TWI708118B - Nanoimprint lithography method, nanoimprint lithography stack, method for manufacturing a semiconductor device and a semiconductor device made by the method, nanoimprint lithography kit, method for pretreating a nanoimprint substrate, and imprint method - 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

Nanoimprint lithography method, nanoimprint lithography stack, method of manufacturing semiconductor device and semiconductor device manufactured by this method, method of pretreatment of nanoimprint lithography substrate, and imprint method [Related Application Case]

This application is related to U.S. Patent Application No. 15/195,789 filed on June 28, 2016 and named "SUBSTRATE PRETREATMENT FOR REDUCING FILL TIME IN NANOIMPRINT LITHOGRAPHY", which claims to be filed on January 22, 2016 U.S. Patent Application No. 15/004,679 named "SUBSTRATE PRETREATMENT FOR REDUCING FILL TIME IN NANOIMPRINT LITHOGRAPHY". The case also claims the name of the application filed on September 8, 2015 as "SUBSTRATE PRETREATMENT FOR REDUCING FILL TIME" IN NANOIMPRINT LITHOGRAPHY" US Patent Application No. 62/215,316 priority, the entire content of each of the above applications is hereby incorporated by reference.

The present invention relates to a technology for improving the yield rate of nanoimprint lithography processing by processing the nanoimprint lithography substrate to increase the spread of the imprint photoresist material on the substrate.

As the semiconductor processing industry strives for greater yields while increasing the number of circuits per unit, attention has been focused on the continued development of reliable high-resolution patterning technologies. One of the techniques used today is generally called imprint lithography. Imprint lithography processing is described in detail in many publications, such as US Patent Application Publication No. 2004/0065252 and US Patent Nos. 6,936,194 and 8,349,241, all of which are incorporated herein by reference. . Developments in other areas where imprint lithography has been used include biotechnology, optical technology, and mechanical systems.

An imprint lithography technique described in each of the aforementioned patent documents includes forming a relief pattern in an imprinted photoresist material and transferring a pattern corresponding to the relief pattern to a bottom On the substrate. The patterning process uses a template spaced apart from the substrate and a polymerizable composition (imprint photoresist material) between the template and the substrate to be deposited. In some cases, the imprinted photoresist material is disposed on the substrate in the form of separate, spaced droplets. Before the imprinted photoresist material contacts the template, the droplets are allowed to expand. After the imprinted photoresist material contacts the template, the photoresist material is allowed to uniformly fill the space between the substrate and the template, and then the imprinted photoresist material is cured to form a layer, which has a A pattern that retains the shape of the template surface. During curing, the template is separated from the patterned layer, so that the template and the substrate are separated.

The yield of an imprint lithography process generally depends on many factors. When the imprinted photoresist material is disposed on the substrate in the form of separated, spaced droplets, the yield depends at least in part on the efficiency and uniformity of the expansion of the droplets on the substrate degree. The expansion of the imprinted photoresist can be limited by a number of factors, such as the air gap between the droplet and the unfinished wetting of the substrate and/or the template by the droplet.

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 imprint photoresist The material part is arranged on the pretreatment coating, and each separated embossed photoresist material part covers a target area of the substrate. The pretreatment composition includes a polymerizable component, and the imprinted photoresist material is a polymerizable component. When each separated portion of the imprinted photoresist material expands beyond its target area, a synthetic polymerizable coating comprising a mixture of the pretreatment composition and the imprinted photoresist material is formed on the substrate. The synthetic polymerizable coating is in contact with a nanoimprint lithography template and is polymerized to produce a synthetic polymerized layer on the substrate. The interfacial surface energy between the pretreatment composition and air is greater than the interfacial surface energy between the imprinted photoresist material and air or between at least one component of the imprinted photoresist material and air.

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

The third aspect includes a method of manufacturing a device using the first aspect. The device can be a processed substrate, an optical component, or a quartz mold replica.

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

In the fifth aspect, a nanoimprint lithography kit includes a pre-processing composition and an imprint photoresist material. The pretreatment composition includes a polymerizable component, the imprinted photoresist material is a polymerizable composition, and the interface between the pretreatment composition and air can be greater than that between the imprinted photoresist material and air. Interfacial energy between at least one component of the imprinted photoresist material and air.

In a sixth aspect, a method for pretreating a nanoimprint lithography substrate includes coating the substrate with a pretreatment composition and disposing a separated part of the imprint photoresist material on the pretreatment composition on. The pretreatment composition includes a polymerizable component. The imprinted photoresist material arranged in the separated parts on the pretreatment composition expands faster than the imprinted photoresist material arranged on the same substrate in the part without the pretreatment composition. After a defined length of time has elapsed between the disposition of the separated portions of the imprinted photoresist material on the pretreatment composition and the contact between the imprinted photoresist material and the nanoimprint lithography template, The imprinted photoresist material is in contact with a nano imprint lithography template. When the imprint photoresist material is in contact with the nanoimprint lithography template, the volume of the gap between the separated portions of the imprint photoresist material disposed on the pretreatment composition is less than After the defined length of time has passed between the dispositions of the separated portions of the imprinted photoresist material in the portion of the substrate without the pretreatment composition The volume of the gap between the same imprinted photoresist materials arranged on the same substrate without the pretreatment composition.

In a seventh aspect, a nanoimprint lithography stack includes a nanoimprint lithography substrate and a synthetic polymer layer formed on a surface of the nanoimprint lithography substrate. The chemical composition of the synthesized polymer layer is not uniform and includes a plurality of central regions separated by boundaries. The chemical composition of the synthetic polymer layer at the boundary is different from the chemical composition of the synthetic polymer layer inside the central regions. In some cases, the nanoimprint lithographic substrate includes an adhesive layer, and the synthetic polymer layer is formed on a surface of the adhesive layer. In some cases, the central area and boundary of the synthetic polymeric layer are formed by a heterogeneous mixture of a pretreatment composition and an imprinted photoresist material.

The implementation of the above aspect may include one or more of the following features or may be formed by a process or component that includes one or more of the following features.

Disposing the pretreatment composition on the nanoimprint lithography substrate can be achieved by spin coating the pretreatment composition on the nanoimprint lithography substrate. In some cases, the nanoimprint lithography substrate includes an adhesive layer, and disposing the pretreatment composition on the nanoimprint lithography substrate includes disposing the pretreatment composition on the adhesive Layer up.

Disposing the separated portions of the imprinted photoresist material on the pretreatment coating may include distributing droplets of the imprinted photoresist material on the pretreatment coating. In some cases, a separate portion of the imprint photoresist material contacts at least one other separate portion of the imprint photoresist material, which contacts the nanoimprint lithography template at the synthetic polymerizable coating Previous form Into a boundary between two separate parts. When the synthetic polymerizable coating contacts the nanoimprint lithography template, each separated portion of the imprinted photoresist material and at least one other separated portion of the imprinted photoresist material can be pre-prepared 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 polymer layer may include covalently bonding a component of the pretreatment composition and a component of the imprinted photoresist material. The chemical composition of the synthesized polymerizable coating may 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 interface energy between the imprinted photoresist material and air is between 0.5 mN/m to 25 mN/m, 0.5 mN/m m to 15mN/m, or 0.5mN/m to 7mN/m. In some cases, the interface 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 interface energy between the pretreatment composition and the 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 1cP to 200cP, 1cP to 100cP, or 1cP to 50cP, and the viscosity of the imprinted photoresist material at 23°C is typically 1cP to 50cP , 1cP to 25cP, or 5cP to 15cP.

The pretreatment composition may include a monomer. In some cases, the pretreatment composition includes a single monomer, which is mainly composed of a single monomer, or a single monomer. In some cases, the pretreatment composition includes two or more monomers (eg, monofunctional, difunctional, or multifunctional 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, nonanediol diacrylate, meta-diacrylate 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; 20wt% to 40wt% 1,12-dodecanediol diacrylate and 60wt% to 80wt% tricyclodecane dimethanol diacrylate; or about 30wt% 1,12-dodecane diacrylate Alcohol diacrylate and about 70wt% tricyclodecane dimethanol diacrylate. In some cases, the pretreatment composition does not contain a polymerization initiator.

The imprinting photoresist material may include 0wt% to 80wt%, 20wt% to 80wt%, or 40wt% to 80wt% of one or more monofunctional acrylates; 20wt% to 98wt% of one or more difunctional groups Or multifunctional acrylate; 1wt% to 10wt% of one or more photoinitiators; and 1wt% to 10wt% of one or more surfactants. In some cases, the imprint photoresist material includes 90 wt% to 98 wt% of one or more difunctional or multifunctional acrylates and substantially no monofunctional acrylates. in In some cases, the imprint photoresist material includes one or more monofunctional acrylates and 20 wt% to 75 wt% of one or more difunctional or multifunctional acrylates.

The polymerizable component of the pretreatment composition and a polymerizable component of the imprint photoresist material can react to form a covalent bond during the polymerization of the synthesized polymerizable coating. The pretreatment composition and the imprint photoresist material may each include a monomer having a common functional group (for example, an acrylate group).

The details of one or more embodiments of the main body of the invention described in this specification are presented in conjunction with the accompanying drawings and the following description. Other features, aspects, and benefits of the subject of the invention will become apparent from the following description, drawings, and scope of patent applications.

100‧‧‧Imprint lithography system

102‧‧‧Substrate

104‧‧‧Substrate Chuck

106‧‧‧table

108‧‧‧Template

110‧‧‧Platform

112‧‧‧Surface pattern

114‧‧‧Spaced depressions

116‧‧‧Protrusion

118‧‧‧Chuck

120‧‧‧Printing 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 polymer layer

204‧‧‧Remaining layer

206‧‧‧Protrusion

208‧‧‧Sag

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‧‧‧Imprinted photoresist material droplets (droplets)

602‧‧‧Target area

604‧‧‧Synthetic coating

606‧‧‧ area

608‧‧‧ area

610‧‧‧Border

900‧‧‧Synthetic coating

902‧‧‧Nano-imprint lithography stack

904‧‧‧Synthetic polymer layer

1000‧‧‧Synthetic coating

1002‧‧‧Nano-imprint lithography stack

1004‧‧‧Aggregate layer

1006‧‧‧area

1008‧‧‧area

1100‧‧‧droplets

1102‧‧‧Adhesive layer

1104‧‧‧ring

1200‧‧‧droplets

1202‧‧‧Pretreatment coating

1204‧‧‧Synthetic coating

1206‧‧‧Border

1208‧‧‧Region

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 on the substrate.

Figures 3A-3D show the spreading 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 a secondary configuration with a pretreatment coating The droplets of imprinted photoresist material on the substrate are formed into a synthetic coating.

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

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

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

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

FIG. 11 is an image of a droplet of an imprinted photoresist material corresponding to Comparative Example 1 after spreading on an adhesive layer of a substrate without a pretreatment coating.

Figure 12 is an image of a droplet of the imprinted photoresist described in Example 1 after spreading on a pretreatment coating.

FIG. 13 is an image of the droplets of the imprinted photoresist described in Example 2 after spreading on a pre-treatment coating.

FIG. 14 is an image of the droplets of the imprinted photoresist described in Example 3 after spreading on a pre-treatment coating.

Figure 15 shows the defect density as a function of the pre-spreading time used for the imprinting photoresist and the pre-processing of Example 2.

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

FIG. 17A shows the viscosity as a function of the fractional of one component in the two-component pretreatment composition. Figure 17B Shows the droplet diameter vs. the different fractions of the two-component pretreatment composition. FIG. 17C shows the surface tension of the two-component pretreatment composition vs. the fraction of one component in the two-component pretreatment composition.

FIG. 1 shows an imprint lithography system 100 used to form a concave-convex pattern on a substrate 102. The substrate 102 may include a substrate and an adhesive layer adhered to the substrate. The substrate 102 may be coupled to the substrate chuck 104. As shown in the figure, the substrate chuck 104 is a vacuum chuck. However, the substrate chuck 104 may include, but is not limited to, a vacuum type, a pin type, a groove type, an electromagnetic type, and/or the like. An exemplary chuck is described in US Patent No. 6,873,087, the content of which is incorporated herein by reference. The substrate 102 and the substrate chuck 104 can be further supported by the table 106. The table 106 can provide movement along the x-axis, y-axis, and z-axis. The table 106, the substrate 102 and the substrate chuck 104 can also be arranged on a base.

Separate from the substrate 102 is a template 108. The template 108 generally includes a rectangular or square mesa 110 that protrudes a certain distance from the surface of the template facing the substrate 102. A surface of the platform 110 may be patterned. In some cases, the platform 110 is referred to as a mold 110 or a mask 110. Template 108, mold 110, or both may include but are not limited to fused silica, quartz, silicon, silicon nitride, organic polymers, silicone polymers, borosilicate glass, fluorocarbon polymers, metals (e.g. Chromium, Tantalum), hardened sapphire and the like, or a combination of these materials. As shown in the figure, the pattern 112 on the surface includes a plurality of The characteristic structures defined by the recess 114 and the protrusion 116, but the embodiments are not limited to these structures. The pattern 112 on 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 chuck 118. The chuck 118 is typically constructed but not limited to vacuum, pin, groove, electromagnetic, or other similar chuck types. An exemplary chuck is described in US Patent No. 6,873,087, the content of which is incorporated herein by reference. In addition, the chuck 108 may be coupled to the imprint head 120 such that the chuck 118 and/or the imprint head 120 may be configured to facilitate the movement of the template 108.

The system 100 may further include a fluid dispensing system 122. The fluid dispensing system 122 can be used to place the imprinted photoresist 124 on the substrate 102. The imprint photoresist material 124 can use, for example, droplet dispensing, spin coating, immersion coating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thin film deposition, thick film deposition, or the like. Technology to deposit on the substrate 102. In the droplet dispensing method, the imprinted photoresist material 124 is arranged on the substrate 102 in the form of separated, spaced droplets, as shown in FIG. 1.

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

The imprint head 120 can apply a force to the template 108 so that the mold 110 contacts the imprint photoresist material 124. After the desired space has been filled with the imprinted photoresist material 124, the energy source 126 generates energy (eg, electromagnetic radiation energy or thermal energy), causing the imprinted photoresist material 124 to cure (eg, polymerize and/or crosslink) ), conform to the shape of the surface 134 of the substrate 102 and pattern the surface 112. After the imprint photoresist material 124 is cured to form a polymer layer on the substrate 102, the mold 110 is separated from the polymer layer.

FIG. 2 shows the formation of a nano-imprint lithography stack 200 by curing the imprint photoresist material 124 to produce a patterned polymer layer 202 on the substrate 102. The imprinted photoresist material 124 of the patterned layer 202 may include a residual layer 204 and multiple features, which are shown as protrusions 206 and recesses 208, wherein the protrusions 206 have a thickness t ₁ and the residual layer 204 has a thickness t ₂ . In nanoimprint lithography, the length of one or more protrusions 206, depressions 208, or both parallel to the substrate 102 is less than 100 nm, less than 50 nm, or less than 25 nm. In some cases, the length of one or more protrusions 206, recesses 208, or both is between 1 nm and 25 nm, or between 1 nm and 10 nm.

The above system and processing can be further implemented in other imprint lithography processing and systems, such as described in US Patent No. 6,932,934; No. 7,077,992; No. 7,197,396; and No. 7,396,475 in imprint lithography processing and system The contents of these patents are incorporated into this case by reference.

For the imprinted photoresist material 124 is arranged on the substrate 102 as a separate part ("droplet") as shown in FIG. For drop-on-demand or drop-on-demand nanoimprint lithography processing, the droplets of the imprinted photoresist material typically spread on the substrate before and after the mold 110 contacts the imprinted photoresist material.材102上. If the expansion of the droplets of the imprinted photoresist 124 is not sufficient to cover the substrate 102 or fill the recess 114 of the mold 110, the polymer layer 202 may be formed with defects in the form of voids. Therefore, the liquid-on-demand nanoimprint lithography process typically includes a process between the imprinting photoresist 124 droplet starting to dispense and the mold 110 starting to move toward the imprinting photoresist material on the substrate 102 ( And the subsequent filling of the space between the substrate and the template). Therefore, the output rate of an automated nanoimprint lithography process is usually limited by the diffusion rate of the imprinted photoresist on the substrate and the filling rate of the template. Therefore, the yield rate of liquid-on-demand or droplet-dispensing nanoimprint lithography processing can be reduced by shortening the "filling time" (that is, completely filling the space between the template and the substrate so that The gap does not exist) to improve.

One way to shorten the filling time is to increase the expansion rate of the imprinted photoresist material droplets and the coverage rate of the imprinted photoresist material to cover the substrate before the movement of the mold toward the substrate is started. Improving the coverage of the substrate is to reduce the volume of the gaps between the droplets of the imprinted photoresist material, thereby reducing the amount of space trapped in the gaps when the imprinted photoresist material contacts the mold. The amount of gas and reduce the number and severity of defects in the formed patterned layer. As described herein, the expansion rate of the imprinted photoresist and the uniformity of substrate coverage can be improved by pretreating the substrate with a liquid that can promote the compression during the formation of the patterned layer. The separated parts of the printed photoresist material are rapidly and uniformly expanded and the printed photoresist The material polymerizes so that the amount of gas trapped in the gap when the imprinted photoresist material contacts the mold and the number and severity of defects in the resulting patterned layer are reduced.

The expansion of the separated portion of a second liquid on a first liquid can be understood by referring to FIGS. 3A-3D. 3A-3D show the first liquid 300 and the second liquid 302 on the substrate 304 and in contact with a gas 306 (eg, air, a passivation gas, such as helium or nitrogen, or a combination of passivation gas). The first liquid 300 appears on the substrate 304 in the form of a coating or layer (coating and layer are used interchangeably herein). In some cases, the first liquid 300 appears as a layer having a thickness of several nanometers (eg, between 1 nm and 15 nm, or between 5 nm and 10 nm). The second liquid 302 appears as a separate part ("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 interface energy, or surface tension, between the second liquid 302 and the first liquid 300 is denoted as γ _L1L2 . The interface energy between the first liquid 300 and the gas 306 is labeled γ _L1G . The interface energy between the second liquid 302 and the gas 306 is labeled γ _L2G . The interface between the first liquid 300 and the substrate 304 can be labeled γ _SL1 . The interface between the second liquid 302 and the substrate 304 can be labeled as _γSL2 .

則θ=0°，且第二液體302完全擴展於第一液體300上。如果第一及第二液體彼此相混的話，則在一段時間之後，γ _L1L2=0 (3)在此情況下，第二液體302完全擴展在第一液體300上的條件是

對於第一液體300是薄膜且第二液體302是小液滴而言，彼此相混可藉由擴散處理來限制。因此，為了要使第二液體302擴展於第一液體300上，當第二液體302以液滴的形式被滴在第一液體300上時，不等式(2)更適用於擴展的初始階段。 FIG. 3A shows the second liquid 302 as a droplet 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 in the figure, 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. In equilibrium, the contact angle of the second liquid 302 on the first liquid 300 is θ, which is related to the interface energy γ _L1G , γ _L2G and γ _L1L2 through 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 spread on the first liquid 300. If the first and second liquids are mixed with each other, after a period of time, γ _{L 1 L 2} =0 (3) In this case, the condition that the second liquid 302 is completely spread on the first liquid 300 is

For the first liquid 300 being a thin film and the second liquid 302 being small droplets, mixing with each other can be restricted by diffusion treatment. Therefore, in order to expand the second liquid 302 on 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 very thick. In this example, the droplet does not touch the substrate 304. The droplet of the second liquid 302 and the layer of the first liquid 300 intersect at angles α , β, and θ, where α + β + θ = 2 π (5) The force balance along each interface has three conditions: 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, then γ _{L 1 L 2} =0 (9) and equations (6)-(8) It 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)

以及α=0,π (14)當第二液體302弄濕該第一液體300時，α=π (15) γ _{L 2 G.} cos( α )+ γ _{L 1 G} =0 (12) Equations (10) and (12) give

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) combining this result with equations (5) and (15) gives θ =0 (18)

時，該等界面之間沒有平衡。等式(12)變成一不等式，即使 是α=π，且第二液體302連續地擴展於該第一液體300上。 β = π (19) Therefore, equations (15), (18), and (19) give solutions to the angles α , β, and θ. when

At this time, 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.

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

The interface area 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 a solution to the angle α . In this example, assume that α = 0 (22) and θ ₁ = π (23)

時，第二液體302的液滴和第一液體300之間沒有平衡，且液滴沿著第二液體和氣體之間的界面連續地擴展直到被其他物理限制(如，體積的守衡及相互混合)所侷限為止。 β = π (24) when

At this time, there is no equilibrium between the droplets of the second liquid 302 and the first liquid 300, and the droplets continue to expand along the interface between the second liquid and the gas until they are restricted by other physical conditions (such as volume balance and mutual Mixed) is limited.

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

該液滴完全地擴展，且θ₂=0。

The droplet expands completely, and θ ₂ =0.

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

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

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

The different relationships among the four terms in inequality (29) will determine the droplet expansion characteristics. If the inequality (25) is valid and the equation (28) is invalid, the droplets of the second liquid 302 may initially spread along the surface of the first liquid 300. Or, as long as inequality (28) can be maintained but not equation (25) cannot be maintained, the droplet can begin to expand along the liquid-solid interface. Eventually, the first liquid 300 and the second liquid 302 will mix with each other, thus introducing more complexity.

γ_SL1)時，隨著液滴的擴展，θ₁接近於0°且θ₂接近180°。亦即，第二液體302的該液滴沿著該第一液體300和該第二液體之間的界面擴展且不會沿介於該第二液體和該基材304之間的界面擴展。 FIG. 3D shows a diagram of a droplet of the second liquid 302 that contacts the substrate 304 and has an interface with the first liquid 300. As shown in FIG. 3D, there are two droplets of the second liquid 302 on each side with two intersecting interface regions. A first interface region 300 is a first liquid, the second liquid 302 and gas 306 meet place, which is an angle α, β, and θ ₁ are denoted. Will intersect the second interface region 300 is a first liquid, the second liquid 302, and substrate 304 meet place, which is denoted by the angle θ _2. Here, when the surface tension of 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

γ _SL1 ), as the droplet expands, θ ₁ approaches 0° and θ ₂ approaches 180°. 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 expand along the interface between the second liquid and the substrate 304.

Equations (6)-(8) can be applied 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 will not mix with each other, so γ _{L 1 L 2} =0 (30).

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

時，第二液體302的液滴和第一液體300之間沒有平衡，且液滴沿著第二液體和氣體之間的界面連續地擴展直到被其他物理限制(如，體積的守衡及相互混合)所侷限為止。 β = π (34) when

At this time, there is no equilibrium between the droplets of the second liquid 302 and the first liquid 300, and the droplets continue to expand along the interface between the second liquid and the gas until they are restricted by other physical conditions (such as volume balance and mutual Mixed) is limited.

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

且該等液體是彼此不相混的話，亦即，γ _L1L2→0 (39) in case

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

，則角度θ₂接近180°，然後變成是未界定的。亦即，第二液體302具有沿著基材界面收縮且沿著第一液體300和氣體306之間的界面擴展的傾向。

, 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 interface of the substrate and expand along the interface between the first liquid 300 and the gas 306.

γ _L2G )時，第二液體302的液滴的完全擴展可發生在第一液體300的層上。在第二種情況中，第二液體302的液滴被配置在該第一液體300的層上，同時接觸該基材304並同一時間擴展於該基材304上。第一液體300和第二液體302是彼此不相混的。 在理想狀況下，當：(i)第一液體300在氣體中的表面能量大於或等於第二液體302在氣體中的表面能量(γ _L1G

γ _L2G )時；及(ii)第一液體和基材304之間的界面的表面能量大於第二液體和基材之間的界面的表面能量(γ _SL1

γ _SL2)時，完整的擴展就會發生。在第三種情況中，第二液體302的液滴被配置在該第一液體300的層上，同時接觸該基材304。擴展會沿著第二液體302和第一液體300之間的界面或是第二液體和基材304之間的界面發生。第一液體300和第二液體302是彼此不相混的。在理想狀況下，完整的擴展是在(i)第一液體300在氣體中的表面能量和第一液體與基材304之間的界面的表面能量的總合大於或等於第二液體302在氣體中的表面能量和第二液體與基材之間的界面的表面能量的總合(γ _L1G +γ _SL1

γ _L2G +γ _SL2)，同時第一液體300在氣體中的表面能量大於或等於第二液體302在氣體中的表面能量(γ _L1G

γ _L2G )時，或在(ii)介於第一液體和基材304之間的界面的表面能量大於第二液體和基材之間的界面的表面能量(γ _SL1

γ _SL2)時發生。當第二液體302包括多於一個成分時，完整的擴展係在(i)第一液體300在氣體中的表面能量和第一液體與基材304之間的界面的表面能量的總合大於或等於第二液體302在氣體中的表面能量和第二液體與基材之間的界面的表面能量的總合(γ _L1G +γ _SL1

γ _L2G +γ _SL2)，同時第一液體300在氣體中的表面能量大於或等於第二液體302的至少一成分在氣體中的表 面能量時，或在(ii)介於第一液體和基材304之間的界面的表面能量大於第二液體的成分中的一種成分和基材之間的界面的表面能量時發生。 The relationship between the expansion of the second liquid 302 on the first liquid 300 and the surface energy for complete expansion can be summarized into three different situations. In the first case, the droplets of the second liquid 302 are arranged on the layer of the first liquid 300, and the droplets of the second liquid 302 do not contact the substrate 304. The layer of the first liquid 300 can be thick or thin, and the first liquid 300 and the second liquid 302 are immiscible 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}

When γ _{L 2 G} ), the complete expansion of the droplets of the second liquid 302 can occur on the layer of the first liquid 300. In the second case, the droplets of the second liquid 302 are arranged on the layer of the first liquid 300 while contacting the substrate 304 and spreading on the substrate 304 at the same time. The first liquid 300 and the second liquid 302 are immiscible 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}

γ _{SL 2} ), complete expansion will occur. In the third case, the droplets of the second liquid 302 are arranged on the layer of the first liquid 300 while contacting the substrate 304. The expansion will 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 immiscible with each other. Under ideal conditions, the complete expansion is when (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 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} ), and 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 when (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} ). When the second liquid 302 includes more than one component, the complete expansion is based on (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 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} ), and 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 when (ii) between the first liquid It occurs when the surface energy of the interface with the substrate 304 is greater than the surface energy of the interface between one of the components of the second liquid and the substrate.

By using a selected liquid pretreatment composition to pretreat a nanoimprint lithographic substrate to have a surface energy greater than that of the imprint photoresist material in an ambient atmosphere (e.g., air or inert gas) Surface energy. In the liquid-on-demand nanoimprint lithography process pressure, the rate of expansion of the imprint photoresist material on the substrate can be increased, and before the imprint photoresist material contacts the template, the imprint A more uniform thickness of the photoresist material on the substrate can be established, thereby promoting 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 imprinted photoresist droplets before imprinting. As used herein, "dispensing time" generally refers to the time between the dispensing of a droplet and the contact of the droplet with the template. If the pretreatment composition includes a polymerizable component that can be mixed with the imprinted photoresist material, this can make an advantageous contribution to the formation of a polymer layer without adding unwanted components, and a more uniform The curing result, thereby providing more uniform mechanical and etching characteristics.

FIG. 4 is a flowchart showing a process 400 for increasing the yield of the liquid-on-demand nanoimprint lithography process. Process 400 includes operations 402-410. In operation 402, a pretreatment composition is disposed on a nanoimprint lithographic substrate to form a pretreatment coating on the substrate. In operation 404, separated 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 imprint photoresist material are selected so that the interface energy between the pretreatment composition and the air is higher than the interface energy between the imprint photoresist material and the air.

In operation 406, when each droplet of the imprinted photoresist material expands beyond its target area, a synthetic polymerizable coating ("synthetic coating") is formed on the substrate. The synthesized coating includes a homogeneous or heterogeneous mixture of the pretreatment composition and the imprinted photoresist material. In operation 408, the synthesized 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 polymerized layer on the substrate. After the polymerization of the synthetic coating, the template is separated from the polymerized layer, leaving a stack of nanoimprint lithography. As used herein, "nanoimprint lithography stack" generally refers to the substrate and the polymer layer adhered to the substrate, and each or both of the substrate and the polymer layer can be Includes one or more additional (eg, intervening) layers. In one example, the substrate includes a base and an adhesive layer adhered to the base.

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 on both sides of the capillary meniscus formed is proportional to the surface energy of the liquid. The higher the surface energy, the greater the driving force for liquid expansion. Therefore, typically, an imprinted photoresist with a higher surface energy is better. While interacting with a pretreatment composition, the dynamics of the expansion of the photoresist material droplet depends on the viscosity of both the imprinted photoresist material and the pretreatment composition. An imprint photoresist or pretreatment composition with a higher viscosity tends to slow down the droplet expansion 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. For fast filling in nanoimprint lithography processing, imprint photoresist materials with high surface tension and low contact angle are desirable. The contact angle of the imprint photoresist material on the surface of a nanoimprint lithography template is typically less than 90°, less than 50°, or less than 30°.

In process 400, the pretreatment composition and the imprinted photoresist material include, for example, those described 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-25nm 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 and other documents. The contents of all these patents and documents 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 multifunctional derivatives. In some love In this case, the pretreatment composition, the imprinted photoresist, or both are substantially free of silicon. In other cases, the pre-treatment composition, the imprinted photoresist, or both contain silicon. Examples of silicon-containing monomers include siloxane and disiloxane. The resin may be a silicon-containing resin (for example, silsesquioxane) and a non-series resin (for example, a phenol resin). The pretreatment composition, the imprint photoresist material, or both may also include one or more polymerization initiators or free radical generators. The types of polymerization initiators include, for example, photoinitiators (for example, acyloin, xanthones, and benzophenones), photoacid generators (for example, sulfonates and onium salts), and photobase generators. Agents (e.g., ortho-nitrobenzyl carbamates, urethane oximes, and O-acyl oximes).

Suitable monomers include monofunctional, difunctional or polyfunctional acrylates, methacrylates, vinyl ethers and epoxides, where the mono-, di- and poly-respectively refer to one , Two and three or more functional groups as shown. Some or all of these monomers can be fluorinated (e.g., perfluorinated). For example, in the case of acrylate, the pretreatment composition, the imprint photoresist material, or both may contain one or more monofunctional acrylates, one or more difunctional acrylates, One or more multifunctional acrylates or combinations 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- Base) methacryl 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 (e.g., Mn, avg= 575), 1,2-propylene glycol 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-decane Glycol diacrylate, 1,12-dodecanediol diacrylate, neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A diacrylate Acrylate, ethoxylated bisphenol A diacrylate, m-xylene diacrylate, ethoxylated (3) bisphenol A diacrylate, ethoxylated (4) bisphenol A diacrylate, Ethoxylated (10) bisphenol A diacrylate, dicyclopentane diacrylate, 1,2-adamantanediol diacrylate, 2,4-diethylpentane-1,5-di Alcohol diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (300) diacrylate, 1,6-hexanediol (EO) ₂ diacrylate, 1,6-hexanediol ( EO) ₅ diacrylate and alkoxylated aliphatic diacrylate.

Examples of suitable polyfunctional acrylates include trihydroxy Methylpropane triacrylate, propoxylated trimethylolpropane triacrylate (e.g., propoxylated (3) trimethylolpropane triacrylate, propoxylated (6) trimethylolpropane Triacrylate), trimethylolpropane ethoxy triacrylate (for example, n~1.3,3,5), di(trimethylolpropane) tetraacrylate, propoxylated glyceryl triacrylate ( For example, propoxylated (3) glyceryl triacrylate), tris(2-hydroxyethyl) isocyanuric 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 multifunctional acrylates described herein.

The photoinitiator is preferably a radical generator. Examples of suitable free radical generators include, but are not limited to, optionally substituted 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole Dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer 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; α- Amino aromatic ketone derivatives such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(form Sulfuryl)phenyl]-2-morpholinyl-propan-1-one; quinones such as 2-ethylanthraquinone, phenanthrenequinone, 2-t-butyl Anthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; derived from benzoin ethers Examples are benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin derivatives such as benzoin, methyl benzoin, ethyl benzoin, and propyl benzoin; benzyl Derivatives such as benzyldimethyl ketal; acridine derivatives such as 9-phenylacridine 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 (acetophenone benzyl ketal), 1-hydroxycyclohexyl phenyl ketal, and 2 , 2-Dimethoxy-2-phenylacetophenone; thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone, Phosphine oxide derivatives such as 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, and bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (2,6-Dimethoxybenzyl)-2,4,4-trimethylpentylphosphine; oxime ester derivatives such as 1,2-octanedione, 1-[4-(phenylthio )-, 2-(O-benzyl ester)], ethyl ketone and 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]- ,1-(O-Acetyl oxime); and xanthone, stilton, benzaldehyde stilbene, fluorene, anthraquinone, triphenylamine, carbazole, 1-(4-cumylphenyl)-2-hydroxy- 2-Methylpropan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

Examples of commercially available products of these 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 (produced by BASF) ; And EBECRYL P36 produced by UCB.

An oxyphosphine-based polymerization initiator or an alkylphenol-based polymerization initiator is preferable. In the examples listed above, the phosphine oxide-based polymerization initiator is an oxidized phosphine-based compound such as 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4 ,6-Trimethylbenzyl)phenylphosphine, and bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide. In the examples listed above, the alkylphenol polymerization initiator is benzoin ketone derivatives such as benzoin ketone, benzoin ethyl ether, and benzoin phenyl ether; benzoin derivatives such as benzoin Benzoin, 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-amino aromatic ketone derivatives such as 2 -Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-methanone Alkylpropan-1-one.

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

When the content of the photoinitiator is the total weight excluding the solvent components When the amount is 1 wt% 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 wt% or less of the total weight excluding the solvent components, the cured product obtained may be a cured product with 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 imprint lithography template, can be added to the imprint lithography photoresist, or both to reduce the cured photoresist and The separation force between the templates reduces the defects in the imprint pattern formed in the imprint lithography process and increases the number of successful imprints that can be manufactured with an imprint lithography template. Factors for selecting a release agent for imprinting photoresist include, for example, affinity with the surface, the desired surface characteristics of the surface to be treated, and the shelf life of the release agent in the imprinting photoresist ( shelf life). Although some liberating agents form a covalent bond with the template, the fluorinated nonionic surfactant interacts with the template through non-covalent bond interactions (for example, hydrogen bonding and Van der Waal interactions).

Examples of suitable surfactants include fluorinated and non-fluorinated surfactants. The fluorinated and non-fluorinated surfactants can be ionic or non-ionic surfactants. Suitable nonionic fluorinated surfactants include fluorine-aliphatic polymerizable esters, perfluoroether surfactants, polyoxyethylene fluorosurfactants, polyalkyl ethers fluorosurfactants , Fluoroalkyl polyethers and so on. Suitable nonionic non-fluorinated surfactants include ethoxylated alcohols, ethoxylated alkylphenols, polyoxyethylene-polyoxy Propylene block copolymer.

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

In addition, without detracting from the effect of the present invention, in addition to the above-mentioned components, the pretreatment composition and the imprinted photoresist material may include one or more non-polymerizable components according to different purposes. Examples of such ingredients include sensitizers, hydrogen donors, antioxidants, polymer ingredients, 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 excited by absorbing light with a specific wavelength A compound that is excited to interact with the photoinitiator as component (B). When used herein, interaction refers to the transfer of energy, electrons, etc. from the sensitizing dye in the activated state to the photoinitiator as component (B).

Examples of suitable sensitizing dyes include but are not limited to anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthones Derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, Ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes and pyrylium 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 reacts with the initiation radicals generated by the photoinitiator as the component (B) or the free radicals at the growth end of the polymer to generate more reactive free radicals. The hydrogen donor is preferably added when the component (B) is one or more light radical 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 aminobenzoate, N,N-Dimethylaminobenzoic acid isoamyl Esters, pentyl-4-dimethylaminobenzoate, triethanolamine and N-phenylglycine; and mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionate.

One kind of these hydrogen donors may be used alone, or two or more of these hydrogen donor systems may be used as a mixture. Moreover, these hydrogen donors have the same functions as sensitizers.

The content of these components (non-polymerizable components) in the imprint photoresist material is 0wt% or more and 50wt% or less of the total weight of all components (except components used for solvents) , Preferably 0.1 wt% or more and 50 wt% or less, more preferably 0.1 wt% or more and 20 mass% or less.

In addition, the imprint photoresist material may include one or more solvents as additional ingredients. Preferred solvents include, but are not limited to, solvents having a boiling point of 80°C or higher and 200°C or lower under 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, ethyl 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. A single solvent or a mixed solvent selected from these solvents is preferred.

In some examples, the pretreatment composition may be combined with one or more solvents. In an example in which the pretreatment composition is applied by spin coating, the pretreatment composition is combined with one or more solvents to promote expansion on the substrate. After expansion, substantially all solvents are Is evaporated to leave the pretreatment composition on the substrate.

Solvents suitable for combining with the pretreatment composition generally include the solvents described in relation to the imprint photoresist material. For applying the pretreatment composition by spin coating, from the viewpoint of coating characteristics, one is selected from 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, coating characteristics, film thickness, etc., and preferably the pretreatment composition and the solvent 70wt% or more, 90wt% or more, more preferably 95wt% or more of the total weight of A larger content of solvent components can make the film thickness of the pretreatment composition thinner. If the content of the solvent component is 70 wt% or less of the solvent/pretreatment composition mixture, proper coating characteristics cannot be obtained.

Although these solvents can be used in the imprinted photoresist material, it is better that the imprinted photoresist material contains no solvent. When used herein, the term "substantially free of solvent" means that there is no other solvent (eg, impurities) contained in the solvent other than the solvent. For example, the solvent content in the imprinted photoresist material according to this embodiment is preferably The photoresist material is 3wt% or less, more preferably 1wt% or less. When used herein, a solvent refers to a solvent that is generally used in a curable composition or a photoinitiator. In other words, the solvent is not limited to their types, as long as the solvent can dissolve and uniformly spread the compounds used in the present invention and does not react with these compounds.

In some examples, the imprinted photoresist material includes 0wt% to 80wt% (for example, 20wt% to 80wt% or 40wt% to 80wt%) of one or more monofunctional acrylates; 90wt% to 98wt% of one or more Bifunctional or multifunctional acrylate (for example, the imprinting photoresist material may be substantially free of monofunctional acrylates) or one or more difunctional or multifunctional acrylates (for example, 20wt% to 75wt%) , When one or more monofunctional acrylates are present); 1wt% to 10wt% of one or more photoinitiators; and 1wt% to 10wt% of one or more surfactants. In one example, the imprint photoresist material includes about 40wt% to about 50wt% of one or more monofunctional acrylates, about 45wt% to about 55wt% of one or more difunctional acrylates, and about 4wt% to about About 6 wt% of one or more photoinitiators, and about 3 wt% of surfactants. In another example, the imprint photoresist material includes about 44wt% of one or more monofunctional acrylates, about 48wt% of one or more difunctional acrylates, about 5wt% of one or more photoinitiators, And about 3wt% surfactant. In yet another example, the imprint photoresist material includes about 10wt% of the first monofunctional acrylate (for example, isobornyl acrylate), about 34wt% of the second monofunctional acrylate (for example, benzyl acrylate) Acrylate), about 48wt% of difunctional acrylate (for example, neopentyl glycol diacrylate), about 2wt% of the first photoinitiator (for example, IRGACURE TPO), about 3wt% of the second photoinitiator Agent (for example, DAROCUR 4265), and about 3wt% surfactant. Examples of suitable surfactants include XR-(OCH ₂ CH ₂ ) _n OH, where R=alkyl, aryl or poly(propylene glycol), X=H or -(OCH ₂ CH ₂ ) _n OH, and n is 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 fluorine-containing Surfactant, where X=perfluoroalkyl or perfluoroether, or a combination thereof. The viscosity of the imprinted 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 interface 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 interface energy are defined as in the examples described herein.

In one example, a pretreatment composition includes 0wt% to 80wt% (for example, 20wt% to 80wt% or 40wt% to 80wt%) of one or more monofunctional acrylates; 90wt% to 100wt% of one or A variety of difunctional or multifunctional acrylates (for example, the pretreatment composition system is substantially free of monofunctional acrylates) or 20wt% to 75wt% of one or more difunctional or multifunctional acrylates (For example, when there are one or more monofunctional acrylates); 0wt% to 10wt% of one or more photoinitiators; and 0wt% to 10wt% 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 so that it maintains the form of a thin film on the substrate until the synthetic coating is polymerized. In one example, the vapor pressure of the pretreatment composition at 25°C is less than 1×10 ^-4 mmHg. 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 interface 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 so that it does not decompose during use.

The pretreatment composition and the imprinted photoresist material should preferably include impurities in as small a content as possible. When used herein, impurities refer to anything other than the ingredients mentioned above. Therefore, the pretreatment composition and the imprinted photoresist material are preferably obtained through a purification process. This purification treatment is preferably filtered using a filter or the like. In detail, for filtration using a filter, the above-mentioned ingredients and optional additional ingredients should preferably be mixed, and then passed through a filter (which has a size of, for example, 0.001 micron or greater and 5.0 Micron or smaller hole size) to filter. For filtration using a filter, it is better that this filtration should be implemented in multiple stages or repeated multiple times. Moreover, the filtered solution can be filtered again. Multiple filters with different hole sizes can be used in this filtration. Filters made of polyethylene resin, polypropylene resin, fluororesin, nylon resin or the like can be used in The filtering, but the filter is not limited to this. Impurities (such as particles) mixed in the composition can be removed by this purification treatment. This prevents impurities (for example, particles) from causing pattern defects, which are formed in the cured film due to careless unevenness during curing of the curable composition.

In the example of using the pretreatment composition and the imprinted photoresist material to manufacture a semiconductor integrated circuit, it is preferable to avoid as much as possible impurities containing metal atoms (metal impurities) into the curable composition, To prevent the operation of the product from being prohibited. In this case, the concentration of 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 (for example, a monomer such as monofunctional acrylate, difunctional acrylate or multifunctional acrylate), a mixture of two or more polymerizable components (for example, two or A mixture of multiple monomers), or a mixture of one or more polymerizable components and one or more other components (for example, a mixture of multiple monomers; two or more monomers and a surfactant, a photoinitiator, or both Mixture of those, 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, nonanediol diacrylate, meta-xylene diacrylate, dicyclopentyl diacrylate, or any combination thereof.

Mixtures of polymerizable ingredients can produce complementary effects (synergistic effects), the pretreatment composition produced has a combination of more favorable characteristics (such as low viscosity, good etching resistance and film stability) than the pretreatment composition with 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 usually selected so that one or more components of the pretreatment composition polymerize (eg, covalently bond) with one or more components of the imprinted photoresist during the polymerization of the synthetic polymerizable coating Knot). In some cases, the pretreatment composition includes a polymerizable component that is also in the imprinted photoresist material, or includes a polymerizable component that has one and one or more components in the imprinted photoresist material. Functional groups shared by polymerizable components (eg, acrylate groups). Suitable examples of the pretreatment composition include, for example, the multifunctional acrylates described herein, including propoxylated (3) trimethylolpropane triacrylate, trimethylolpropane triacrylate, and dipentaerythritol Five acrylates.

The pretreatment composition can be selected so that the etching resistance can be similar to the etching resistance of the imprinted photoresist material, thereby improving the etching uniformity. In some cases, the pretreatment composition is selected so that the interface energy at the interface between the pretreatment composition and air is greater than the interface energy between the imprinted photoresist material and the pretreatment composition, thereby It promotes the rapid expansion of the liquid imprinting photoresist material on the liquid pretreatment composition, so as to form a uniform synthetic coating on the substrate before the synthetic coating contacts the template. The interface energy between the pretreatment composition and air is typically The interface energy between the imprinted photoresist material and air or the interface energy between at least one component of the imprinted photoresist material and air is greater than 0.5mN/m to 25mN/m, 0.5mN/m to 15mN /m, 0.5mN/m to 7mN/m, 1mN/m to 25mN/m, 1mN/m to 15mN/m, or 1mN/m to 7mN/m, but these ranges can be based on the pretreatment composition and the pressure The chemical and physical properties of the photoresist and the interaction between the two liquids change. When the difference between the surface energies is too small, it will result in too little expansion of the imprinted photoresist material, and the droplets will remain cap-shaped spherical and kept separated by the pretreatment composition. When the difference between the surface energies is too large, it will result in the excessive expansion of the imprinted photoresist material, that is, too much imprinted photoresist material moves toward the adjacent droplet, resulting in a vacancy in the center of the droplet, making the composite coating There is a concave area at the center of the droplet. Therefore, when the difference between the surface energies is too small or too large, the resulting composite coating is not uniform, but has significant concave or convex areas. When the difference between the surface energies is appropriately selected, the imprinted photoresist material expands rapidly to obtain a substantially uniform composite coating. The advantageous selection of the pretreatment composition and the imprinted photoresist material allows the filling time to be reduced by 50-90%, so that filling 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. The substrate 500 is typically a silicon wafer. Other suitable materials for the substrate 500 include fused silica, quartz, silicon germanium, gallium arsenide, and indium phosphide. The adhesive layer 502 is used to enhance the adhesion of the polymer layer to the substrate 500, thereby reducing the After the polymerization of the coating, defects are formed in the polymer layer during the separation of the template from the polymer layer. The thickness of the adhesive layer 502 is typically between 1 nanometer and 10 nanometers. Examples of materials suitable for the adhesive layer 502 include those 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 composed of ISORAD 501, CYMEL 303ULF, CYCAT 4040 or TAG 2678 (quaternary ammonium block trifluoromethanesulfonic acid), and PM Acetate (a type of Eastman Chemical Company of Kingsport, Tennessee) Provided, formed by the composition of 2-(1-methoxy)propyl acetate (solvent). In some examples, the substrate 102 includes one or more additional layers between the substrate 500 and the adhesive layer 502. In some cases, the substrate 102 includes one or more additional layers on the adhesive layer 502. For simplicity, the substrate 102 is shown as including 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, the pretreatment coating 506 is directly formed on the adhesive layer 502 of the substrate 102. In some cases, the pretreatment coating 506 is formed on the other surface of the substrate 102 (eg, directly formed 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 the case of spin coating, immersion 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 the like) to be applied to the substrate, and the solvent is then evaporated to leave the pretreatment coating. The thickness t _{p of the} pretreatment coating 506 is typically between 1 nanometer and 100 nanometers (eg, between 1 nanometer and 50 nanometers, between 1 nanometer and 25 nanometers, or Between 1nm and 10nm).

Referring again to FIG. 4, operation 404 of process 400 includes arranging droplets of imprinted photoresist material onto the pretreatment composition so that each droplet of imprinted photoresist material covers a target area of the substrate. The volume of the droplets of the imprinted 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, when each droplet of the imprinted photoresist material expands beyond its target area to form a composite coating, a composite coating is formed on the substrate. As used herein, "pre-expansion" refers to the two times that the droplet of the imprinted photoresist material contacts the pretreatment coating at the beginning of the droplet and expands beyond its target area and the template contacts the composite coating. Spontaneous expansion that occurs between.

6A-6D show the top view of the imprinted photoresist material droplet on the pretreatment coating when the imprinted photoresist material droplet is deployed on the target area, and the resultant coating before, during, and during the droplet expansion Top view at the end. Although the droplets are displayed as a square grid, the droplet patterns are not limited to square or geometric patterns.

Figure 6A shows that the droplet is initially configured to the pretreatment coating When layered, the top view of the drop 600 on the pretreatment coating 506 is such that the drop covers the target area 602 but does not extend beyond the target area. After the droplets 600 are arranged on the pretreatment coating 506, the droplets spontaneously expand to cover a surface area of the substrate larger than the target area, thereby forming a synthetic coating on the substrate . Figure 6B shows the resultant coating 604 during the pre-expansion period (after the part of the droplet 600 expands beyond the target area 602) and typically after partial mixing between the imprinted photoresist material and the pretreatment composition Top view. As shown in the figure, the synthetic coating 604 is a mixture of the liquid pretreatment composition and the liquid imprinted photoresist, where the region 606 contains most of the imprinted photoresist ("rich" imprint Photoresist), 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 pretreatment composition and the imprinted photoresist material.

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

Figures 7A-7D are along w-w, x-x, and Sectional view of y-y and z-z lines. FIG. 7A is a cross-sectional view along line w-w of FIG. 6A, which shows a droplet 600 of the imprinted photoresist material covering a surface area of the substrate 102 corresponding to the target area 602. Each target area (and each droplet initially arranged) has a center marked by a c-c line, and the b-b line marks an equidistant position between the centers of two target areas 602. For simplicity, the drop 600 is shown as contacting the adhesive layer 502 of the substrate 102, and the imprinted photoresist material and the pretreatment composition are shown as not being mixed with each other. FIG. 7B is a cross-sectional view along the line x-x of FIG. 6B, which shows the composite coating 604 with areas 608 exposed between the areas 606 after the area 606 has expanded beyond the target area 602. Fig. 7C is a cross-sectional view taken along the line y-y of Fig. 6C at the end of the pre-expansion, which shows the synthesized coating 604 as a homogeneous mixture of the pretreatment composition and the imprinted photoresist material. As shown, the area 606 has been expanded to cover a larger substrate surface than that shown in FIG. 7B, and the area 608 has been reduced accordingly. The area 606 initially starting from the droplet 600 is shown to be convex, however, the resultant coating 604 may be substantially flat or include concave areas. In some cases, because the imprinted photoresist material forms a continuous layer on the pre-treatment composition (not mixed with each other or completely or partially mixed with each other), the pre-expansion can continue to exceed that shown in FIG. 7C. The range shown. Fig. 7D is a cross-sectional view along line zz of Fig. 6D, which shows that because the resultant coating meets at the boundary 610 at the concave region near the center cc of the droplet, at the end of the expansion, the resultant coating The layer 604 becomes a homogeneous mixture of the pretreatment composition and the imprinted photoresist material, so that the thickness of the polymerizable coating at the boundary of the droplet is greater than that of the synthetic at the center of the droplet. The thickness of the coating. As shown in Figures 7C and 7D, when the synthesized coating contacts the nanoimprint lithography template, the thickness of the synthesized coating 604 at an equidistant position between the centers of the two target regions is different from the two The thickness of the resultant coating at the center of one of the target areas.

4 again, operations 408 and 410 of process 400 respectively include contacting the synthesized coating with a template, and polymerizing the synthesized coating to produce a nanoimprint lithography stack, which has a composite The coating on the nano-imprint lithographic substrate.

In some examples, as shown in FIGS. 7C and 7D, the synthesized coating 604 is a homogeneous mixture or substantially homogeneous at the end of the pre-expansion (ie, immediately before the synthesized coating and the template are in contact) Mixture (eg, at the air-synthetic coating interface). Therefore, the template contacts a homogeneous mixture, and the majority of the mixture comes from the imprinted photoresist material. Therefore, the release characteristics of the imprinted photoresist material will generally dominate the interaction between the synthesized coating and the template, as well as the separation of the polymer layer from the template, which includes the result of the template and the polymer layer. The separation force between the formation of defects (or no defect formation).

However, as shown in FIGS. 8A and 8B, the synthesized coating 604 may include regions 608 and 606, which are rich in pretreatment composition and rich in imprinted photoresist material, so that the template 110 contacts the synthesized coating 604 has different physical and chemical properties. For the sake of simplicity, the imprinted photoresist material in the area 606 is shown as having displaced the pretreatment coating so that the area 606 and the substrate are in direct contact, and shown not to be mixed with each other. Therefore, the thickness of the pretreatment composition in the region 608 It is not uniform. In FIG. 8A, the maximum height p of the area 606 is greater than the maximum height i of the pretreatment composition, so that the template 110 mainly contacts the area 606. In FIG. 8B, the maximum height i of the region 608 is greater than the maximum height p of the imprinted photoresist material, so that the template 110 mainly contacts the region 608. Therefore, the separation of the template 110 from the resultant synthetic polymer layer and the defect density associated therewith are non-uniform and this is because there are different mutual differences between the template and the imprinted photoresist and between the template and the pretreatment composition. effect. Therefore, for certain pretreatment compositions (for example, pretreatment compositions that include a single functional group or a mixture of two or more monomers, but no surfactant), the synthetic coating is applied to the template and The gas-liquid interface contacted by the synthetic coating forms a homogeneous mixture, or at least a substantially homogeneous mixture is preferred.

9A-9C and 10A-10C are cross-sectional views, which show the template 110 and the coating 604 synthesized on the substrate 102 with the substrate 500 and the adhesive layer 502 before and during the contact between the synthesized coating and the template. And the situation where a nano-imprint lithography stack is produced after the template is separated from the synthetic polymer layer. In Figures 9A-9C, the synthetic coating 604 is shown as a homogeneous mixture of the pretreatment composition and the imprinted photoresist. In FIGS. 10A-10C, the synthetic coating 604 is shown as a heterogeneous mixture of the pretreatment composition and the imprinted photoresist.

9A shows a cross-sectional view of the template 110 at the beginning of contact with the homogeneous synthetic coating 900 on the substrate 102. In FIG. 9B, the template 110 continues to advance toward the substrate 102 so that the composite coating 900 fills the recesses of the template 110. The synthesized coating 900 is polymerized to produce a After the homogeneous polymer layer is on the substrate 102, the template 110 is separated from the polymer layer. Figure 9C shows a cross-sectional view of a nanoimprint lithography stack 902 with a homogeneous synthetic polymeric layer 904.

FIG. 10A shows a cross-sectional view of the template 110 at the beginning of contact with the coating 604 synthesized on the substrate 102. The heterogeneous synthetic coating 1000 includes regions 606 and 608. As shown in the figure, the imprinted photoresist in the area 606 and the pre-treatment composition in the area 608 have little or no mixing with each other. In FIG. 10B, the template 110 continues to advance toward the substrate 102 so that the resultant coating 1000 fills the recesses of the template 110. After the synthetic coating 1000 is polymerized to produce a heterogeneous polymer layer on the substrate 102, the template 110 is separated from the polymer layer. 10C shows a cross-sectional view of a nanoimprint lithography stack 1002 with a heterogeneous synthetic polymeric layer 1004, where regions 1006 and 1008 correspond to regions 606 and 608 of the heterogeneous synthetic coating 1000. Therefore, the chemical composition of the synthesized polymer layer 1002 is heterogeneous or heterogeneous, and includes area 1006 (which has a composition derived from a mixture rich in imprinted photoresist material) and area 1008 (which has a composition derived from The ingredients of the mixture rich in the pretreatment composition). The relative size of regions 1006 and 1008 (eg, exposed surface area, surface area covered by the template, or volume) will be due at least in part to the degree of pre-expansion of the synthetic coating before contacting the template or expansion caused by contact with the template And change. In some cases, the region 1006 may be separated or surrounded by the region 1008, so that the synthesized polymer layer includes a plurality of central regions separated by boundaries, wherein the synthesized polymer layer 1004 has a different chemical composition at the boundary. Synthetic polymerization layer inside the central area Learn ingredients.

The contact between the synthetic coating 604 and the template 110 mentioned above can be performed in an atmosphere containing a condensable gas (which is hereinafter referred to as "condensable gas atmosphere"). As used herein, the condensable gas system refers to a gas condensed and liquefied by capillary pressure, which is a fine patterned depression formed on the template 110 and between a mold and a substrate The gap between is filled with gas in the atmosphere, the pretreatment composition and the imprinted photoresist material. When the synthesized coating is in contact with the template, the condensable gas exits like a gas in the atmosphere before the pretreatment composition and the imprinted photoresist material contact the template 110.

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

The boiling point of the condensable gas is not limited, as long as the temperature is equal to or lower than the ambient temperature when the synthesized coating is in contact with the template. The boiling point is preferably -10°C to 23°C, more preferably 10°C to 23°C. Within this range, better filling characteristics can be obtained.

The vapor pressure of the condensable gas at the ambient temperature when the synthetic coating and the template are in contact is not limited, as long as the pressure is equal to or lower than the pressure of the imprinting mold when the synthetic coating and the template are in contact. The vapor pressure is preferably 0.1 to 0.4 MPa. Within this range, better filling characteristics can be obtained. A vapor pressure greater than 0.4 MPa at ambient temperature It tends to be insufficiently effective in terms of letting air bubbles disappear. On the other hand, a vapor pressure of less than 0.1 MPa at ambient temperature tends to have to lower the pressure and require complicated equipment.

The environmental pressure when the synthesized coating is in contact with the template is not limited and is preferably 20°C to 25°C.

Specific examples of suitable condensable gases include frons, which include chlorofluorocarbons (CFC) such as trichlorofluoromethane, fluorocarbons (FC), hydrochlorofluorocarbons (HCFC), hydrofluorocarbons (HFC) such as 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, from the viewpoint that the synthesized coating and template have excellent filling characteristics when they are in contact at an ambient temperature of 20°C to 25°C, 1,1,1,3,3-pentafluoropropane (23 °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 preferable from the viewpoint of excellent safety. One of these condensable gases may be used alone, or two or more of these condensable gases may be used in a mixture.

These condensable gases can be used in a mixture with non-condensable gases (for example, air, nitrogen, carbon dioxide, helium, and argon). From the viewpoint of filling characteristics, helium gas is preferably used as a mixture of non-condensable gas and a condensable gas. The helium gas can penetrate the mold 205. Therefore, when the fine pattern recesses formed on the mold 205 are filled with these gases (condensable gas and helium) in a template in the atmosphere When in contact with the synthetic coating, while helium gas penetrates the mold, the condensable gas and the pretreatment composition and/or the imprinted photoresist material are liquefied together.

The polymer layer obtained by separating the template from the synthesized polymer layer has a special pattern shape. As shown in FIG. 2, the residual layer 204 may be maintained in a region other than the region having the pattern shape formed. In this case, the residual layer 204 present in the region to be removed of the cured layer 202 having the obtained pattern shape is removed by gas etching. Therefore, it is possible to obtain a patterned cured layer without the residual layer (that is, the all on the surface of the substrate 102) having the desired pattern shape (for example, the pattern shape obtained from the shape of the template 110). 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 in the recess of the cured layer 202 having a pattern shape by a technique such as etching to expose a pattern thereon. A method to shape the surface of the substrate 102 in the recesses 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 this field can be used, for example, Dry etching using an etching gas. Conventional dry etching equipment known in this field can be used in this dry etching process. The dry etching gas is appropriately selected according to the basic composition of the cured layer to be etched. For example, 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 ), and oxygen-containing gas can be used (For example, O ₂ , CO and CO ₂ ), inert gas (for example, He, N ₂ and Ar) or gas like H ₂ or NH ₃ . These gases can be used in the form of a mixture.

When the substrate 102 (the substrate to be processed) is a substrate in which the adhesion of the cured layer 202 is improved by surface treatment (for example, silane coupling treatment, silazane treatment, and organic film formation) The surface-treated layer can also be removed by etching after etching the residual layer 204 in the recess of the cured layer 202 with a pattern shape.

The manufacturing process described above can produce a patterned cured layer having a desired pattern shape (eg, a pattern shape obtained from the shape of the template 110) at a desired position without the residual layer, and An object with the patterned cured layer can be produced. The substrate 102 may 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 element (including as a part of the optical element), such as a diffraction grating or a polarization Pole device to obtain an optical component. In this example, an optical element 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 etching is not required. However, it should be understood that the adhesion layer etching is compatible with the photoresist etching.

After the residual layer is removed, the patterned cured layer 304 without the residual layer is used as a resist film when etching a part of the substrate 102 whose surface is exposed. Conventional dry etching equipment known in this field can be used in this dry etching process. The etching gas is appropriately selected according to the basic components of the cured layer to be etched and the basic components of the base material 102. For example, 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 ), and oxygen-containing gas can be used (For example, O ₂ , CO and CO ₂ ), inert gas (for example, He, N ₂ and Ar) or gas like 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 above-mentioned residual layer 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 may be formed in the cured layer 202 having a pattern shape.

The pretreatment composition preferably has an anti-dry etching agent substantially the same as the anti-dry etching agent of the imprint photoresist material. This allows the substrate 102 to be favorably processed even in an area with a high concentration of pretreatment composition. Therefore, the substrate 102 can be uniformly processed.

In addition to the series of steps (manufacturing processes) mentioned above, an electronic component may be formed to form a circuit structure on the substrate 102 according to the pattern shape 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. This circuit substrate can also be connected to, for example, a circuit substrate Road control mechanism to form electronic equipment such as displays, cameras and medical equipment.

Similarly, the patterned hardened product without a residual layer can also be used as an anti-etching film when the substrate is processed by dry etching to manufacture an optical member.

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

When preparing a circuit substrate or an electronic component, the patterned hardened product 202 can be finally removed from the processed substrate, or can be constructed as a component constituting the device and retained Come down.

Instance

In the following example, the interface energy reported at the interface between the imprinted photoresist and air is measured using the maximum bubble pressure method. These measured values are measured using a BP2 bubble pressure tensiometer manufactured by Krüss GmbH of Hamburg in Germany. In the maximum bubble pressure method, the maximum internal pressure in a bubble formed in a liquid by a capillary tube is measured. With a capillary with a known diameter, the surface tension can be calculated using the Young-Laplace formula. 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 the number reported by the manufacturer Value obtained.

Viscosity is measured with Brookfield DV-II+Pro and implemented with a small sample adapter set in a temperature-controlled bath at 23°C. The reported viscosity value is the average of five measurements.

The adhesive layer is prepared on the substrate by curing a viscous composition. The viscous composition is prepared by mixing about 77 grams of ISORAD 501, about 22 grams of CYMEL 303ULF, and about 1 grams of TAG 2678. , This mixture is added to about 1900 grams of PM acetate to obtain. The viscous composition is spin-coated on a substrate (such as a silicon wafer) rotating at a speed of 500 to 4000 revolutions per minute to provide a substantially smooth (if not flat) with uniform thickness的)layer. The spin-coated composition was exposed to thermal actinic energy at 160°C for about 2 minutes. The resulting adhesive layer is about 3 nm to about 4 nm thick.

In Comparative Example 1 and Examples 1-3, an imprinted photoresist with a surface tension of 33mN/m at the air/imprinted photoresist interface was used to demonstrate the expansion of the imprinted photoresist on different surfaces . The imprint photoresist material is a polymerizable composition, which includes about 45wt% monofunctional acrylate (for example, isobornyl acrylate and benzyl acrylate), about 48wt% difunctional acrylate (for example, new Pentanediol diacrylate), and about 5wt% photoinitiator (for example, TPO and 4265), and about 3wt% surfactant (for example, a mixture of XR-(OCH ₂ CH ₂ ) _n OH, where 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, where X=perfluoroalkyl.

In Comparative Example 1, the imprinted photoresist material is directly disposed on the adhesive layer of a nano imprint lithographic substrate. FIG. 11 is an image of the imprinted photoresist droplet 1100 on the adhesive layer 1102 of the substrate 17 seconds after the imprinted photoresist droplet started to be applied in a grid pattern. As seen in the image, the droplet 1100 has expanded 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 ring visible in this image and other images, such as ring 1104, is a Newton interference ring, which shows the difference in thickness in different droplet regions. The droplet size of the imprinted photoresist material is about 2.5 pL. In Figure 11, there is a 2x7 (pitch) ² staggered droplet grid (for example, 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 respectively arranged on a nanoimprint lithographic substrate to form a pretreatment coating. Droplets of imprinted photoresist material are arranged on the pretreatment coatings. Figures 12-14 show the image of the pretreatment coating after the droplets of the imprinted photoresist have been applied. Although the pretreatment composition and the imprinted photoresist material are mixed with each other in these examples, for the sake of simplicity, the following description of the imprinted photoresist material and the pretreatment coating does not consider The situation of mixing with each other. The pretreatment composition is arranged on a wafer substrate through spin coating. More specifically, the pretreatment composition is dissolved in PGMEA (0.3wt% pretreatment composition/99.7wt% PGMEA) and spin-coated on the wafer substrate. When the solvent evaporates, the thickness of the pretreatment coating obtained on the substrate is typically in the range of 5 nanometers and 10 nanometers (eg, 8 nanometers). The droplets of the imprinted photoresist in Figures 12-14 are about 2.5 pL. In Figures 12 and 14, there are 2×7 (pitch) ² staggered droplet grids (for example, 2 units in the horizontal direction and 3.5 units between the lines). Each subsequent line is offset by 1 unit in the horizontal direction. Figure 13 shows a 2×6 (pitch) ² staggered droplet grid. The pitch value is 84.5 microns. The volume ratio of the imprinted photoresist material and the pretreatment layer is in the range of 1 to 15 (eg, 6 to 7).

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

In Example 1 (see Table 1), the droplets of imprinted photoresist material were arranged on a substrate with a pretreatment composition A coating (Sartomer 492 or "SR492"). The SR492 (available from Sartomer, Pennsylvania, USA) is propoxylated (3) trimethylolpropane triacrylate (a multifunctional acrylate). Figure 12 shows the separated The image of the photoresist material droplet 1200 and the obtained pre-treatment coating 1204 are imprinted on the pre-treatment coating 1202 after 1.7 seconds after part of being applied in a staggered grid pattern. In this example, the drop can maintain its spherical cap-like shape and the expansion of the imprinted photoresist is very limited. As seen in Figure 12, when the droplet 1200 expands beyond the expansion of the imprinted photoresist on the adhesive layer in Comparative Example 1, the droplet remains separated by the pretreatment coating 1202, which is A boundary 1206 is formed around the droplet. Certain components of the imprinted photoresist material extend beyond the center of the droplet, which forms an area 1208 surrounding the droplet 1200. Zone 1208 is separated by pretreatment coating 1202. This limited expansion is at least partly due to the slight difference in surface tension (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 (for example, friction) are also believed to have an influence on the degree of expansion.

In Example 2 (see Table 1), droplets of imprinted photoresist material were arranged on a substrate with a pretreatment composition B coating (Sartomer 351HP or "SR351HP"). The SR351HP (available from Sartomer, Pennsylvania, USA) is trimethylolpropane triacrylate (a multifunctional acrylate). FIG. 13 shows a photoresist droplet 1300 of imprinted photoresist material on the pre-treatment coating 1302 and the obtained pre-treatment coating 1.7 seconds after the droplet starts to be dispensed in the separated part in a staggered grid pattern. Image of layer 1304. After 1.7 seconds, the droplet 1300 covers most of the surface area of the substrate and is separated by the pretreatment coating 1302, which forms a boundary 1306 around the droplet. The droplet 1300 is more uniform than the droplet 1200 of Example 1, so that it can be observed to expand compared to Example 1. Significantly improved expansion results. The greater degree of expansion is at least partly due 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 in Example 1. The difference in surface tension between.

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

The defect density was measured as a function of the pre-expansion time of the imprinted photoresist materials of Examples 1-3 and the pretreatment composition B of Example 2. Figure 15 shows the density of defects (voids) due to the underfill of the template. The curve 1500 shows the defect density (the number of defects per cm ² ) as a function of the expansion time (seconds) of the 28 nanometer line/space pattern area, where the defect density is close to 0.1/cm ² at 0.9 seconds. The curve 1502 shows the defect density (the number of defects per cm ² ) as a time function of the expansion time (seconds) in the entire area having a feature structure size range, where the defect density is close to 0.1/cm ² at 1 second. Comparing the two, without pretreatment, the defect density for the entire area is close to 0.1/cm ² when the spreading time is between 2.5 seconds and 3 seconds.

The properties of the pretreatment compositions PC1-PC9 are shown in Table 2. The keys of PC1-PC9 are shown below. The viscosity is measured at a temperature of 23°C as described above. In order to calculate the diameter ratio (diameter ratio) at 500ms as shown in Table 2, droplets of imprinted photoresist material (droplet size ~ 25pL) are allowed to spread on a substrate, and a pretreatment composition (about 8nm to 10nm thick) is coated on an adhesive layer, and the droplet diameter is recorded in a period of 500ms. The droplet diameter of each pretreatment composition was divided by the 500ms droplet diameter of the imprinted photoresist on an adhesive layer without the pretreatment composition. As shown in Table 2, the droplet diameter of the imprinted photoresist on PC1 at 500 ms is 60% larger than the droplet diameter of the imprinted photoresist on an adhesive layer without pretreatment coating. Figure 16 shows the droplet diameter (μm) as a function of time (ms) of the pretreatment compositions PC1-PC9. The relative etching resistance is the Ohnishi parameter of each pretreatment composition divided by the Ohnishi parameter of the imprinted photoresist. 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 imprint 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: Nonanediol diacrylate

PC8: m-xylene diacrylate

PC9: Tricyclodecane dimethanol diacrylate (Sartomer)

The pretreatment compositions PC3 and PC9 were combined in different weight ratios to obtain pretreatment compositions PC10-PC13, the weight ratios of which are shown in Table 3. Comparison of the properties of PC3 and PC9 and the mixtures they form reveals complementary effects. For example, PC3 has relatively low viscosity and relatively fast template filling, but has relatively poor etching resistance. In contrast, PC9 has relatively good etching resistance and film stability (low evaporation loss), but is relatively sticky and exhibits relatively slow template filling. However, the combination of PC3 and PC9 can obtain a combined pretreatment composition with favorable characteristics, including relatively low viscosity, relatively fast template filling, and relatively good The etching resistance. For example, a pretreatment composition with 30 wt% PC3 and 70 wt% 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 curve of the viscosity of the pretreatment composition containing different proportions of PC3 and PC9 (ie, from 100% by weight of PC3 to 100% by weight of PC9). Figure 17B shows the droplet diameters of PC3, PC13, PC12, PC11, PC10 and PC9 (which were measured as described in relation to Table 2). Figure 17C shows the ratio of surface tension (mN/m) vs. PC3 and PC9.

Several embodiments have been described. However, it should be understood that various modifications can be achieved without departing from the spirit and scope of the content of the disclosure. Therefore, other embodiments fall within the scope defined by the scope of the following patent applications.

102‧‧‧Substrate

500‧‧‧Base

502‧‧‧Adhesive layer

504‧‧‧Pretreatment composition

506‧‧‧Pretreatment coating

Claims (23)

A nanoimprint lithography method includes: disposing a pretreatment composition on a substrate to form a pretreatment coating on the substrate, wherein the pretreatment composition includes a polymerizable component (polymerizable component). ); A separated portion of an imprinted photoresist material is configured on the pretreatment coating, each separated portion of the imprinted photoresist material covers a target area of the substrate, wherein the imprinted photoresist material Is a polymerizable composition; when each separated portion of the imprinted photoresist material expands beyond its target area, a synthetic polymerizable coating including a mixture of the pretreatment composition and the imprinted photoresist material is formed Layer on the substrate; contact the synthetic polymerizable coating with a nanoimprint lithography template; and polymerize the synthetic polymerizable coating to produce a synthetic polymerized layer on the substrate, Wherein the interfacial surface energy between the pretreatment composition and air is greater than the interface between the imprinted photoresist material and air or between at least one component of the imprinted photoresist material and air can. Such as the method of item 1 in the scope of patent application, wherein the difference between the interface energy between the pretreatment composition and air and the interface energy between the imprinted photoresist material and air is 0.5 mN/m To 25mN/m, 0.5mN/m to 15mN/m, or 0.5mN/m to 7mN/m; and/or wherein the interface energy between the imprinted photoresist material and air is 20 mN/m to 60mN/m, 28mN/m to 40mN/m, or 32mN/m to 35mN/m; and/or where the interface energy between the pretreatment composition and air is 30mN/m Within the range of 45mN/m. Such as the method of item 1 in the scope of the patent application, wherein the viscosity of the pretreatment composition at 23°C is in the range of 1cP to 200cP, 1cP to 100cP, or 1cP to 50cP; and/or wherein the imprinted photoresist material The viscosity at 23°C is in the range of 1cP to 50cP, 1cP to 25cP, or 5cP to 15cP. For example, the method of item 1 in the scope of the patent application, wherein the pretreatment composition includes a monomer; and/or wherein the pretreatment composition includes a monofunctional, bifunctional, or multifunctional acrylate monomer. Such as the method of the first item of the patent application, wherein the imprinted photoresist material comprises: 0wt% to 80wt%, 20wt% to 80wt%, or 40wt% to 80wt% of one or more monofunctional acrylates; 20wt% To 98wt% of one or more difunctional or multifunctional acrylates; 1wt% to 10wt% of one or more photoinitiators; and 1wt% to 10wt% of one or more surfactants. Such as 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 the polymerization of the synthesized polymerizable coating A covalent bond; and/or wherein each of the pretreatment composition and the imprint photoresist material includes a monomer having a common functional group. For example, the method of claim 1, wherein the pretreatment composition is disposed on the nanoimprint lithography substrate comprising spin coating the pretreatment composition on the nanoimprint lithography substrate And/or where a separate portion of the imprinted photoresist material contacts at least one other separate portion of the imprinted photoresist material, which is before the synthetic polymerizable coating contacts the nanoimprint lithography template Form a boundary between two separate parts. A nanoimprint lithography stack formed by the method of the first item of the scope of patent application, wherein the nanoimprint lithography stack includes the synthetic polymer layer on the substrate. A method of manufacturing a semiconductor device, the method includes the nanoimprint lithography method of the first patent application. A semiconductor device formed by the method described in item 9 of the scope of the patent application. A nano-imprint lithography kit includes: a pretreatment composition; and an imprint photoresist material; wherein the pretreatment composition includes a polymerizable component, and the imprint photoresist material is a polymerizable composition, And the interface energy between the pretreatment composition and air is greater than the interface energy between the imprinted photoresist material and air or between at least one component of the imprinted photoresist material and air. A method for pretreating a nanoimprint lithography substrate, the method comprising: coating the substrate with a pretreatment composition, wherein the pretreatment composition includes a polymerizable component; A separated part of an imprinted photoresist material is arranged on the pretreatment composition, wherein the imprinted photoresist material arranged in the separated part on the pretreatment composition is expanded more than that is arranged without the pretreatment The same imprinted photoresist material on the same substrate of the processing composition; and the separated parts of the imprinted photoresist material are arranged on the pretreatment composition and the imprinted photoresist material and the After the defined period of time between the contact of the nanoimprint lithography template has elapsed, the imprint photoresist material is contacted with a nanoimprint lithography template, wherein the imprint photoresist material is in contact with the nanoimprint lithography template. When the template is in contact, the gap volume between the separated portions of the imprint photoresist material disposed on the pretreatment composition is smaller than when the imprint photoresist on the substrate without the pretreatment composition The disposition of the separated parts of the material defines the gap volume between the same imprinted photoresist materials disposed on the same substrate without the pretreatment composition after a defined period of time. Such as the method of item 12 of the scope of patent application, wherein the pretreatment composition does not have a polymerization initiator. A nano-imprint lithography stack, comprising: a nano-imprint lithography substrate; and a synthetic polymer layer formed on a surface of the nano-imprint lithography substrate, wherein the synthetic polymer layer The chemical composition of is not uniform and contains multiple central regions separated by boundaries, where the chemical composition of the synthetic polymer layer at the boundary is different from the chemical composition of the synthetic polymer layer inside the central regions. For example, the nano-imprint lithography stack of item 14 in the scope of patent application, its The central area and boundary of the polymer layer are formed by a heterogeneous mixture of a pretreatment composition and an imprinted photoresist material, wherein during the formation of the synthetic polymer layer, a part of the imprinted photoresist material The polymerizable component and a polymerizable component of the pretreatment composition react to form a covalent bond. An imprinting method, comprising: disposing a separated portion of an imprinted photoresist material on a liquid pretreatment coating of a substrate, so that the separated portion of the imprinted photoresist material is spread on the liquid pretreatment coating to Generating an expanded imprinted photoresist, wherein the liquid pretreatment coating contains a polymerizable component and the imprinted photoresist is a polymerizable component; contacting the expanded imprinted photoresist with the template; The expanded imprint photoresist material and the liquid pretreatment coating are polymerized to produce a polymerized layer on the substrate; wherein the surface tension of the liquid pretreatment coating is greater than the surface tension of the imprint photoresist material. Such as the imprint method of item 16 in the scope of patent application, wherein the liquid pretreatment coating has no polymerization initiator. For example, the imprinting method of item 16 of the scope of the patent application, wherein before the expanded imprinted photoresist material contacts the template, the expanded imprinted photoresist material and the liquid pretreatment coating form a synthetic polymerizable coating Floor. For example, the imprinting method of the 16th patent application further includes separating the template from the polymer layer. Such as the imprinting method of the 16th patent application, wherein the thickness of the liquid pretreatment coating on the substrate is between 1 nanometer and 15 nanometers between. Such as the imprinting method of item 16 in the scope of patent application, wherein the surface tension of the liquid pretreatment coating is 0.5mN/m to 25mN/m greater than the surface tension of the imprinted photoresist material. A method of manufacturing a semiconductor device, comprising: providing a liquid pretreatment coating on a substrate, wherein the liquid pretreatment coating contains a polymerizable component; disposing a separated portion of the imprinted photoresist material on the liquid pretreatment coating Above, so that the separated portion of the imprinted photoresist material is spread on the liquid pretreatment coating to produce an expanded imprinted photoresist material, wherein the imprinted photoresist material is a polymerizable component, and the liquid pretreatment The surface tension of the treatment coating is greater than the surface tension of the imprinted photoresist material; the expanded imprinted photoresist material is contacted with the template; the expanded imprinted photoresist material and the liquid pretreatment coating are polymerized To produce a polymerized layer on the substrate; separate the template from the polymerized layer; and etch the substrate through the polymerized layer. For example, the method of claim 22, wherein providing the liquid pretreatment coating includes spin coating, immersion coating, chemical vapor deposition (CVD), physical vapor deposition (PVD) to coat the liquid pretreatment The layer is coated on the substrate, and further includes: treating the substrate with an imprint lithography system to produce the polymerized layer on the substrate; and Reactive ion etching or high density etching is used to etch the substrate.

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