As shown, region 606 has been expanded to cover a larger substrate surface than that shown in Figure 7B, and region 608 is correspondingly shrunk. Region 606, which initially begins with droplet 600, is shown to be convex, however, composite coating 604 can be substantially flat or include a recessed region. In some cases, since the imprinted photoresist material forms a continuous layer on the pretreatment composition (not mixed with each other or completely or partially mixed with each other), the pre-expansion may continue beyond that in Figure 7C. The range shown. Figure 7D is a cross-sectional view along line zz of Figure 6D showing that the resultant coating meets at the boundary 610 at a depressed region near the center cc of the droplet, so at the end of the expansion, the resultant coating Layer 604 becomes a homogeneous mixture of the pretreatment composition and the imprinted photoresist material such that the thickness of the polymerizable coating at the droplet boundary is greater than the resultant at the center of the droplet The thickness of the coating. As shown in Figures 7C and 7D, when the resultant coating contacts the nanoimprint lithography template, the thickness of the resultant coating 604 at an equidistant position between the centers of the two target regions is different from the two The thickness of the composite coating at the center of one of the target areas.

Referring again to FIG. 4, operations 408 and 410 of process 400 include respectively contacting the composite coating with a template and polymerizing the resultant coating to produce a nanoimprinted lithographic stack having a composite The coating is applied to the nanoimprint lithographic substrate.

In some examples, as shown in Figures 7C and 7D, the composite coating 604 is a homogeneous mixture or substantially homogeneous at the end of the pre-expansion (i.e., immediately before the combined coating and the template are in contact). Mixture (eg, at the air-synthetic coating interface). Thus, the template is in contact with a homogeneous mixture, the vast majority of which is derived from the imprinted photoresist material. Thus, the release characteristics of the imprinted photoresist material will generally dominate the interaction of the composite coating with the template, as well as the separation of the polymeric layer from the template, including the template and the polymeric layer. The formation of defects between the separation forces (or no defect formation).

However, as shown in Figures 8A and 8B, the composite coating 604 can include regions 608 and 606 that are respectively enriched with a pretreatment composition and an embossed photoresist material such that the template 110 contacts the composite coating. 604 areas with different physical and chemical properties. For simplicity, the imprinted photoresist material in region 606 is shown to have displaced the pretreatment coating such that region 606 is in direct contact with the substrate and is shown not to be mixed with one another. Therefore, the thickness of the pretreatment composition in region 608 It is not uniform. In FIG. 8A, the maximum height p of the region 606 is greater than the maximum height i of the pre-treatment composition such that the template 110 is primarily in contact with the region 606. In FIG. 8B, the maximum height i of the region 608 is greater than the maximum height p of the imprinted photoresist material such that the template 110 is primarily in contact with the region 608. Thus, the separation of the template 110 from the resulting synthetic polymeric layer and the associated defect density are not uniform and because of the different mutualities between the template and the imprinted photoresist material and between the template and the pretreatment composition. effect. Thus, for certain pretreatment compositions (eg, including a single functional group or a mixture of two or more monomers, but no pretreatment composition of the surfactant), the synthetic coating is in the template The gas-liquid interface of the synthetic coating contacts forms a homogeneous mixture, or at least a substantially homogeneous mixture is preferred.

9A-9C and 10A-10C are cross-sectional views showing a template 110 and a coating 604 synthesized on a substrate 102 having a substrate 500 and an adhesive layer 502 prior to contact, contact, contact between the composite coating and the template, And the case where the template is separated from the synthetic polymeric layer to produce a nanoimprinted lithographic stack. In Figures 9A-9C, the composite coating 604 is shown as a homogeneous mixture of the pretreatment composition and the imprinted photoresist material. In Figures 10A-10C, the composite coating 604 is shown as a heterogeneous mixture of the pretreatment composition and the imprinted photoresist material.

FIG. 9A shows a cross-sectional view of the initial beginning of contact of the template 110 with the homogeneous synthetic coating 900 on the substrate 102. In FIG. 9B, the template 110 continues to advance toward the substrate 102 such that the resultant coating 900 fills the depressions of the template 110. The synthesized coating 900 is polymerized to yield one After the homogeneous polymeric layer is on substrate 102, template 110 and the polymeric layer are separated. 9C shows a cross-sectional view of a nanoimprint lithography stack 902 having a homogeneous synthetic polymeric layer 904.

FIG. 10A shows a cross-sectional view of the initial stage of contact of the template 110 with the coating 604 synthesized on the substrate 102. The heterogeneous synthetic coating 1000 includes regions 606 and 608. As shown, the imprinted photoresist material in region 606 and the pre-treatment composition in region 608 are few or even not mixed with each other. In FIG. 10B, the template 110 continues to advance toward the substrate 102 such that the resultant coating 1000 fills the depressions of the template 110. After the synthetic coating 1000 is polymerized to produce a heterogeneous polymeric layer on the substrate 102, the template 110 and the polymeric layer are separated. 10C shows a cross-sectional view of a nanoimprint lithography stack 1002 having a heterogeneous synthetic polymeric layer 1004, wherein regions 1006 and 1008 correspond to regions 606 and 608 of the heterogeneous synthetic coating 1000. Thus, the chemical composition of the synthesized polymeric layer 1002 is heterogeneous or non-homogeneous and includes a region 1006 having a composition derived from a mixture of embossed photoresist materials and a region 1008 (which has In the composition of the mixture enriched in the pretreatment composition). The relative size of regions 1006 and 1008 (e.g., exposed surface area, surface area covered by the stencil, or volume) may be due, at least in part, to the extent of pre-expansion or expansion of the composite coating prior to contact with the stencil. And change. In some cases, region 1006 can be separated or surrounded by region 1008 such that the resultant polymeric layer includes a plurality of central regions separated by boundaries, wherein the chemical composition of the composite polymeric layer 1004 at the boundary is different than the Synthesis of the polymerized layer inside the central region Learning ingredients.

The contact of the synthetic coating 604 and the template 110 mentioned above may be carried out in an atmosphere containing a coagulating gas (which is hereinafter referred to as "condensable gas atmosphere"). As used herein, the coagulated gas system refers to a gas that is coagulated and liquefied by capillary pressure, the capillary pressure being a depression of a fine pattern formed on the template 110 and interposed between a mold and a substrate. The gap between the spaces is filled with the gas in the atmosphere as well as the pretreatment composition and the imprinted photoresist material. When the resultant coating is in contact with the stencil, the condensable gas exits as a gas in the atmosphere before the pretreatment composition and the embossed photoresist material are in contact with the stencil 110.

When the resultant coating and a template are contacted in the coagulated gas atmosphere, the gas filled in the depression of the fine pattern is liquefied, so that a bubble disappears, resulting in excellent filling characteristics. The coagulated gas can be dissolved in the pretreatment composition and/or the imprinted photoresist material.

The boiling point of the coagulated gas is not limited as long as the temperature is equal to or lower than the ambient temperature at which the synthetic coating and the template are in contact. The boiling point is preferably from -10 ° C to 23 ° C, more preferably from 10 ° C to 23 ° C. Better filling characteristics are obtained within this range.

The vapour pressure of the condensable gas at the ambient temperature at which the synthetic coating is contacted with the stencil is not limited as long as the pressure is equal to or lower than the embossed mold pressure at which the synthetic coating contacts the stencil. The vapor pressure is preferably from 0.1 to 0.4 MPa. Better filling characteristics are obtained within this range. a vapor pressure greater than 0.4 MPa at ambient temperature There is a tendency to make the air bubbles disappear and not sufficiently effective. On the other hand, a vapor pressure of less than 0.1 MPa at ambient temperature tends to have to be reduced in pressure and a complicated equipment is necessary.

The ambient pressure at which the synthetic coating is contacted with the stencil is not limited and is preferably from 20 ° C to 25 ° C.

Specific examples of suitable coagulating gases include foreheads (frons) comprising chlorofluorocarbons (CFCs) such as trichlorofluoromethane, fluorocarbons (FC), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), for example 1,1,1,3,3-pentafluoropropane (CHF ₂ CH ₂ CF ₃ , HFC-245fa, PFP), and hydrofluoroether (HFE) such as pentafluoroethyl methyl ether (CF ₃ CF ₂ OCH ₃ , HFE-245mc). Among these, 1,1,1,3,3-pentafluoropropane (23) from the viewpoint that the synthesized coating and the template have excellent filling characteristics when contacted at an ambient temperature of from 20 ° C to 25 ° C °C vapor pressure: 0.14 MPa, boiling point: 15 ° C), trichlorofluoromethane (23 ° C vapor pressure: 0.1056 MPa, boiling point: 24 ° C), and pentafluoroethyl methyl ether are preferred. In addition, 1,1,1,3,3-pentafluoropropane is particularly good from the standpoint of excellent safety. One of these coagulation gases may be used alone, or two or more of these coagulation gases may be used in a mixture.

These coagulated gases can be used in combination with non-condensable gases such as air, nitrogen, carbon dioxide, helium, and argon. From the standpoint of the filling property, it is preferable that helium is used as a mixture of a non-condensable gas and a condensable gas. Helium can penetrate the mold 205. Therefore, when the depression of the fine pattern formed on the mold 205 is filled with the gas (condensable gas and helium) in the atmosphere When the synthetic coating is contacted, the coagulation gas is liquefied together with the pretreatment composition and/or the imprinted photoresist material while the helium gas penetrates the mold.

The polymeric layer obtained by separating the template from the synthesized polymeric layer has a special pattern shape. As shown in FIG. 2, the residual layer 204 can be held in an area other than the area having the pattern shape formed. In this case, the residual layer 204 appearing in the region to be removed of the cured layer 202 having the obtained pattern shape is removed by gas etching. Thus, a patterned cured layer without the residual layer (i.e., the substrate on the surface of the substrate 102) having the desired pattern shape (e.g., the pattern shape obtained from the shape of the template 110) can be obtained. The desired part is exposed.)

In this context, an example of a suitable method for removing the residual layer 204 includes removing the residual layer 204 at the recess of the cured layer 202 having a pattern shape by a technique such as etching to expose a pattern there. A method of shaping the surface of the substrate 102 at the depression in the pattern of the cured layer 202.

In the example of removing the residual layer 204 at the recess of the cured layer 202 having a pattern shape by etching, a specific method is not limited, and a conventional method known in the art can be used, for example, Dry etching using an etching gas is used. Conventional dry etching apparatus known in the art can be used in the dry etching process. The dry etching gas is appropriately selected depending on the basic composition of the solidified layer that will receive this etching. For example, a halogen gas (for example, CF ₄ , C ₂ F ₆ , C ₃ F ₈ , CCl ₂ F ₂ , CCl ₄ , CBrF ₃ , BCl ₃ , PCl ₃ , SF _{6 ,} and Cl ₂ ), an oxygen atom-containing gas may be used. (eg, O ₂ , CO, and CO ₂ ), an inert gas (eg, He, N _{2 ,} and Ar) or a gas such as H ₂ or NH ₃ . These gases can be used in the form of a mixture.

When the substrate 102 (substrate to be treated) used is a substrate to which the adhesion to the cured layer 202 is improved by surface treatment (for example, decane coupling treatment, decane treatment, and organic film formation) The surface treated layer may also be removed by etching after etching of the residual layer 204 at the recess of the cured layer 202 having a pattern shape.

The manufacturing process described above can produce a patterned cured layer without the residual layer having a desired pattern shape (eg, a pattern shape obtained from the shape of the template 110) at a desired location, and An article having the patterned cured layer can be produced. Substrate 102 can be further processed as described herein.

The obtained patterned cured layer can be used, for example, in the semiconductor processing mentioned later or can also be used as an optical member (including as a part of the optical member), such as a diffraction grating or a bias. A pole piece for obtaining an optical member. In this example, an optical component having at least a substrate 102 and the patterned cured layer disposed on the substrate 102 can be prepared. For a reverse tone process, a separate residual layer etch is not required. However, it should be understood that the adhesion layer etch can be etched compatible with the photoresist material.

After the residual layer is removed, the patterned cured layer 304 having no residual layer is used as a resist film when etching a portion of the exposed substrate 102. Conventional dry etching apparatus known in the art can be used in the dry etching process. The etching gas is appropriately selected depending on the basic components of the solidified layer that will receive the etching and the basic components of the substrate 102. For example, a halogen gas (for example, CF ₄ , C ₂ F ₆ , C ₃ F ₈ , CCl ₂ F ₂ , CCl ₄ , CBrF ₃ , BCl ₃ , PCl ₃ , SF _{6 ,} and Cl ₂ ), an oxygen atom-containing gas may be used. (eg, O ₂ , CO, and CO ₂ ), an inert gas (eg, He, N _{2 ,} and Ar) or a gas such as H ₂ or NH ₃ . These gases can be used in the form of a mixture. The etching gas used for the removal of the residual layer mentioned above and the etching gas used for the substrate processing may be the same or different.

As already mentioned, a heterogeneous mixture of the pretreatment composition and the imprinted photoresist material can be formed in the cured layer 202 having a pattern shape.

The pretreatment composition preferably has an anti-dry etchant that is substantially the same as the dry etch resist of the imprinted photoresist material. This allows the substrate 102 to be advantageously processed even in a region having a high concentration of the pretreatment composition. Therefore, the substrate 102 can be uniformly processed.

In addition to the series of steps (manufacturing process) mentioned above, an electronic component can be formed to form a circuit structure on the substrate 102 in accordance with the shape of the pattern obtained from the shape of the template 110. Therefore, a circuit substrate used in a semiconductor device or the like can be manufactured. Examples of such semiconductor devices include LSI, system LSI, DRAM, SDRAM, RDRAM, D-RDRAM, and NAND flash memory. The circuit substrate can also be connected to, for example, an electrical circuit for a circuit substrate A road control mechanism for forming electronic devices such as displays, cameras, and medical devices.

Similarly, the patterned hardened product having no residual layer can also be used as an etch-resistant film when the substrate is treated by dry etching to fabricate an optical member.

Alternatively, a quartz substrate can be used as the substrate 102, and the patterned hardened product 202 can be used as an anti-etching film. In this example, the quartz substrate can be processed by dry etching to produce a replica of a quartz imprint mold (replica mold).

The patterned hardened product 202 may eventually be removed from the treated substrate during preparation of a circuit substrate or an electronic component, or may be constructed to be retained as an element constituting the device. Come down.

Instance

In the example below, the interface energy reported at the interface between the imprinted photoresist material and air is measured using the maximum bubble pressure method. These measurements were measured using a BP2 bubble pressure tensiometer manufactured by Krüss GmbH of Hamburg, Germany. In the maximum bubble pressure method, the maximum internal pressure within a bubble formed in a liquid by a capillary is measured. The surface tension can be calculated by the Young-Laplace formula by a capillary having a known diameter. For the pretreatment composition, the interface energy at the interface between the pretreatment composition and the air is measured by the maximum bubble pressure method or by the number reported by the manufacturer. The value is obtained.

Viscosity was measured using a Brookfield DV-II+Pro and was carried out using a small sample adapter set to a temperature control bath at 23 °C. The reported viscosity value is the average of the five measurements.

The adhesive layer is prepared on the substrate by curing a viscous composition by mixing about 77 grams of ISORAD 501, about 22 grams of CYMEL 303ULF, and about 1 gram of TAG 2678. This mixture was obtained by adding it to about 1900 g of PM acetate. The viscous composition is spin coated onto a substrate (e.g., a wafer) that rotates at a speed of 500 to 4000 revolutions per minute to provide a substantially smooth (if not planar) layer having a uniform thickness. Layer). The spin-coated composition was exposed to thermal actinic energy at 160 ° C for about 2 minutes. The resulting adhesive layer is from about 3 nanometers to about 4 nanometers thick.

In Comparative Example 1 and Examples 1-3, an embossed photoresist material having a surface tension of 33 mN/m at the interface of the air/imprinted photoresist material was used to demonstrate the expansion of the embossed photoresist material on different surfaces. . The embossed photoresist material is a polymerizable composition comprising about 45 wt% monofunctional acrylate (e.g., isobornyl acrylate and benzyl acrylate), about 48 wt% difunctional acrylate (e.g., new) a mixture of pentanediol diacrylate), and about 5 wt% of a photoinitiator (eg, TPO and 4265), and about 3 wt% of a surfactant (eg, XR-(OCH ₂ CH ₂ ) _n OH, wherein R = Alkyl, aryl or poly(propylene glycol), X=H or -(OCH ₂ CH ₂ ) _n OH, and n is an integer (for example, 2 to 20, 5 to 15 or 10-12) (for example, X =-(OCH ₂ CH ₂ ) _n OH, R = poly(propylene glycol), and n = 10-12), and a fluorosurfactant wherein X = perfluoroalkyl.

In Comparative Example 1, the embossed photoresist material was directly disposed on the adhesive layer of a nanoimprint lithography substrate. Figure 11 is an image of a droplet 1100 of an imprinted photoresist material on an adhesive layer 1102 of a substrate after the droplets of the imprinted photoresist material have been dispensed in a grid pattern for 17 seconds. As seen in the image, the drop 1100 has expanded outward from the target area on the substrate. However, the expansion beyond the target area is still limited, and the area of the exposed adhesive layer 1102 is larger than the area of the droplet 1100. The rings visible in this and other images, such as ring 1104, are Newton interference rings that exhibit thickness differences in different droplet regions. The size of the embossed photoresist material droplets is about 2.5 pL. In Figure 11, there is a 2x7 (pitch) ² interlaced droplet grid (eg, 2 units in the horizontal direction, 3.5 units between the line and the line). Each subsequent line is offset by 1 unit in the horizontal direction.

In Examples 1-3, the pretreatment compositions AC were each disposed on a nanoimprint lithography substrate to form a pretreatment coating. Droplets of imprinted photoresist material are disposed on the pretreatment coatings. Figures 12-14 show images of the pretreatment coating after the droplets of the imprinted photoresist material begin to be dispensed. Although mixing occurs between the pretreatment composition and the imprinted photoresist material in these examples, for the sake of simplicity, the droplets of the imprinted photoresist material and the pretreatment coating are not considered in the following description. Mixed with each other. The pretreatment composition is disposed on a wafer substrate by spin coating. More specifically, the pretreatment composition was dissolved in PGMEA (0.3 wt% of the pretreatment composition / 99.7 wt% of PGMEA) and was spin coated on the wafer substrate. When the solvent evaporates, the thickness of the resulting pretreatment coating on the substrate is typically in the range of 5 nm and 10 nm (e.g., 8 nm). The size of the embossed photoresist material droplets in Figures 12-14 is about 2.5 pL. In Figures 12 and 14, there are 2 x 7 (pitch) ² interlaced droplet grids (e.g., 2 units in the horizontal direction, 3.5 units between line and line). Each subsequent line is offset by 1 unit in the horizontal direction. Figure 13 shows a 2 x 6 (pitch) ² interlaced droplet grid. The pitch value is 84.5 microns. The volume ratio of the imprinted photoresist material to the pretreatment layer is in the range of 1 to 15 (e.g., 6 to 7).

Table 1 lists the surface tension (air/liquid interface) of the pretreatment compositions A-C and imprinted photoresist materials used in Examples 1-3.

In Example 1 (see Table 1), the droplets of the imprinted photoresist material were placed on a substrate having a pretreatment composition A coating (Sartomer 492 or "SR492"). The SR 492 (available from Sartomer, Inc., of Pennsylvania, USA) is propoxylated (3) trimethylolpropane triacrylate (a polyfunctional acrylate). Figure 12 shows the separation An image of the embossed photoresist material droplets 1200 and the obtained pretreatment coating 1204 on the pretreatment coating 1202 after 1.7 seconds of initial application in a staggered grid pattern. In this example, the droplets retain their spherical cap shape and the expansion of the imprinted photoresist material is limited. As seen in Figure 12, when the droplets 1200 expand beyond the expansion of the imprinted photoresist material on the adhesive layer in Comparative Example 1, the droplets remain separated by the pretreatment coating 1202, which is A perimeter 1206 is formed around the droplet. Some of the composition of the imprinted photoresist material extends beyond the center of the droplet, which forms a region 1208 that surrounds the droplet 1200. Region 1208 is separated by a pretreatment coating 1202. This limited expansion is due, at least in part, to the slight surface tension difference (1 mN/m) between the pretreatment composition A and the imprinted photoresist material, so that there is no significant energy advantage for droplet expansion. Other factors (such as friction) are also considered to have an impact on the extent of the expansion.

In Example 2 (see Table 1), the droplets of the imprinted photoresist material were placed on a substrate having a pretreatment composition B coating (Sartomer 351HP or "SR351HP"). The SR351HP (available from Sartomer, Inc., of Pennsylvania, USA) is trimethylolpropane triacrylate (a polyfunctional acrylate). Figure 13 shows droplets 1300 of imprinted photoresist material on the pretreated coating 1302 in 1.7 seconds after the droplets begin to be dispensed in a staggered grid pattern at the separated portions and the resulting pretreatment coating Image of layer 1304. After 1.7 seconds, the droplets 1300 cover a substantial portion of the surface area of the substrate and are separated by the pretreatment coating 1302, which forms a boundary 1306 around the droplets. Droplet 1300 is more uniform than droplet 1200 of Example 1, and thus an extension to Example 1 can be observed Significantly improved expansion results. A greater degree of expansion is due, at least in part, to the difference in surface tension (3.1 mN/m) between the pretreatment composition B and the imprinted photoresist material, which is greater than the pretreatment composition A and the imprinted photoresist material of Example 1. The difference in surface tension between.

In Example 3 (see Table 1), the droplets of the imprinted photoresist material were placed on a substrate having a pretreatment composition C coating (Sartomer 399LV or "SR399LV"). The SR399LV (available from Sartomer, Inc., of Pennsylvania, USA) is dipentaerythritol pentaacrylate (a polyfunctional acrylate). Figure 14 shows droplets 1400 of imprinted photoresist material on the pretreatment coating 1402 after 1.7 seconds in which the droplets begin to be dispensed in a staggered grid pattern at the separated portions and the pretreatment coating obtained. Image of layer 1404. As seen in Figure 14, the droplets 1400 are separated by a pretreatment coating 1402 at a boundary 1406. However, most of the imprinted photoresist material is deposited at the droplet boundaries such that a majority of the polymerizable material is at the droplet boundary and the droplet center is substantially empty. The extent of the expansion is due, at least in part, to the large surface tension difference (6.9 mN/m) between the pretreatment composition C and the imprinted photoresist material.

The defect density was measured as a function of the pre-expansion time of the imprinted photoresist material of Examples 1-3 and the pre-treatment composition B of Example 2. Figure 15 shows the unfilled defect density (void) resulting from the template. Curve 1500 shows the defect density (number of defects per cm ² ) as a function of the spread time (seconds) of the 28 nm line/space pattern region, where the defect density approaches 0.1/cm ² at 0.9 seconds. Curve 1502 displays the defect density (number of defects per cm ² ) as a function of time in extended time (seconds) over the entire area having a range of feature configurations, with the defect density approaching 0.1/cm ² at 1 second. Comparing the two phases, when there is no pretreatment, the defect density is close to 0.1/cm ² for the entire region from 2.5 seconds to 3 seconds.

The characteristics of the pretreatment compositions PC1-PC9 are shown in Table 2. The key to PC1-PC9 is shown below. The viscosity was measured at a temperature of 23 ° C as described above. In order to calculate the diameter ratio (diameter ratio) at 500 ms as shown in Table 2, the droplets of the imprinted photoresist material (droplet size ~25 pL) were allowed to spread over a substrate, a pretreatment composition (about 8 nm to 10 nm thick was coated on an adhesive layer, and the droplet diameter was recorded during a period of 500 ms. The droplet diameter of each pretreatment composition was divided by the embossed photoresist material on the adhesive layer without the pretreatment composition at a droplet diameter of 500 ms. As shown in Table 2, the embossed photoresist material on PC1 had a droplet diameter of 500% greater than the droplet diameter of the embossed photoresist material on the adhesive layer without the pretreatment coating. Figure 16 shows the droplet diameter (μm) as a function of time (ms) of the pretreatment compositions PC1-PC9. The relative etch resistance is the Ohnishi parameter of each pretreatment composition divided by the Ohnishi parameter of the imprinted photoresist material. The relative etching resistance of the pretreatment compositions PC1-PC9 (the ratio of the etching resistance of the pretreatment composition to the etching resistance of the imprinted photoresist material) is shown in Table 2.

PC1: Trimethylolpropane triacrylate (Sartomer)

PC2: Trimethylolpropane ethoxy triacrylate, n~1.3 (Osaka Organic)

PC3: 1,12-dodecanediol diacrylate

PC4: polyethylene glycol diacrylate, Mn, avg = 575 (Sigma-Aldrich)

PC5: tetraethylene glycol diacrylate (Sartomer)

PC6: 1,3-adamantanediol diacrylate

PC7: decanediol diacrylate

PC8: m-xylene diacrylate

PC9: tricyclodecane dimethanol diacrylate (Sartomer)

The pretreatment compositions PC3 and PC9 were combined at different weight ratios to obtain a pretreatment composition PC10-PC13, the weight ratios of which are shown in Table 3. A comparison of the properties of PC3 and PC9 with the mixture they form reveals a complementary effect. For example, PC3 has a relatively low viscosity and has a relatively fast template fill, but has relatively poor etch resistance. Conversely, PC9 has relatively good etch resistance and film stability (low evaporation loss), but is relatively viscous and exhibits relatively slow template filling. However, PC3 and PC9 combine to obtain a combination of advantageous properties of the pretreatment composition, including relatively low viscosity, relatively fast template filling, and relatively good Resistance to etching. For example, a pretreatment composition having 30 wt% of PC3 and 70 wt% of PC9 was found to have a surface tension of 37.2 nM/m, a diameter ratio of 1.61, and an Ohnishi parameter of 3.5.

Figure 17A shows a plot of viscosity of a pretreatment composition comprising different PC3 and PC9 ratios (i.e., from 100 wt% PC3 to 100 wt% PC9). Figure 17B shows the droplet diameters of PC3, PC13, PC12, PC11, PC10 and PC9 (which were measured as described with respect to Table 2). Fig. 17C shows the ratio of surface tension (mN/m) vs. PC3 and PC9.

Several embodiments have been described. However, it is to be understood that various modifications may be made without departing from the spirit and scope of the disclosure, and other embodiments are within the scope of the following claims.

102‧‧‧Substrate

500‧‧‧Base

502‧‧‧Adhesive layer

504‧‧‧Pretreatment composition

506‧‧‧Pretreatment coating

Claims (15)

A nanoimprint lithography method comprising: disposing a pretreatment composition on a substrate to form a pretreatment coating on the substrate, wherein the pretreatment composition comprises a polymerizable component Separating a separate portion of an imprinted photoresist material on the pretreatment coating, each separate portion of the imprinted photoresist material covering a target region of the substrate, wherein the imprinted photoresist material Is a polymerizable composition; when each separated portion of the embossed photoresist material expands beyond its target region, a synthetic polymerizable coating comprising a mixture of the pretreatment composition and the embossed photoresist material is formed Layered on the substrate; contacting the synthetic polymerizable coating with a nanoimprint lithography template; and polymerizing the synthetic polymerizable coating to produce a synthetic polymeric layer on the substrate, Wherein the interfacial surface energy between the pretreatment composition and the air is greater than the interface between the imprinted photoresist material and the air or between at least one component of the imprinted photoresist material and the air can. The method of claim 1, wherein the difference between the interfacial composition between the pretreatment composition and the air and the interfacial energy between the imprinted photoresist material and the air is 0.5 mN/m. Up to 25 mN/m, 0.5 mN/m to 15 mN/m, or 0.5 mN/m to 7 mN/m; and/or wherein the interface energy between the imprinted photoresist material and air is 20 mN/m to 60 mN/m, 28 mN/m to 40 mN/m, or 32 mN/m to 35 mN/m; and/or wherein the interfacial composition between the pretreatment composition and air is 30 mN/m Up to 45mN/m. The method of claim 1, wherein the pretreatment composition has a viscosity at 23 ° C ranging from 1 cP to 200 cP, 1 cP to 100 cP, or 1 cP to 50 cP; and/or wherein the imprinted photoresist material The viscosity at 23 ° C is in the range of 1 cP to 50 cP, 1 cP to 25 cP, or 5 cP to 15 cP. The method of claim 1, wherein the pretreatment composition comprises a monomer; and/or wherein the pretreatment composition comprises a monofunctional, difunctional, polyfunctional acrylate monomer. The method of claim 1, wherein the embossed photoresist material comprises: 0 wt% to 80 wt%, 20 wt% to 80 wt%, or 40 wt% to 80 wt% of one or more monofunctional acrylates; 20 wt% Up to 98% by weight of one or more difunctional or polyfunctional acrylates; from 1% to 10% by weight of one or more photoinitiators; and from 1% to 10% by weight of one or more surfactants. The method of claim 1, wherein the polymerizable component of the pretreatment composition and a polymerizable component of the imprinted photoresist material react to form during polymerization of the synthetic polymerizable coating layer. a covalent bond; and/or wherein the pretreatment composition and the imprinted photoresist material each comprise a monomer having a common functional group. The method of claim 1, wherein the pretreatment composition is disposed on the nanoimprint lithography substrate comprising spin coating the pretreatment composition onto the nanoimprint lithography substrate And/or wherein a separate portion of the imprinted photoresist material contacts at least one other discrete portion of the imprinted photoresist material prior to contacting the synthetic polymerizable coating with the nanoimprint lithography template A boundary is formed between two separate portions. A nanoimprint lithography stack formed by the method of claim 1, wherein the nanoimprint lithography stack comprises the synthesized polymeric layer on the substrate. A method of fabricating a device comprising the nanoimprint lithography method of claim 1 of the patent application. A device formed by the method of claim 9 of the patent application. A nanoimprint lithography kit comprising: a pretreatment composition; and an embossed photoresist material; wherein the pretreatment composition comprises a polymerizable component, the imprinted photoresist material being a polymerizable composition, And an interface energy between the pretreatment composition and the air is greater than an interface energy between the imprinted photoresist material and the air or between at least one component of the imprinted photoresist material and the air. A method of pretreating a nanoimprint lithography substrate, the method comprising: coating the substrate with a pretreatment composition, wherein the pretreatment composition comprises a polymerizable component; Separating a portion of the embossed photoresist material on the pretreatment composition, wherein the embossed photoresist material disposed in the separated portion of the pretreatment composition is expanded to be disposed without the pre-preparation Treating the same imprinted photoresist material on the same substrate of the composition faster; and disposing the separate portions of the imprinted photoresist material on the pretreatment composition and the imprinted photoresist material and the After the defined length of time between the nanoimprint lithography template contacts, the imprinted photoresist material is contacted with a nanoimprint lithography template, wherein the imprinted photoresist material and the nanoimprint lithography are When the template is in contact, a gap volume between the separated portions of the imprinted photoresist material disposed on the pretreatment composition is less than the imprint photoresist on the substrate without the pretreatment composition The configuration of the separate portions of the material defines a gap volume between the same imprinted photoresist material disposed over the same substrate without the pretreatment composition over a period of time. The method of claim 12, wherein the pretreatment composition has no polymerization initiator. A nanoimprint lithography stack comprising: a nanoimprint lithographic substrate; and a synthetic polymeric layer formed on a surface of the nanoimprint lithography substrate, wherein the synthetic polymeric layer The chemical composition is non-uniform and comprises a plurality of central regions separated by boundaries, wherein the chemical composition of the synthesized polymeric layer at the boundary is different from the chemical composition of the synthetic polymeric layer within the central regions. A nanoimprint lithography stack as claimed in claim 14 The central region and boundary of the polymeric layer are formed by a heterogeneous mixture of a pretreatment composition and an embossed photoresist material, wherein during the formation of the synthetic polymeric layer, one of the imprinted photoresist materials The polymerizable component reacts with a polymerizable component of the pretreatment composition to form a covalent bond.