JP5020079B2 - Method and composition for providing a layer having uniform etching characteristics - Google Patents

Description

  The field of invention relates generally to microfabrication of structures. More particularly, the present invention is directed to a method and imprint material for forming a layer having uniform etching characteristics.

  Microfabrication includes, for example, processing of very small structures having features of about a few micrometers or less. One area where microfabrication has had a significant impact is in the processing of integrated circuits. As the semiconductor processing industry continues to strive to obtain higher product yields while increasing the circuits per unit area formed on the substrate, microfabrication is becoming increasingly important. Microfabrication provides better process control while reducing the minimum feature size of the structure being formed. Other development areas where microfabrication has been used include biotechnology, optical technology, and mechanical systems.

  A typical microfabrication technique is shown in US Pat. Willson et al. Disclose a method for forming a relief image in a structure. The method includes providing a substrate having a transfer layer. The transfer layer is coated with a polymerizable fluid composition. The imprint device is in mechanical contact with the polymerizable fluid. The imprint apparatus includes a relief structure formed from lands and grooves. The polymerizable fluid composition is determined by the thickness of the polymerizable fluid that fills the relief structure and the remaining thickness overlies the land. The polymerizable fluid composition is then placed under conditions to solidify and polymerize the polymerized solids on a transfer layer that includes a relief structure that is complementary to the relief structure of the imprint apparatus. Form a layer. The imprint apparatus is then separated from the solidified polymer layer such that a replica of the relief structure in the imprint apparatus is formed in the solidified polymer layer. The polymer layer solidified with the transfer layer is placed in an environment for selectively etching the transfer layer relative to the solidified polymer layer so that a relief image is formed in the transfer layer. A conventional etching process can then be used to transfer the relief structure pattern to the substrate.

  Conventional etching processes have formed a desired pattern in the layer using an appropriate mask, such as a photoresist mask. A mask is usually deposited on the layer and patterned to form a patterned mask. The patterned mask is then exposed to an etchant, such as ions in a dry etching process or a liquid acid in a wet etching technique, to remove portions of the layer exposed through the patterned mask.

  A desirable property of any etching process is to obtain a uniform etch rate across the surface being etched. To that end, the prior art is full of attempts to control the etch rate during the etching process. For example, Hanney et al., U.S. Pat. No. 6,057,077 discloses a method and apparatus for achieving etch rate uniformity in a reactive ion etcher. The reactive ion etcher localizes the etch rate across the cathode so that the plasma is generated from the top plate of the reactor can and produces a uniform etch rate distribution across the cathode as a result of the localized magnetic field. A plasma is generated in the vacuum chamber to etch the substrate located at the cathode of the reaction can in the vacuum chamber, which is affected by the local magnetic field that is controlled. A magnet array may be placed between the top plate and the vacuum chamber to provide a localized magnetic field. The magnet array includes a plurality of individual magnets and a grid plate that holds the individual magnets in place.

  Daugherty et al., US Pat. No. 5,677,077 discloses a method and apparatus for ion-assisted etching processing in a plasma processing system. According to various aspects of the invention, a high edge ring, a grooved edge ring, and an RF coupled edge ring are disclosed. The invention serves to improve the etch rate uniformity across the substrate (wafer). The improvement in etch rate uniformity provided by the invention not only improves manufacturing yield, but is also cost effective and does not run the risk of particulate and / or heavy metal contamination.

U.S. Patent No. 5,677,096 to Meador et al. Discloses an antireflective coating composition having an improved etch rate. The composition is prepared from certain acrylic polymers and copolymers, such as glycidyl methacrylate reacted with non-polycyclic carboxylic acid dyes and non-polycyclic phenolic dyes, all absorbing light at a wavelength of 193 nm. .
US Pat. No. 6,334,960 US Pat. No. 6,132,632 US Pat. No. 6,344,105 US Pat. No. 6,576,408

  Accordingly, there is a need to provide an etching technique with improved control of the etching rate of the imprint material being processed.

  The present invention includes methods and compositions for forming a layer having uniform etching characteristics on a substrate. To that end, the method includes depositing a polymerizable liquid on the substrate as a multi-component composition. Each component has an evaporation rate associated with it. The polymerizable composition then solidifies. A relative evaporation rate associated with the subset of components is defined to be within a predetermined range. Specifically, the present invention is based on the discovery that etch non-uniformity within a layer, formed by solidification of the deposited liquid, is a function of the relative evaporation rate of the components that form the layer. As a result, the composition is formed from multiple components, a subset of which has substantially the same evaporation rate over a time interval. These and other embodiments are discussed more fully below.

  FIG. 1 depicts a lithographic system 10 according to an embodiment of the invention that includes a pair of spaced bridge supports 12 having a bridge 14 and a stage support 16 extending therebetween. The bridge 14 and the stage support 16 are separated. Coupled to the bridge 14 is an imprint head 18 that extends from the bridge 14 toward the stage support 16. A moving stage 20 is disposed on the stage support 16 so as to face the imprint head 18. The moving stage 20 is configured to move with respect to the stage support 16 along the X and Y axes, and can also move along the Z axis. A radiation source 22 is coupled to the system 10 to cause actinic radiation to enter the moving stage 20. As shown, the radiation source 22 includes a generator 23 coupled to the bridge 14 and connected to the radiation source 22.

Referring to both FIGS. 1 and 2, connected to the imprint head 18 is a template 24 having a patterned mold 26. Patterned mold 26 includes a plurality of features formed by a plurality of spaced recesses 28 and protrusions 30. The protrusion 30 has a width W ₁ and the recess 28 has a width W ₂ , both of which are measured in a direction extending across the Z axis. The plurality of features form the original pattern that forms the basis of the pattern to be transferred to the substrate 32 positioned on the moving stage 20. To that end, the imprint head 18 is configured to move along the Z axis and change the distance “d” between the patterned mold 26 and the substrate 32. Alternatively, or in conjunction with the imprint head 18, the moving stage 20 can move the template 24 along the Z axis. In this way, the features of the patterned mold 26 can be imprinted on the flowable region of the substrate 32. More fully discussed below. The radiation source 22 is placed such that the patterned mold 26 is positioned between the radiation source 22 and the substrate 32, and actinic radiation generated by the radiation source 22 propagates through the patterned mold 26. As a result, it is desirable that the patterned mold 26 be made from a material that is substantially transparent to actinic radiation. Typical materials from which the patterned mold 26 can be manufactured include fused quartz, quartz, silicon, organic polymers, siloxane polymers, borosilicate glasses, fluorocarbon polymers, metals, and combinations thereof, depending on the actinic radiation used. A typical system is available from Molecular Imprints, Inc., having offices in Austin, TX 78758, 1807-C Braker Lane, Suite 100. Available under the trade name IMPRIO 100 ™. The system description for the IMPRIO 100 ™ is www. molecularimprints. com.

  With reference to FIG. 2, a flowable region, such as imprint layer 34, is formed on a portion of surface 36 that exhibits a substantially smooth, if not planar, surface facing template 24. In one embodiment of the present invention, the flowable region is deposited as a plurality of spaced apart discrete droplets 38 of imprint material on the substrate 32, as discussed more fully below. The imprint material is selectively polymerized and crosslinked to internally record the inverse of the original pattern that forms the recorded pattern. The features on the patterned mold 26 are shown as recesses 28 that extend along a direction parallel to the projections 30 that give the cross-section of the patterned mold 26 the shape of the intercostal chest wall. However, the recesses 28 and the protrusions 30 can accommodate virtually any feature needed to create an integrated circuit, and 0. It may be as small as a few nanometers.

  With reference to FIGS. 2 and 3, the pattern recorded in the imprint layer 34 is partially generated by mechanical contact with the patterned mold 26. To that end, the distance “d” is reduced so that the imprint layer 34 can be in mechanical contact with the patterned mold 26 and small so as to form the imprint layer 34 by continuous formation of the imprint material across the surface 36. Spread the drop 38. In one embodiment, the distance “d” is reduced so that a portion 46 of the imprint layer 34 enters and fills the recess 28.

In this embodiment, the portion 48 of the imprint layer 34 superimposed with the protrusion 30 remains after reaching the desired, usually minimum distance “d”, and the portion 46 of thickness t ₁ and the thickness t _1. Leave a portion 48 of ₂ . The thickness t ₂ is called the residual thickness. The thicknesses “t ₁ ” and “t ₂ ” may be any desired thickness depending on the application. The total volume contained in the droplet 38 is large, while obtaining the desired thicknesses t ₁ and t ₂ by the patterned mold 26, the capillary attraction of the imprint material by the surface 36, and the surface adhesion of the imprint material. The imprint material may be avoided or minimized to extend beyond the area of the surface 36 that is superimposed with the patterned mold 26.

  Referring to FIG. 2, after reaching the desired distance “d”, the radiation source 22 generates actinic radiation that polymerizes and crosslinks the imprint material to form a solidified imprint layer 134. The composition of the imprint layer 34 is transformed from a fluid imprint material to a solidified material. This provides the solidified imprint layer 134 with a surface having a shape that matches the shape of the surface 50 of the patterned mold 26, more clearly shown in FIG. As a result, the solidified imprint layer 134 is formed to have the concave portion 52 and the convex portion 54. After the solidified imprint layer 134 is formed, the distance “d” is increased so that the patterned mold 26 and the solidified imprint layer 134 are separated. This process is typically repeated several times to pattern different regions (not shown) of the substrate 32 and is referred to as a step-and-repeat process. A typical step-and-repeat process was filed on Jul. 11, 2002 as application No. 10/194414, assigned to the assignee of the present invention, and entitled “Step and Repeat Imprint Lithography”. Further, it is disclosed in US Patent Application Publication No. 2004/0008334.

The benefits of this patterning process are numerous. For example, the difference in thickness between the convex portion 54 and the concave portion 52 facilitates formation of a pattern in the substrate 32 corresponding to the pattern in the solidified imprint layer 134. Specifically, the difference in thickness between t ₁ and t ₂ of the convex portion 54 and the concave portion 52, respectively, is compared to the time required to expose the region of the substrate 32 that is superimposed on the concave portion 52, More etching time is required to expose the region of the substrate 32 that overlaps the convex portion 54. Thus, for a given etching process, etching begins earlier in the area of the substrate 32 that overlaps the recess 52 than in the area that overlaps the protrusion 54. This facilitates the formation of a pattern in the substrate 32 that corresponds to the pattern in the solidified imprint layer 134. By appropriate selection of the imprint material and etch chemistry, the relative dimensions between the different features of the pattern that are ultimately transferred to the substrate 32 can be controlled as desired. To that end, it is desirable that the etching characteristics of the solidified imprint layer 134 be substantially uniform for a given etch chemistry.

As a result, the properties of the imprint material are important for efficiently patterning the substrate 32 in light of the unique patterning process used. As described above, the imprint material is deposited on the substrate 32 as a plurality of discrete and spaced droplets 38. The combined volume of the droplets 38 is such that the imprint material is properly distributed over the area of the surface 36 where the imprint layer 34 is to be formed. In this manner, the total volume of imprint material within the droplet 38 is imprinted into the gap formed between the superimposed patterned mold 26 and the portion of the substrate 32 once the desired distance “d” is reached. The distance “d” to be obtained is determined so that the total volume occupied by the print material is substantially equal to the total volume of the imprint material in the droplets 38. As a result, the imprint layer 34 is spread and patterned simultaneously, and the pattern is subsequently set substantially by exposure to actinic radiation. To facilitate the deposition process, the imprint material is small across the surface 36 such that all thicknesses t ₁ are substantially uniform and all residual thicknesses t ₂ are substantially uniform. It is desirable for the imprint material to spread rapidly and evenly within the drops 38.

A typical composition of an imprint material consists of:
Composition 1
Isobornyl acryloxymethyl bis (trimethylsiloxy) methyl silane acrylate ethylene glycol 2-hydroxy-2-methyl-1-phenyl-propan-1-one composition 2
Isobornyl acryloxymethyl tris (trimethylsiloxy) silane acrylate ethylene glycol 2-hydroxy-2-methyl-1-phenyl-propan-1-one composition 3
Isobornyl acrylate 3-acryloxypropylbis (trimethylsiloxy) methylsilane ethylene glycol diacrylate 2-hydroxy-2-methyl-1-phenyl-propan-1-one composition 4
Isobornyl acrylate 3-acryloxypropyltris (trimethylsiloxy) silane diethylene glycol ethylene 2-hydroxy-2-methyl-1-phenyl-propan-1-one composition 5
Isobornyl acryloxymethyl bis (trimethylsiloxy) methyl silane acrylate ethylene glycol 2-hydroxy-2-methyl-1-phenyl-propan-1-one R ₁ R ₂
Composition 6
Isobornyl acryloxymethyl tris (trimethylsiloxy) silane acrylate ethylene glycol 2-hydroxy-2-methyl-1-phenyl-propan-1-one R ₁ R ₂
Composition 7
Isobornyl acrylate 3-acryloxypropylbis (trimethylsiloxy) methylsilane ethylene glycol diacrylate 2-hydroxy-2-methyl-1-phenyl-propan-1-one R ₁ R ₂
Composition 8
Isobornyl acrylate 3-acryloxypropyltris (trimethylsiloxy) silane diacrylate ethylene glycol 2-hydroxy-2-methyl-1-phenyl-propan-1-one R ₁ R ₂

In compositions 1, 2, 3, and 4, the first silicon-free acrylate salt, isobornyl acrylate, is about 42% of the composition, but the amount present therein is in the range of 20-60%. But it ’s okay. The silicon-containing acrylic acid will be about 37% of any of compositions 1, 2, 3, 4 but the amount present therein may be in the range of 30-50%. The second silicone-free acrylate, the cross-linking agent ethylene glycol diacrylate, is about 18% of any of compositions 1, 2, 3, 4 but the amount present is also in the range of 10-40% good. The initiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, is about 0.5% to 5%, and UV light is used to promote crosslinkability and polymerization of compositions 1-4. To react. For improved release properties, compositions 5, 6, 7, and 8 each contain about 0.5% surfactant R ₁ R ₂ of the composition in addition to the components of compositions 1-4. The remaining components of compositions 5, 6, 7, and 8 are reduced proportionally to compensate for the addition of surfactant. For the purposes of the present invention, a surfactant is defined as any molecule that is hydrophobic at one end. The surfactant may be fluorine-containing, for example, either containing a fluorine chain, or not containing any fluorine in the molecular structure of the surfactant.

A typical surfactant is R ₁ R ₂ , where R ₁ = F (CF ₂ CF ₂ ) _Y , y is in the range of 1-7, and R ₂ = CH ₂ CH ₂ O ( CH ₂ CH ₂ O) _X H, where X is in the range of 0-15], available from DUPONT ™ under the trade name ZONYL® FS0-100. However, other surfactants may be used in place of or in addition to the F (CF ₂ CF ₂ ) _Y CH ₂ CH ₂ O (CH ₂ CH ₂ O) _X H surfactant, compositions 5, 6, 7, It should be understood that 8 may be added. Additional surfactants may include fluorinated polymeric surfactants available from 3M Company under the designations FLUORAD® FC4432 and / or FLUORAD® FC4430. Moreover, other ultraviolet photoinitiators can be used in conjunction with or in place of 2-hydroxy-2-methyl-1-phenyl-propan-1-one. It should be understood that non-photoinitiators such as thermal initiators may be used. As a result, the actinic radiation used to promote crosslinkability and polymerization is thermal in nature, such as infrared.

  Referring to FIG. 4, a typical method for forming a solidified imprint layer 134 is to deposit a plurality of droplets as a pattern 100 to minimize gas trapping as the imprint material is spread across the surface 36. Including. To that end, the pattern 100 is formed of a plurality of droplets 101-149 that are sequentially deposited in the order in which the droplet 101 is dispensed first and the droplet 149 is dispensed last. However, it has been discovered that the etching characteristics of the solidified imprint layer 134 vary depending on the position of the droplets in the droplet distribution sequence, referred to as the sequential etch difference (SED).

  It was determined that the SED was due to variations across the area of the solidified imprint layer 134 of the cross-linked and polymerized components that formed the solidified imprint layer 134. It has been discovered that component variations within the solidified imprint layer 134 occur while the imprint material is in a fluid state due to evaporation. Specifically, it has been discovered that the composition of the imprint material changes before it is polymerized and crosslinked. During the imprint process, evaporation occurs during several time intervals. The time interval between the dispensing of the droplet 101 and the contact of the pattern 100 with the mold 26 is about 20 seconds. This is considered the interval at which maximum evaporation occurs. During this interval, evaporation of the imprint material occurs and the loss of the imprint material is proportional to the length of the interval between deposition and contact with the mold 26. After contact with the mold 26, a second time interval is necessary to spread the droplets 101-149 and form an adjacent silicon-containing layer on the substrate 32. During the second time interval, typically about 10 seconds, additional evaporation of the imprint material occurs.

  The present invention overcomes SED by ensuring that certain polymerizable components are present in the desired amount in the solidified imprint layer 134. In this example, the preferred polymerizable components are the silicon-containing acrylic acid component and the non-silicon-containing / silicon-free acrylic acid component including IBOA and the crosslinker component EDGA, all of which are acrylates. Specifically, it is recognized that the non-uniformity in the etching characteristics of the solidified imprint layer 134 is due to variations in silicon content across that region.

  It has been discovered that prior art silicon-containing compositions in which the silicon-containing acrylate has evaporated faster than the remaining components of the composition exhibit etch non-uniformity. This can be understood by examining FIGS. In FIG. 5, the silicon-containing layer 150 formed from the prior art silicon-containing composition appears substantially smooth and uniform in contour. After subjecting the layer 150 to a plasma etching step, non-uniformities can be observed by the myriad concave regions 152 appearing in the etching layer 154. This is due to the faster etch rate associated with the recessed region 152 compared to the etch rate of the protruding region 156. It is believed that the faster etching rate of the recessed region 152 is due to the presence of a lower silicon content compared to the silicon content of the protruding region 156. The non-uniformity of silicon content in layer 150 results in an uneven etching of etch layer 152, which is undesirable.

The present invention avoids etching non-uniformities in the silicon-containing layer by setting a composition of the imprint material in which the desired component has the desired evaporation rate during the desired time interval. To alleviate. Although it is possible to provide a composition in which the evaporation rate of the desired component is substantially the same over an infinite period, it has been determined to be unnecessary. Rather, the polymerizable components of compositions 1-8 are selected to have a desired relative evaporation rate in the time interval between deposition and exposure to actinic radiation. The remaining components of Compositions 1-4, i.e., the photoinitiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, become part of the polymerized structure, but are considered polymerizable components. Not done. Thus, the photoinitiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, does not substantially contribute to the structural properties of the resulting imprint layer, which reduces the evaporation rate. Minimize the need to match the evaporation rate of the acrylic acid component. Similarly, the remaining components of compositions 5-8, namely photoinitiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and surfactant, R _f CH ₂ CH ₂ O (CH ₂ CH ₂ O) _X H is not considered a polymerizable component. Furthermore, it is desirable that the non-polymerizable components of compositions 1-8 evaporate at a rate slower than the evaporation rate of the acrylic acid component.

  Referring to FIG. 7, various curves showing the relative evaporation rates of specific components within a 400 pL droplet of Composition 1 are shown. Specific components are as follows: ethylene glycol diacrylate (EDGA), acryloxymethylbis (trimethylsiloxy) methylsilane (AMBMS), isobornyl acrylate (IBOA). The 400 pL droplet was formed by the deposition of a plurality of droplets each having a volume of 80 pL in the common area to provide a 400 pL droplet having a radius of about 82 microns. The relative evaporation rate between the components of Composition 1 has been shown to be less than 0.1% / second, which is less than 2% for a 20 second interval and about 5% over a 60 second interval. change. Similar evaporation rates for the polymerizable components of compositions 2-8 were also discovered. As a result, Compositions 1-8 have a substantially uniform evaporation rate whose polymerizable components provide a substantially uniform silicon density across the volume of solidified imprint layer 134 as shown in FIG. In particular, each has desirable characteristics. Specifically, the solidified imprint layer 134 is provided with a desired silicon content of 8 wt% or more over a given region of the solidified imprint layer 134. The maximum weight variation of silicon content between any two regions of the solidified imprint layer 134 should be 5% or less.

  Moreover, Compositions 1-8 provide the desired viscosity, which may be in the range of 1-20 centipoise, preferably less than 5 centipoise. This facilitates deposition using droplet dispensing techniques. Similarly, compositions 1-8 provide solidified imprint layer 134 with the desired mechanical strength such that the fracture stress is 15 MPa or greater.

  2 and 8, similarly, it is desirable to provide substrate 32 with a smooth, if not planar, surface on which imprint layer 34 is formed. To that end, the substrate 32 can include an undercoat layer 96. When the surface 36 of the substrate 32 appears rough compared to the feature dimensions formed in the imprint layer 34, the primer layer 96 has proven useful. The primer layer 96 also provides a standard interface with the imprint layer 34, among other things, thereby reducing the need to customize each process to the imprint material on which the substrate 32 is formed. In addition, the primer layer 96 can be formed from an organic imprint material having the same or different etching characteristics as the imprint layer 34. As a result, the primer layer 96 is manufactured in such a way as to have a continuous, smooth and relatively defect-free surface that exhibits excellent adhesion to the imprint layer 34. A typical material used to form the primer layer 96 is Rolla Missouri's Brewer Science, Inc. under the trade name DUV30J-6. Is available from The primer layer 96 typically has a certain thickness to facilitate providing a desired surface profile and is used to detect patterns such as alignment marks on the surface of the substrate 32. The sensing device is not opaque.

  With reference to FIGS. 8 and 9, it has been discovered that it is beneficial to deposit a primer layer 196 when the imprint layer 34 is present on the surface 136 of the pre-patterned substrate 32. To that end, like the primer layer 96, the primer layer 196 can be deposited using any known deposition method, including droplet dispensing techniques, spin-on techniques, and the like. Further, in order to improve the smoothness of the surface of any of the undercoat layers 96, 196, it is desirable to contact it with a planarization mold 80 that has a substantially smooth contact surface, if not planar.

  In order to reduce the likelihood that the solidified primer layer 96, 196 will adhere to the planarization mold 80, it is treated with a low surface energy coating 98. The low surface energy coating 98 can be applied using any known method. For example, processing techniques include chemical vapor deposition, physical vapor deposition, atomic layer deposition or various other techniques, brazing, and the like. Similarly, a low surface energy coating (not shown) can be applied to the mold 26 shown in FIG.

  In addition to the surfactant and low surface energy coating, fluorinated additives can be used to improve the peelability of the imprint material. The fluorinated additive, like a surfactant, has a surface energy associated therewith that is lower than the surface energy of the imprint material. A typical method using the aforementioned fluorinated additives is described by Bender et al. In MULTIIPLE IMPRINTING IN UV-BASED NANOIMPRINT LITHOGRAPHY: RELATED MATERIAL ISSUES, Microelectronic Engineering, pp. 61-62 (2002). The low surface energy of the additive provides the desired peelability in order to reduce the adhesion of the crosslinked and polymerized imprint material to the molds 26,80. It should be understood that surfactants can be used in conjunction with or in place of compositions 5-8 containing surfactants.

  Referring to FIGS. 5 and 10, it should be understood that the benefits provided by the present invention apply equally to layers formed using other techniques in which evaporation occurs during layer formation. Typical deposition techniques that can be used to form the solidified layer 234 include spin-on techniques, laser-assisted direct imprint (LADI) techniques, and the like. Exemplary LADI technology is described by Chou et al., “Ultrafast and Direct Imprint of Nanostructure in Silicon” Nature, Col. 417, pp. 835-837, June 2002. For example, any of compositions 1-8 can be deposited on substrate 32 as layer 234 by using a spin-on technique. Thereafter, layer 234 can be patterned using mold 26. If the layer 234 to be patterned uses a step in which different regions of the layer 234 are patterned and then solidified sequentially, and the technique is repeated, the benefits of the present invention become significant.

  The above-described embodiments of the present invention are typical. Numerous changes and modifications can be made to the disclosure described above while remaining within the scope of the invention. For example, the component ratio of each composition described above can be varied. Moreover, while the present invention has been discussed for controlling the silicon content in a layer to improve etch uniformity, the present invention is not limited to adhesive strength, preferential or non-preferential, stress, thickness, The same can be applied to improve other properties of the layer, such as thickness uniformity, roughness, strength, density, etc. Accordingly, the scope of the invention should not be limited by the above description, but should instead be determined by reference to the appended claims, along with their full scope of equivalents.

1 is a perspective view of a lithographic system according to the present invention. FIG. 2 is a simplified elevation view of the lithographic system shown in FIG. 1 used to make a patterned imprint layer according to an embodiment of the present invention. FIG. 2 is a simplified elevation view of the imprint apparatus spaced from the patterned imprint layer shown in FIG. 1 after patterning in accordance with the present invention. FIG. 3 is a top-down view of the region of the substrate shown in FIG. 2 where patterning occurs using a pattern of polymerizable fluid droplets disposed thereon. FIG. 3 is a cross-sectional view of a layer formed from a polymerizable material of a prior art imprint material deposited on a substrate. FIG. 6 is a cross-sectional view of the layers shown in FIG. 4 is a graph showing evaporation rates of different components of a silicon-containing polymerizable material of an imprint material according to the present invention. FIG. 3 is a cross-sectional view showing a release layer and an undercoat layer that may be used in accordance with the present invention. It is sectional drawing which shows the peeling layer applied to the planarization mold shown in FIG. FIG. 6 is a cross-sectional view illustrating the formation of a layer on a substrate according to an alternative embodiment of the present invention.

Explanation of symbols

  10 Lithographic system, 18 Imprint head, 20 Moving stage, 22 Radiation source, 24 Template, 32 Substrate

Claims (25)

A composition for forming a layer having uniform etching characteristics on a substrate,
A plurality of polymerizable components including a silicon-containing polymerizable component and a silicon-free polymerizable component;
An initiator component for facilitating a change in phase state of the plurality of polymerizable components between a fluid phase state and a solidified phase state;
Including
The silicon-containing polymerizable component includes acryloxymethylbis (trimethylsiloxy) methylsilane, or acryloxymethyltris (trimethylsiloxy) silane,
The silicon-free polymerizable component includes an acrylate ester ,
A composition wherein the relative evaporation rate between the plurality of polymerizable components is less than 0.1% per second.   2. The composition of claim 1, wherein each of the plurality of polymerizable components has a relative evaporation rate within a predetermined range for a predetermined time interval. The composition of claim 1, wherein the composition has a viscosity that facilitates the formation of a plurality of droplets on a substrate, each droplet having a volume of 80 pL.   The composition of claim 1, wherein the composition is deposited on the substrate using a spin-on technique.   The composition of claim 1, wherein the silicon-free polymerizable component comprises isobornyl acrylate.   6. The composition of claim 5, wherein the silicon-free polymerizable component further comprises ethylene glycol diacrylate.   The silicon-containing polymerizable component includes 3-acryloxypropylbis (trimethylsiloxy) methylsilane, and the silicon-free polymerizable component includes isobornyl acrylate. The composition as described.   The silicon-containing polymerizable component includes 3-acryloxypropyltris (trimethylsiloxy) silane, and the silicon-free polymerizable component includes isobornyl acrylate. Composition.   The composition of claim 1, wherein the silicone-free polymerizable component includes a crosslinker component.   The composition of claim 1, wherein the initiator component comprises 2-hydroxy-2-methyl-1-phenyl-propan-1-one.   The composition according to claim 1, further comprising a surfactant.   The silicon-free polymerizable component includes first and second subcomponents, the first subcomponent being a crosslinker component, in the range of about 10-40% of the composition, The second subcomponent is comprised in the range of about 20-60% of the composition, and the silicon-containing polymerizable component is comprised in the range of about 30-50% of the composition. Composition. A composition for forming a layer having uniform etching characteristics on a substrate,
A plurality of acrylic acid ester components including a silicon-containing acrylic acid ester component and first and second silicon-free acrylic acid ester components;
An initiator component for facilitating a change in phase state of the plurality of acrylate components between a fluid phase state and a solidified phase state;
Including
The silicon-containing acrylic ester component includes acryloxymethylbis (trimethylsiloxy) methylsilane, or acryloxymethyltris (trimethylsiloxy) silane,
Acrylic acid ester component without the first silicon includes isobornyl acrylate,
The second silicone-free acrylic ester component comprises ethylene glycol diacrylate;
A composition wherein the relative evaporation rate between the plurality of acrylic ester components is less than 0.1% per second. 14. The composition of claim 13, wherein the composition has a viscosity that facilitates the formation of a plurality of droplets on a substrate, each droplet having a volume of 80 pL.   14. The composition of claim 13, wherein the composition is deposited on the substrate using a spin-on technique. Acrylate wherein the silicon-containing acrylate ester component containing b carboxymethyl bis (trimethylsiloxy) methylsilane, constitute 30-50% of the composition, the first acrylic acid ester component without silicon composition comprising isobornyl acrylate It comprises about 20% to 60% of an acrylic acid ester component without the second silicon containing diacrylate ethylene glycol according to claim 13, characterized in that comprises about 10-40% of the composition Composition. Acryloxymethyl tris (trimethylsiloxy) the silicon-containing acrylate ester component containing silane constitute 30-50% of the composition, an acrylic acid ester component without the first silicon containing isobornyl acrylate is constituting about 20% to 60% of the composition, according to claim 13 acrylic acid ester component without the second silicon containing ethylene glycol diacrylate, characterized in that the comprise about 10-40% of the composition A composition according to 1. 3-acryloxypropyl-bis (trimethylsiloxy) the silicon-containing acrylate ester component containing methylsilane constitute 30-50% of the composition, wherein the first silicon-free acrylate containing isobornyl acrylate billing component comprises from about 20% to 60% of the composition, an acrylic acid ester component without the second silicon containing ethylene glycol diacrylate, characterized in that the comprise about 10-40% of the composition Item 14. The composition according to Item 13. 3-acryloxypropyltris (trimethylsiloxy) the silicon-containing acrylate ester component containing silane constitute 30-50% of the composition, no acrylic acid ester of the first silicon containing isobornyl acrylate billing component comprises from about 20% to 60% of the composition, an acrylic acid ester component without the second silicon containing ethylene glycol diacrylate, characterized in that the comprise about 10-40% of the composition Item 14. The composition according to Item 13. Acrylic acid ester component without the silicon composition according to claim 13, characterized in that it comprises a crosslinker component.   14. The composition of claim 13, wherein the initiator component includes 2-hydroxy-2-methyl-1-phenyl-propan-1-one. A composition for forming a layer having uniform etching characteristics on a substrate,
An isobornyl acrylate component;
Ethylene glycol diacrylate and
A photoinitiator component;
Acryloxymethyl bis (trimethylsiloxy) methylsilane, and acryloxymethyl tris (trimethylsiloxy) silane, 3-acryloxypropyl-bis (trimethylsiloxy) silicon-containing acrylic acid ester component selected from the set consisting of methylsilane,
Including
The isobornyl acrylate component, the ethylene glycol diacrylate, and relative evaporation rate of between polymerizable components containing the silicon-containing acrylic acid ester component composition and less than 0.1 per second%. The silicon-containing acrylate ester component comprises 30-50% of the composition, the isobornyl acrylate component comprises about 20-60% of the composition, and the ethylene glycol diacrylate component is about 10-40% of the composition. 23. The composition of claim 22, comprising:%.   24. The composition of claim 23, further comprising a surfactant. A composition for forming a layer having uniform etching characteristics on a substrate,
An isobornyl acrylate component;
Ethylene glycol diacrylate and
A photoinitiator component;
A silicon-containing acrylic acid ester component comprising 3-acryloxypropyltris (trimethylsiloxy) silane;
Including
The isobornyl acrylate component, the ethylene glycol diacrylate, and relative evaporation rate of between polymerizable components containing the silicon-containing acrylic acid ester component composition and less than 0.1 per second%.

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