# Patent

## Title
Amorphous oxide release layers for imprint lithography, and method of use

## Abstract

Amorphous inorganic oxides are used as release layers on templates for nanoimprint lithography. Such a layer facilitates the release of a template from a cured, hardened composition into which the template has transferred a pattern, by reducing the adhesion energy between the release layer and the cured, hardened composition. The release layer may include one or more metallic or semiconductor elements such as Al, Cu, Co, Sb, Ti, Ta, W and Ge.

## Background
TECHNICAL FIELD
The invention relates to release layers for templates used in imprint lithography, and more particularly, to layers that facilitate the releasing of templates from curable compositions used in step and flash nanoimprint lithography processes.
BACKGROUND
Imprint lithography has received attention as a possible alternative to conventional photolithography because of its ability to print small features at low cost. Step and flash imprint lithography is one kind of imprint lithography that is amenable to the resolution and overlay requirements necessary for the fabrication of advanced semiconductor devices. With step and flash imprint lithography, a photosensitive material is squeezed between a substrate and a mechanically rigid, ultraviolet (UV) transparent template having a relief pattern. The photosensitive material is then exposed to actinic radiation, causing it to cure in situ. The resulting cured, hardened layer, which has a pattern of features defined by the relief pattern, can be used as an etch mask to transfer this pattern into an underlying substrate.
Unfortunately, such a process is prone to a large number of defects, the primary sources of which are particles and cohesive failure of the cured material during debonding (see, for example, W. J. Dauksher et al., Proc. SPIE 6517, 651714, 2007). Cohesive failure occurs when the bond between the cured material and the template is stronger than the bonds within the cured material itself For this reason, it is generally necessary to pre-coat the template with a release agent or coating, so that the template does not stick to the cured material. Unfortunately, release coatings are not necessarily effective and durable (see, for example, F. A. Houle et al., J. Vac. Sci. Technol. B 23, 2427, 2007). If a coating is ineffective, the cured material will become bonded to the coating as a result of the curing step, with the bond between the cured material and the coating being potentially as strong as, or even stronger than, what the bond would be between the cured material and the bare (uncoated) template surface. On the other hand, if a coating is not durable, its repeated contact (e.g., as in a step and repeat patterning process) with photosensitive material during the curing process will eventually result in its degradation. In both cases, patches of highly adhesive regions can eventually develop on the template surface to which the curable material can bind. These patches will create defects in the corresponding imprinted patterns, thus requiring the template to be either refurbished or discarded.
Fluorosilanes have been widely used as release agents, but tend to degrade over time when used with curable materials. Both an alkane silane film (specifically SAMLAYTM from Nippon Soda Co., Ltd, as reported by K. Kumazawa et al., Nanoprint Nanoimprint Technology Conference, San Francisco, 2006) and a diamond-like carbon film (see F. A. Houle et al., Appl. Phys. Lett. 90, 213103, 2007) have been shown to be as effective or even better than fluorosilanes when used with acrylate and methacrylate-based resists, respectively. However, diamond-like carbon does not work well with vinyl ether resists. All of these release agents are chemically vulnerable and subject to degradation with use.
Accordingly, there is a need in the art for improved release layers for templates used in step and flash imprint lithography.
SUMMARY OF THE INVENTION
One aspect of the invention is a method that includes imprinting a template onto a curable composition, in which the template has a patterned surface (e.g., a relief-patterned surface), and in which a release layer that is located at the patterned surface includes an amorphous inorganic oxide having a chemical composition that differs from that of the template. The release layer contacts the curable composition and thereby transfers a pattern into the curable composition. The composition is then cured while the amorphous oxide is in contact with the curable composition, thereby forming a cured, imprinted composition. The template is then removed from the cured, imprinted composition. The amorphous oxide is selected so that the adhesion energy of the cured, imprinted composition to the release layer is less than what the adhesion energy of the cured, imprinted composition to the template would be in the absence of the release layer. The method preferably includes directing ultraviolet radiation through the template, through the release layer, and onto the curable composition. A pattern may be transferred into an underlying substrate by etching through portions of the cured, imprinted composition and into that substrate. The curable composition may include at least one crosslinkable material and a photoinitiator, or it may include at least one crosslinkable material and a photoacid generator.
Another aspect of the invention is a method that includes coating a surface of a patterned template (e.g., a template having a relief pattern thereon) with a release layer that includes an amorphous inorganic oxide selected to reduce adhesion to a curable composition. The template is brought into proximity with a layer of the curable composition, so that the release layer imprints a pattern into the curable composition. Ultraviolet radiation is directed onto the curable composition, so that the curable composition is cured while it is in contact with the release layer, and the template is then moved away from the cured composition.
One implementation of the invention is an apparatus that includes a template having a surface that defines a pattern of features (e.g., a relief pattern), with at least some of the features having a characteristic dimension of between 5 nanometers and 1000 nanometers. The template is configured to be used in a nanoimprint lithography process, in which the pattern is imprinted onto a curable composition that upon exposure to ultraviolet radiation forms a cured composition. A release layer is in contact with the aforementioned surface, and the release layer includes an amorphous inorganic oxide. In a preferred embodiment, at least some of the features have a characteristic dimension of between 5 nanometers and 100 nanometers.
Another implementation of the invention is an apparatus that includes a template having a surface that defines a pattern of features (e.g., a relief pattern), with at least some of the features having a characteristic dimension of between 5 nanometers and 1000 nanometers. The template is configured to be used in a nanoimprint lithography process, in which the pattern is imprinted onto a curable composition that upon exposure to ultraviolet radiation forms a cured composition. A release layer at the surface includes an amorphous inorganic oxide having a chemical composition that differs from that of the template. The amorphous oxide includes at least one element selected from the group consisting of the elements of groups 4, 5, 6, 8, 9, 10, 11, 12, 13, and 14 of the Periodic Table and P, As, Sb, and Bi.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1, which includes FIGS. 1A, 1B, 1C, 1D, 1E, 1F, and 1G, illustrates cross sectional views of an imprint lithography process that is one preferred implementation of the invention;
FIG. 2 presents compositions of test formulations used in demonstrating principles of the invention;
FIG. 3 presents adhesion energy measurements made for various oxide coatings in the presence of dry nitrogen; and
FIG. 4 presents adhesion energy measurements made for various oxide coatings in the presence of humid air.



DETAILED DESCRIPTION OF THE INVENTION
Release layers are disclosed herein that in the context of this invention are unreactive, mechanically durable, optically thin, and conformal. The preferred thickness of these layers is on the order of nanometers, so that they are suitable for nanoscale lithography. Furthermore, the adhesion energy of certain curable materials to certain ones of these release layers is nominally in the range of van der Waals interactions (0.1 J/m2), thereby reducing the possibility of the cohesive failure problem discussed above. To this end, amorphous inorganic oxides are disclosed as release layer materials for use with UV-curable compositions as part of a nanoimprint lithographic process. These oxide layers advantageously enjoy extremely weak interfaces with the UV-cured compositions. As used herein, an “oxide” is a stoichiometric or non-stoichiometric chemical composition that contains oxygen and at least one other element. As used herein, inorganic refers to chemical compositions that are not hydrocarbons or their derivatives.
Process Overview
A variety of nanoimprint lithographic processes may be used in conjunction with the amorphous inorganic oxide release layers described herein, such as a multilayer stack process, a single curable layer process, and processes that utilize sacrificial and/or permanent layers. By way of example, exemplary implementations of the invention are now described with respect to FIG. 1, and in particular, with respect to a step and imprint lithography process, which may be carried out at room temperature. As shown in FIG. 1A, the method includes providing a rigid template 14 onto which an oxide release layer 12 (described in greater detail below) has been formed (e.g., deposited). The template 14 includes a patterned surface of features (represented schematically by the crenellated or notched pattern in FIG. 1A), at least some of which have a characteristic dimension (i.e., a width, length, height, diameter, etc.) on the order of nanometers. For example, at least some of the features have a characteristic dimension of between 5 and 1000 nanometers, and some may have a characteristic dimension of between 5 and 100 nanometers. As described below, these features are imprinted into photocurable material 16 and then transferred to another layer 18 that resides over a substrate 20.
The template 14 may be of SiO2 (e.g., quartz or glass) or sapphire, for example, and may be formed previously in a separate process (not shown) by applying a layer of photoresist over a block of silica or sapphire, exposing the resist to a predetermined pattern of an e-beam or UV light, developing the image, and transferring the resulting developed image into the underlying block; alternatively, a focused ion beam may be used to form features directly into the block, thereby forming the template 14. The photocurable material 16 (which may be drop-coated, spin-coated, or otherwise dispensed onto the layer 18) may include at least one crosslinkable material and a photoacid generator (PAG), or alternatively at least one crosslinkable material and a photoinitiator. The to-be-patterned layer 18 is a patternable material (preferably an appropriate polymeric material), which may be deposited over the substrate 20. The substrate 20 may be made of Si, for example; it may itself be a previously patterned layer over which another layer of features is to be formed. In this manner, an entire electronic structure or device may be “built up” one layer at a time.
As shown in FIG. 1B, the pattern transfer process is implemented by squeezing the photocurable material 16 between the structure made up of the template 14/release layer 12 and the structure made up of the to-be-patterned layer 18/substrate 20. An imprinter apparatus (not shown) may be used that applies the required pressure. Before the components are brought together, the features of the template 14 may be aligned in a predetermined way with the layer 18/substrate 20. To this end, the imprinter apparatus may first utilize a coarse mechanical alignment step, so that the components are brought very nearly into the desired alignment. A subsequent alignment step relying on optical alignment techniques (such as those used with mask aligners, photolithography steppers, and scanners) may then be employed, so that the template 14 is brought into the desired alignment with the layer 18/substrate 20. This subsequent alignment step may make use of special alignment marks (not shown) in both the template 14 and the substrate 20, for example.
FIG. 1C shows the entire assembly when it is being held together tightly. At this stage, ultraviolet light 21 (such as that from a Hg lamp or a laser) is directed onto the photocurable composition 16, whereupon it is cured in situ into a hardened layer 16a. This ultraviolet light may be advantageously directed through the template 14, the release layer 12, and onto the photocurable composition 16. (Alternatively, if the underlying layer 18 and substrate 20 are UV-transparent, then UV light may be directed through them onto the photocurable composition 16.)
In FIG. 1D, the template 14 has been removed from the structure made up of the cured composition 16a/layer 18/substrate 20. The release layer 12 facilitates the separation of the template 14 from this structure, so that the cured composition 16a includes the (inverse of) features in the template 14—but without the defects (tears, pockets, etc.) that would have otherwise been introduced into the cured composition 16a if an unsuitable release layer were used. Likewise, the release layer 12 protects the integrity of the template 14 in the sense that cured material from the cured composition 16a does not readily attach itself to the release layer 12, thereby ensuring that the template 14 will stamp out the same pattern each time it is used.
One specific continuation of the process shown in FIGS. 1A through 1D is now described with respect to FIGS. 1E through 1G. A breakthrough etch (e.g., an oxygen or halogen etch) is employed, as shown in FIG. 1E. In this step, portions 22 (indicated by the hatched regions) of the cured composition 16a are removed, leaving behind only portions of the cured composition 16a. These remaining portions are designated by the alphanumeric 16b in FIG. 1E. The resulting structure is shown in FIG. 1F, and shows that certain regions of the to-be-patterned layer 18 are now exposed, while others remain masked by the portions 16b of the cured composition.
As shown in FIG. 1G, another etch process (e.g., a reactive ion etch) then transfers the pattern of features into the layer 18, while exposing portions of the underlying substrate 20. This “transfer etch” step leaves behind only those portions 18a of the original layer 18 that are masked by the cured composition portions 16b. Thus, this etch process effectively amplifies the aspect ratio of the imprinted pattern.
Release Layer
The release layer 12 disclosed herein is advantageously an oxide of at least one element that by itself is non-gaseous at standard temperature and pressure (0 degrees Celsius and 1 atmosphere pressure); the chemical composition and/or structure of the release layer necessarily differs from that of the template 14 onto which it is coated. In particular, oxides of Al, Cu, Co, Sb, Ti, Ta, W and Ge have been demonstrated to have desirable release characteristics. The oxide includes at least one element selected from the group consisting of the elements of groups 4, 5, 6, 8, 9, 10, 11, 12, 13, and 14 of the Periodic Table and P, As, Sb, and Bi (although pure silicon oxides are not preferred). The oxide materials used for the release layer 12 are amorphous—note from the Examples below, sapphire (crystalline alumina) does not work nearly as well as amorphous alumina. The oxygen content of the oxide is preferably at least 20 atomic %, and may be up to 50 or 75 atomic % or more (e.g., 80 atomic %).
A thin film of such an oxide is deposited onto the template 14 using, for example, plasma, vapor, or solution-based methods, or for example, the release layer may be formed in the template by ion implantation. In the Examples below, sputter deposition was used (resulting in films that were typically 3-10 nm thick), but any suitable deposition method that results in ultrathin, conformal, continuous, smooth films will work, e.g., an atomic layer deposition technique or chemical vapor deposition could also be used.
Silica, the material commonly used for UV-cure nanoimprint templates, usually adheres strongly to cured material. This adhesion is a result of strong chemical bonds, as well as a mechanically lossy polymer structure that resists debonding. The amorphous inorganic oxide release coatings disclosed herein evidently do not so easily form bonds that are involved in adhesion (e.g., siloxane bonds and hydrogen bonds).
Examples
The adhesion energies of Al, Cu, Co, Sb, Ti, Ta, W and Ge oxides with several different resist formulations have been measured. In addition, crystalline Al oxide (sapphire) was tested, in order to compare it with amorphous Al oxide films. The adhesion energies were measured using a DTS Delaminator operated in double cantilever beam mode. Specimens were prepared using 2 bars, one silicon and one quartz, both 8 mm×65 mm. The quartz bar (representing the template 14, but having a substantially flat surface without any relief features) was precoated with the selected oxide (representing the release coating 12). Another structure (analogous to the structure given by the layer 18 and the substrate 20) was the silicon bar precoated with a selected adhesion promoter to ensure good attachment of cured material to it. Both bars had a tab epoxied at one end, which was attached to the non-coated side of the bar. The bars were placed in a glove box purged with dry nitrogen. 2-3 microliters of the selected curable resist (representing the photocurable composition 16) were dropped onto the adhesion-promoter-coated side of the silicon bar, then immediately covered with the quartz bar, allowing the oxide-coated side to be in contact with the resist composition. The resist was allowed to spread evenly. The sandwich structure was removed from the glove box and immediately irradiated with output from an Optical Associates, Inc. (OAI) mid-UV lamp for a preselected time, receiving a dose of 250-350 mJ/cm2 depending on the resist used. The tabbed ends were fixed into the delaminator grips and debonding measurements commenced immediately after cure. The delaminator was placed in a purged enclosure allowing debonding to take place either in dry nitrogen or in room air at ambient humidity. The delaminator displacement rate was held constant at 2 microns/sec. Data were analyzed to obtain Gc (the critical energy release rate in J/m2), which is a measure of adhesion strength, using conventional beam mechanics.
The oxide films, which were deposited on respective quartz bars, had thicknesses ranging from about 3 to about 10 nm. All but the alumina films were deposited by sputtering a target in the presence of an argon/oxygen mixture with an 8:1 Ar/oxygen ratio, whereas alumina was deposited from an alumina target. The alumina and Co oxide films were nearly transparent at 365 nm, while the Ti oxide film absorbed about 5% of the UV light. The other materials were more absorbing at 365 nm, ranging from 59% absorbance for CuOx to 16% absorbance for TaOx. The optical attenuation can be reduced by using thinner films or higher oxygen concentrations. The Ti and Al oxide films were measured to be atomically smooth.
FIG. 2 presents the various formulations used as the photocurable compositions in these measurements, along with their compositions. Specifically, the five different resist formulations below were used as the photocurable compositions, each of which is designated by the indicated alphanumeric:
“SiA”—a silicon-containing acrylate resist, which as indicated included 44 weight percent of SIA 0210.0 (3-acryloxypropyl)tris(trimethoxysiloxy)silane from Gelest, Inc.);
“MC1”—an all-organic acrylate;
“RS751”—a polyhedral oligomeric silsesquioxane methacrylate resist, which included 31.7 weight percent of mPSS (methacryl polyhedral oligomeric silsesquioxane);
“VEB”—a glycol vinyl ether based resist; and
“BnVE”—an aromatic vinyl ether based resist.
The various photosensitizers used in each of the resist formulations are also indicated, in which the following chemicals from the CIBA Corporation were used:
IRGACURE 819TM: phenyl-bis(2,4,6-trimethyl benzoyl)-phosphine oxide;
IRGACURE 184TM: 1-hydroxycyclohexylphenyl ketone;
DAROCUR 4265TM: diphenyl-(2,4,6-trimethyl benzoyl)-phosphine oxide+2-hydroxy-2-methyl-1-phenyl-1-propanone;
Darocur 1173TM: 2-hydroxy-2-methyl-1-phenyl-1-propanone; and
CGI 1907TM: 2-[2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutylsulfonyloxyimino)-pentyl]-fluorene.
Adhesion energies (Gc) measured by debonding under dry nitrogen conditions are presented in FIG. 3, in which a comparison is made with a fluorosilane release layer. In some cases, adhesion could not be measured because the debonding path was not confined to the quartz-resist interface, resulting in large patches of resist left on the quartz, thereby making it impossible to make a meaningful adhesion measurement. It is clear that in the case of the SiA resist with the alumina release coating, the adhesion energy is very close to the minimum possible (i.e., the van der Waals energy).
Debonding under a humid air atmosphere was tested, and the results are presented in FIG. 4. The data show that in most cases where the same materials are involved, the presence of humidity reduced the measured value of Gc, indicating that water vapor is beneficial for the template separation process. Comparing the amorphous alumina results with the sapphire results shows that, although both surfaces are coated with aluminum oxide, the sputtered (amorphous) film is much preferred to (crystalline) sapphire. Thus, templates made of sapphire are not preferred over amorphous aluminum oxide coated quartz.
Note that there is a wide variability in the adhesion of the cured materials to the oxides studied here, suggesting that to achieve optimum results, it may be necessary to select a specific oxide for use with a specific resist. Carefully controlling the debonding environment may also be advantageous for reducing adhesion, depending on the resist chemistry.
The invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is therefore indicated by the appended claims rather than the foregoing description. All changes within the meaning and range of equivalency of the claims are to be embraced within that scope.

## Claims

1. A method, comprising:
imprinting a template onto a curable composition, wherein the template has a patterned surface, and wherein a release layer that is located at the patterned surface includes an amorphous inorganic oxide having a chemical composition that differs from that of the template, wherein the release layer is unreactive and mechanically durable, the amorphous oxide contacting the curable composition and thereby transferring a pattern into the curable composition, wherein the amorphous oxide includes at least one element selected from the group consisting of the elements of groups 4, 5, 6, 8, 9, 10, 11, 12, 13 of the IUPAC Periodic Table and the elements Ge, P, As, Sb, and Bi;
photocuring the curable composition while the amorphous oxide is in contact with the curable composition, thereby forming a cured, imprinted composition; and
removing the template from the cured, imprinted composition, the amorphous oxide being selected so that the adhesion energy of the cured, imprinted composition to the release layer is less than what the adhesion energy of the cured, imprinted composition to the template would be in the absence of the release layer.

2. The method of claim 1, wherein said photocuring includes directing ultraviolet radiation through the template, through the release layer, and onto the curable composition.

3. The method of claim 2, wherein the curable composition resides on a substrate, and the method comprises:
etching through portions of the cured, imprinted composition and into the substrate, thereby transferring the pattern into the substrate.

4. The method of claim 3, wherein the release layer does not contact the substrate.

5. The method of claim 1, wherein the template is removed from the cured, imprinted composition in an atmosphere having a relative humidity of at least 15%.

6. The method of claim 1, wherein the curable composition includes a crosslinkable material and a photoinitiator.

7. The method of claim 1, wherein the curable composition includes a crosslinkable material and a photoacid generator.

8. The method of claim 1, wherein the oxygen content of the release layer is between 20 and 80 atomic %.

9. The method of claim 1, wherein the amorphous oxide includes at least one element selected from the group consisting of the elements Ti, Ta, W, Ge, Al, Sb, Co, and Cu.

10. The method of claim 1, wherein the amorphous oxide includes Ti.

11. The method of claim 1, wherein the amorphous oxide includes Ta.

12. The method of claim 1, wherein the amorphous oxide includes W.

13. The method of claim 1, wherein the amorphous oxide includes Ge.

14. The method of claim 1, wherein the amorphous oxide includes Al.

15. The method of claim 1, wherein the amorphous oxide includes Sb.

16. The method of claim 1, wherein the amorphous oxide includes Co.

17. The method of claim 1, wherein the amorphous oxide includes Cu.

18. The method of claim 1, wherein the release layer has a thickness of less than 10 nanometers.

19. A method, comprising:
coating a surface of a patterned template with a release layer that includes an amorphous inorganic oxide selected to reduce adhesion to a curable composition, wherein the release layer is unreactive and mechanically durable, wherein the amorphous oxide includes at least one element selected from the group consisting of the elements Ti, Ta, W, Ge, Al, Sb, Co, and Cu;
bringing the template into proximity with a layer of the curable composition, so that the amorphous oxide imprints a pattern into the curable composition;
directing ultraviolet radiation onto the curable composition, so that the curable composition is cured while it is in contact with the release layer; and
removing the template away from the cured composition.

20. The method of claim 19, wherein the curable composition resides on a substrate, and the method comprises:
etching through portions of the cured, imprinted composition and into the substrate, thereby transferring the pattern into the substrate.

21. The method of claim 19, wherein the template is removed from the cured, imprinted composition in an atmosphere having a relative humidity of at least 15%.

22. The method of claim 19, wherein the oxygen content of the release layer is between 20 and 80 atomic %.

23. The method of claim 19, wherein the release layer has a thickness of less than 10 nanometers.