TW200931174A - Porous template and imprinting stack for nano-imprint lithography - Google Patents

Abstract

An imprint lithography template or imprinting stack includes a porous material defining a multiplicity of pores with an average pore size of at least about 0. 4 nm. A porosity of the porous material is at least about 10%. The porous template, the porous imprinting stack, or both may be used in an imprint lithography process to facilitate diffusion of gas trapped between the template and the imprinting stack into the template, the imprinting stack or both, such that polymerizable material between the imprinting stack and the template rapidly forms a substantially continuous layer between the imprinting stack and the template.

Description

200931174 VI. Description of the Invention: [Technical Field of the Invention] Cross-Reference Related Application [0001] This application is based on 35 USC's US Provisional Patent, which was filed on December 3, 5, 10, 15, 20, 20, and November 21, 2008. Priority of the application, the above two provisional patent applications are hereby incorporated by reference. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH DEVELOPMENT FIELD OF THE INVENTION [0002] As provided by the provisions of the National Institute of Standards and Technology (NIST ATP AWARD) 70ΝΑΝΒ4Η3012, the US government has a sponsorship license for the invention and, in limited circumstances The power to require the patent owner to authorize the appropriate terms. BACKGROUND OF THE INVENTION Nanofabrication involves the fabrication of very minute constructions having features of the order of 100 nanometers or less. Nanofabrication has produced an impact on the size of the integrated circuit. The semiconductor processing industry continues to seek greater yields while increasing the number of circuits per unit area formed on the substrate, so nanofabrication is becoming increasingly important. Nanomanufacturing provides greater processing control while continuously reducing the minimum feature size of the resulting construction. Areas that have been developed using nanofabrication include biotechnology, optical technology, mechanical systems, and the like. SUMMARY OF THE INVENTION 2 SUMMARY OF THE INVENTION 3 200931174 [0004] In the modality, the embossed lithography template or embossed stack comprises a porous material defined as having a plurality of average pore sizes of at least about It is a pore of 0.4 nm. The porosity of the porous material is at least about 10%. 5 [Caf 5] In certain embodiments, the average pore size is at least about 0.5 nm or at least about i.o. The porosity of the porous material is at least about 20%. In some cases, the porous material is an organic low dielectric value material. The relative porosity of the porous material to the molten vermiculite is at least about 20%. In some cases, the porous material has a Young's modulus of at least about 2 GPa, at least 10 about 5 GPa, or at least about 1 〇 GPa. [0006] In certain template embodiments, the 'porous material is disposed between a substrate layer and a cover layer. The substrate layer can comprise molten vermiculite. In some cases, the substrate layer includes recesses and the porous material is disposed in the recesses. In some cases, the coverage included Si〇x and 15 χ$2. The thickness of the cover layer can be less than about 1 nanometer, less than about 50 nanometers, or less than about 20 nanometers. Most of the protrusions can be extended by the cover layer. In some embodiments of the embossed stack, the porous material is disposed between a substrate and a cover layer. The substrate can include ruthenium. In another aspect, forming an imprint lithography template includes 20 forming a porous layer on a substrate layer and forming a cap layer on the porous layer. In another aspect, forming an imprint lithography template includes forming a plurality of recesses in a substrate, depositing a porous material in the recesses, and forming a cover layer on the substrate layer. In another aspect, forming an imprint lithography stack includes forming a porous layer on a substrate and forming a cap layer on the 200931174 porous layer. The porous layer defines a plurality of pores having an average pore size of at least about 0.4 nm and the porosity of the porous layer is at least about 1%. [0009] In another aspect, an imprint lithography method includes applying a droplet of a polymerizable material to an imprint stack, contacting the 5 polymerizable material with a template to harden the polymerizable material, and The template is separated from the hardened material. In some cases, the template includes a porous material. In some cases, the embossed stack comprises a porous material, and in some cases the stencil and the embossed stack both comprise a porous material. The porous material defines a plurality of pores having an average pore size of at least about 〇·4 nm and the porosity of the porous material is at least about 〇〇/〇. [0010] In another aspect, an imprint lithography method includes dispensing a polymerizable material onto a surface of an imprint stack, contacting the polymerizable material with a template, and allowing the polymerizable material to be polymerized. The material is capable of diffusing to form a substantially continuous layer on the surface of the embossed stack. The template, the 15print stack or both can comprise a porous material defining a plurality of pores having an average pore size of at least about 4 nanometers and having a porosity of at least about 1 inch. %. Spraying the polymerizable material to form a substantially continuous layer occurs when the similar polymerizable material is similarly distributed to form a substantially continuous layer between a first template and a second imprint stack. About 80% or less, 5% or less, or 2% or less, wherein the second template and the second embossed stack have an average pore size of less than about 〇4 nm. BRIEF DESCRIPTION OF THE DRAWINGS [0011] For a more detailed understanding of the present invention, a description of embodiments of the present invention is provided with reference to the embodiments shown in FIG. 5 200931174. However, it is to be understood that the appended claims are not intended to [0012] Figure 1 shows a simplified side view of a lithography system; 5 [0013] Figure 2 shows a simplified side view of the substrate shown in Figure 1, with a patterned layer disposed on the substrate. [0014] Figure 3 shows a porous template. [0015] Figure 4 shows a porous imprint stack. [0016] Figure 5 shows a portion of layer 10 having a porous material in a plurality of recesses. [0017] Figure 6 shows an imprint lithography procedure using a porous template and a porous embossed stack. [0018] Figure 7 shows an imprint lithography procedure using a uniform porous template and a porous imprint stack. 15 [(8)19] Figure 8 is a photograph of an embossed resist droplet dispensed on a substrate. [0020] Figures 9A-D are photographs of embossed resist droplets sprayed onto an embossed stack. [0021] Figures 10A-D are photographs of droplets of imprinting resist sprayed onto a porous imprint stack 2〇. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0022] An exemplary nanofabrication technique used today is commonly referred to as imprint lithography. Exemplary embossing lithography procedures are described in some of the 200931174 publications, such as U.S. Patent Application Publication No. 2004/0065976, U.S. Patent Application Publication No. 2004/0065252, and U.S. Patent No. 6,936,194, all of which are incorporated herein by reference. This is incorporated herein by reference. [0023] An imprint lithography technique as described in each of the above-mentioned U.S. Patent Application Publications and patents, which is incorporated herein by reference in its entire entire entire entire entire entire disclosure One of the relief patterns is transferred into a substrate disposed below. The substrate can be coupled to a motion stage' to facilitate positioning for the patterning process. The patterning process uses a template spaced from the substrate and a liquid is formed between the template and the substrate. The formable liquid is hardened to form a hard layer having a pattern corresponding to the shape of the template contacting the surface from which the liquid can be formed. After hardening, the template is separated from the hard layer so that the template is separated from the substrate. The stencil and the hardened layer are then further processed to transfer a embossed image to the substrate corresponding to the pattern in the hardened layer. Referring to Fig. 1, there is shown a lithography system 1 for forming a relief pattern on a substrate 12. An embossed stack can include a substrate 12 and one or more layers (e.g., an adhesive layer) adhered to the substrate. The substrate 12 can be joined to the substrate holder 14. As shown, the substrate holder 14 is a vacuum block. However, the substrate holder 14 can be any type of clamp, including but not limited to vacuum, plug, grooved, electromagnetic, and the like, or any combination. An exemplary clip is described in U.S. Patent No. 6,873,087, incorporated herein by reference. The substrate 12 and the substrate holder 14 can be further supported by the table member 16. The table member 16 is capable of providing motion about the χ_, y_, and z axes. 20 200931174 The table member 16, the substrate 12, and the substrate holder 14 can also be disposed on a substrate (not shown). The template 18 is spaced from the substrate 12. The stencil 18 can include a male member 2 延伸 extending from the stencil toward the substrate 12 having a patterned surface 22 thereon. Further, the male member 20 can be referred to as a module 20. Template 18 and/or module 20 can be formed from such materials, including but not limited to: molten twins, quartz, tantalum, organic polymers, siloxane polymers, borosilicate glass, fluorocarbon Polymer, metal, hardened sapphire and the like, or any combination thereof. As shown, the surface 22 includes features defined by a plurality of spaced apart recesses 24 1 〇 and protrusions 26, and embodiments of the present invention are not limited to this configuration. Patterning the surface 22 can define any of the original patterns that open the basis of the pattern to be formed on the surface of the substrate 12. The template 18 can be coupled to the lost piece 28. The clip 28 can be constructed, but not limited to, in the form of a vacuum, plug, groove, electromagnetic, and/or other clip. An exemplary clip is further described in U.S. Patent No. 6,873,087, the disclosure of which is incorporated herein by reference. In addition, the squeegee 28 can be coupled to the embossing head 3 〇 such that the clip and/or the embossing head 30 can be configured to facilitate movement of the stencil 18. [0028] System 1G can include a fluid dispensing system 32. The 20 fluid dispensing system 32 can be used to deposit the polymerizable material 34 on the substrate 12. The polymerizable material M can be disposed on the substrate using several techniques, such as droplet dispensing, spin coating, immersion coating, chemical vapor deposition (cvp), physical vapor deposition (PVD), thin deposition, thick product And similar technology or any group of mouths. The polymerizable material 34 can be disposed on the substrate 12 before and/or after the required volume between the module and the substrate η 200931174, according to » again. Ten exams and squatting. The polymerizable material 34 can include the components described in U.S. Patent No. 7,157, 365, the entire disclosure of which is incorporated herein by reference. 5 e 10 15 ❹ 20 [0029] Referring to Figures 1 and 2, the system further includes a face-energy source 38' to direct energy 4() along path 42. The embossing head 30 and the table member 16 can be constructed such that the splicing path 42 arranges the stencil 18 and the substrate 12. The system 10 can be controlled by a processor 54 that connects the table member 16, the embossing head 3, the fluid dispensing system 32, the energy source 38, or a combination thereof, and can be readable by a computer stored in the memory 56. Take the program and execute it. [0030] The stamping head 30, the table member 16, or both can vary the distance between the module 2 and the substrate 12 to define a volume therebetween that is substantially filled by the polymerizable material 34. For example, the stamping head 3 can apply a force to the template 18 to contact the module 18 with the polymerizable material 34. After the desired volume is substantially filled with the polymerizable material 34, the energy source 38 produces energy 40, such as broadband ultraviolet radiation, such that the polymerizable material 34 conforms to the surface 44 of one of the substrates 12 and the shape of the patterning surface 22. A patterning layer 46 is defined on the substrate 12 by way of hardening and/or crosslinking. The patterning layer 46 can include a retention layer 48 and a plurality of features shown as protrusions 50 and recesses 52, and the protrusions 50 have a thickness h and the recesses 52 have a thickness t2. [0031] The above-described systems and procedures can be further implemented in reference to U.S. Patent No. 6,932,934, U.S. Patent Application Publication No. 2004/0124566, No. 2009 2009 174, U.S. Patent Application Publication No. 2004/ No. 188,381, and U.S. Patent Application Publication No. 2004/ No. 0211754, each of which is incorporated herein by reference. [0032] In a nanoimprint procedure in which the polymerizable material is applied to the substrate 12 by droplet dispensing or spin coating, the gas may be trapped in the recess after the template contacts the polymerizable material. In a nanoimprint process in which a polymerizable material is applied to a substrate by a droplet dispensing method, the gas may also be trapped in a polymerizable material and an imprinting resist disposed on a substrate or an imprint stack. Between the droplets. That is, the gas may trap between the droplets as the droplets are dispersed. [0033] The rate of gas diffusion and decomposition can limit the rate at which the polymerizable material can form a continuous layer on a substrate (or an embossed stack) or the polymerizable material can fill the stencil after it contacts the polymerizable material. – the rate of the feature, thereby limiting the entire nanoimprint procedure. For example, the substrate 15 or a template is substantially inaccessible to the gas trapped between the substrate and the template. In some cases, a polymer layer adhered to the substrate or template is saturated, so that The gas enthalpy between the embossed stack and the stencil is substantially inaccessible to the saturated polymer layer and remains trapped between the substrate and the substrate or p-stack. The gas still trapped between the substrate or the embossed stack and the dies 20 may cause a plague in the polymer layer. ^] In the embossing lithography procedure, the gas trapped between the substrate/imprint stack and the stencil can be vented through the polymerizable material, the substrate edge-stacked stack, or any combination thereof. The amount of gas dissipated through any medium can be affected by the contact area between the trapped gas and the medium. 10 200931174 The contact area between the trapped gas and the polymerizable material can be smaller than that of the trapped gas and the substrate/imprint stack. The contact Φ product is less than the contact area between the trapped gas and the template. For example, the thickness of the polymerizable material on the __substrate/embossed stack can be less than about 1 micron, or less than about 100 nanometers 5 ❹ 10 15 ❹ 20 meters. In some cases, the polymerizable material is capable of absorbing sufficient gas and, upon imprinting, becomes gas saturated such that the trapped gas is substantially inaccessible to the polymerizable material. Conversely, the contact area between the trapped gas and the substrate or imprint stack or the contact area of the trapped gas with the template may be quite large. [0035] In some cases, the substrate/imprint stack or template can include a plurality of porous materials defining a plurality of recesses having an average porosity and a pore density or a relative porosity, the porous material being selected, Used to help the gas diffuse into the substrate/imprint stack or template, respectively. In some cases, the substrate/embossed stack or stencil may include one or more layers or regions of a porous material that are designed to facilitate separation from the substrate/imprint stack, respectively. The polymerizable material between the substrates, and the gas trapped between the substrate/imprint stack and the template is carried toward the substrate 7 in the direction of imprinting the stack or template. [0036] The gas permeability of a vehicle can be expressed as p = DxS, where P is permeability, D is diffusion coefficient, and s is solubility. During a gas transfer, a gas is absorbed onto one of the surfaces of the vehicle and a concentration gradient is established in the medium. This concentration gradient can act as a driving force for diffusing gas through the medium. The gas solubility and the diffusion coefficient month b are sufficient to be based on, for example, the packing density of the medium. Adjusting the bulk density of the medium can change the diffusion coefficient, thereby changing the permeability of the medium. [0037] A gas can be imagined to have an associated kinetic diameter. The kinetic diameter provides a concept of a gas atom or molecule for the size of a gas transport. "Zeolite Molecular Sieves" by DW Breck (New York, john Wiley & s〇ns, 1974, p. 636, incorporated herein by reference) The kinetic diameters of 常见 (0.256 nm), argon (0.341 nm), oxygen (〇346 nm), nitrogen (0.364 nm), and other common gases. ® 10 [0038] In some embossing lithography procedures, a cleaning is used to substantially replace the air between the stencil and the substrate or embossed stack. To simplify the comparison between a helium environment and an air environment in an imprint lithography procedure, the polarity of the interaction between oxygen and vermiculite in the air can be neglected by modifying the air with pure argon. Both helium and argon are 15 inert gases, and argon has a kinetic diameter similar to oxygen. However, unlike oxygen, helium and argon do not react with molten vermiculite or quartz. 〇 [0039] The internal recess (dissolvable) and the structural channel connecting the soluble sites allow gas to permeate through a vehicle. This gas may remain in the 20 soluble place. The internal recess and the size of the passage diameter relative to the size of the gas (or the dynamic diameter) affect the rate at which the gas penetrates into the medium. [0040] The size of the individual interstitial soluble sites of the molten vermiculite exhibits a lognormal distribution as shown by J. F. Shackelford in J. Non-Cryst. Solids 253, 1999, 23, which is incorporated by reference. Incorporated into this article. For example, 12 200931174 = 81 nm; average side 6 nm) and 动力学 and mouse dynamics, (4) The number of transferable systems exceeds the number of soluble points for argon. The total number of inter-f is estimated to be 2.2 X 1〇28 per cubic, with 2.3 X 10 per cubic meter of dissolvable and argon soluble at U x (8) per cubic meter. The average distance between the soluble sites of 氦 is 94 nm and the average volume between the soluble points of argon is 2.6 nm. The binder can be dissolved

The structural channel is conceived to be similar to the 6 noble oxygen cut ring (6__ber ΙΟ πη(4)' and has a diameter of about 3 nanometers. Tables summarize some parameters that affect the permeability of ammonia and argon in the molten vermiculite.

10

[0041] Boiko (GG Boiko et al., ed., "Glass Physics and Chemistry", Vol. 29, No. 2003, pp. 42-48, incorporated herein by reference)) Stone's behavior. In a soluble region, the germanium atoms vibrate at an amplitude that the interstitial volume can provide. The passage of atoms through the channel from the interstitial may be smaller than the interstitial /J\ 〇 [0042] The parameters listed in Table 1 indicate that the permeability of argon in the smelting stone is very low or It can be ignored at room temperature (i.e., the kinetics of argon 20 diameter exceeds the channel size of the molten vermiculite). Due to the kinetics of oxygen and nitrogen, the diameter of the system is greater than the kinetic diameter of argon, so air is generally incapable of penetrating molten vermiculite. On the other hand, helium can diffuse into and penetrate the molten vermiculite. Therefore, when a nano-imprinting process is performed using a helium atmosphere instead of an atmospheric environment, helium gas trapped between the template and the substrate or the imprinted stack can penetrate the five molten vermiculite template. [0043] Figure 3 is a side elevational view of the polymerizable material 34 between the substrate 12 and the porous template 300, and an enlarged cross-sectional view of various porous template embodiments for use in nanoimprint lithography. The arrow symbol indicates the direction in which the gas is transported into the template 300. 10 [0044] The template 3A includes a porous layer 302 between the base layer 304 and the cover layer 306. The porous layer 302 can be formed on the base layer 3〇4 by chemical vapor deposition (CVD), spin coating, thermal growth, or the like. The porous layer 302 can have a thickness of at least about 10 nm. For example, the thickness of the porous layer 3〇2 can range from about 10 nm to about 1 μm, or from about 15 nm to about 10 μm. In some cases, the thicker porous layer 302 is capable of providing higher effective permeability without significantly degrading performance with respect to, for example, UV light transmission, thermal expansion, and the like. The porous layer 3〇2 may be made of, but not limited to, anodized aluminum oxide, organic decane, organic vermiculite, an organic phthalate material, an organic poly σ, an inorganic polymer, and any combination thereof. In some embodiments, the porous material can be a low porosity or ultra low k dielectric film such as spin on glass (SOG) for electronic and semiconductor applications. The porous material is chosen to withstand the re-use of the embossing process including the raw process. Adhesion of the porous layer 302 to the base layer 304 and covering the layers of the 200931174 layer 306 may be at least three pieces of force required to separate the template from the pattern forming layer formed in the 1 lithography procedure. In certain embodiments, the porous material is capable of being substantially transparent to MUv radiation. The tensile modulus of the porous material can be, for example, at least about 2 (jpa, at least about 5 5 Gpa, or at least about 1 〇 GPa. [Xie 6] by varying the program conditions and materials, it is possible to produce different pores. Size and pore density (porosity or relative porosity) of the pore gap rate material. In some cases, for example, ion bombardment can be used to form pores in the material. The porous layer can have pore fans, which are The 10 fused vermiculite has a larger pore size and a higher porosity. As used herein, "porosity" means the percentage of the total volume occupied by the passageway and the open space in an entity. The porosity of the porous layer 302 can range from about 0.1% to about 60%, or from about 5% to about 45%. In some cases, the porosity of the porous layer 302 can be at least about 1% or at least about 2 〇 15 %. The relative porosity of similar materials can be defined as the relative difference in density of the material. For example, (10) (density PsQG = 1.4g / em3) for dioxite (density! 〇 *** w = 2.2 One of g/cm3) relative porosity can be calculated It is l〇〇%x (p(tetra) stone (tetra) stone, or 36%. The molten vermiculite can be used as a reference material for other materials including oxygen bond. In some embodiments, A porous material comprising an oxonium bond has a relative porosity of at least about 10%, at least about 20%, or at least about 30% for the molten vermiculite. [0047] The size of the pores in the porous material Can be well controlled (eg, substantially uniform, or have a desired distribution). In some cases, in 200931174, the pore size or average pore size is at least about 奈4 nm at least about 0.5 nm or That is, the pore size or average pore size can be large enough to provide a sufficient amount of gas to be so soluble that the gas can be made 5 when the gas is trapped between the substrate/imprint stack and the template 300A. Diffusion into the porous layer 302 of the template. [0048] The sesquioxane polymer is an exemplary porous material. "Highly porous polyhedral sesquiterpene polymer-composites and properties" by Zhang et al. J. Am. Chem. Soc., 1998, 120, The intracube pores and the larger mtercube pores within the sesquiterpene oxide poly10 complex are described in the paper by 8389-8391, which is incorporated herein by reference. The square pore system is about 〇3~〇4 nanometer spheres, and the inter-matrix pore system is an 椭圆·5~0.6 nm diameter and an ellipse having a length of 1〇~1.2 nm. As described in the text, it has at least about A pore having a diameter of 4 nanometers, such as a sesquiterpene oxide polymer, is believed to provide a soluble size of 15 and shape suitable for absorbing a gas having a kinetic diameter smaller than the size of the soluble sites. In some cases, the configuration of a porous material that is soluble allows the absorbed gas to remain substantially in the soluble state rather than diffusing away from the material. [0049] A porogen can be added to the material to form a porous layer 302 to increase the porosity and pore size of the porous layer. The porogen includes, for example, an organic compound capable of evaporating such as norbornene, ?-terpinene, polyoxyethylene, and polyoxyethylene/polyoxypropylene copolymers and the like, and any combination thereof. The porogen can be, for example, a straight line or a star. The porogen and program conditions can be selected to form a microporous low _k porous 200931174 layer, for example having an average pore diameter of less than about 2 nanometers, thereby increasing the amount of soluble point for a range of gases. In addition, the introduction of a porogen and an increase in porosity can expand the structural passage where the connecting gas is soluble. For pore sizes of about 0.4 nm or more, a low _k film may penetrate 5 ❹ 10 15 ❹ 20 permeability may exceed the 氦 permeability of the vitreous fused vermiculite. [0050] Base layer 304 and cover layer 306 can be made of the same or different materials. In some embodiments, the base layer 304 can be a molten vermiculite, and the cover layer 306 can comprise SiOx, and 1 g x $2, which is grown by a vapor deposition process. The thickness and composition of the cover layer 306 can be selected to provide mechanical strength and selected surface properties, as well as gas trapped between a substrate/embossed stack and a template in an imprint lithography procedure. Permeability. In certain embodiments, the cover layer 3〇6 has a thickness of less than about 1 奈 nanometer, less than about 50 nanometers, or less than about 2 nanometers. In one example, the cover layer 306 is about 1 nanometer thick. The cover layer 3〇6 can be formed by selecting materials for achieving the desired wetting and release properties during an embossing lithography procedure. The cover layer 306 is also capable of inhibiting the penetration of the polymerizable material 314 into the porous layer while allowing gas to diffuse through the cover layer and into the porous layer 302. [0051] For a multilayer film, the effective permeability can be calculated from an I5 force model, such as by F. Peng et al. at j. Membrane SC1. 222 (2003) 225-234 and A. Ranjit Prakash et al., Analog Devices and Actuators, Bl 13 (2006) 398-409, an analogy of electronic circuits, both of which are incorporated herein by reference. The resistance of a village material to the penetration of a steam is defined as the permeability resistance. 17 200931174 Force Rp ° For a two-layer composite film, the layer thickness is 丨丨 and 丨2, and the corresponding osmosis is immersed, and the osmotic resistance _ is defined as: ηρ^=1ψ7ϊΰ Ο) 5 where Δρ is the pressure difference across the film, 】 is the flux, and the lanthanum is the area. Resistance model prediction

Rp = Ri + R_2 When the cross-sectional area is the same as that of materials 1 and 2 (2) Equation (2) can be re-displayed

10 [0052] For a thickness of about 1 〇 nanometer and permeability? For the template 3A of the Si〇x cover layer 306, the template permeability can be adjusted by selecting the porosity and pore size of the porous layer 3G2. The effect of the permeability and thickness of the porous layer 3 〇 2 on the effective permeability of the multilayer composite embossed stack having a thickness of 310 nm is shown in Table 2. 15

JgiOx) 涿 性 p, 1 〇 nano 10 nm 10 nm 10 nm Table 2

m ^〇〇ϊ5Γ

Permeability ratio Basement thickness 〇2 culverts 0 100nm Ρ2=1000Ρι 4000Ρ! 301Ρ^~~~· ~2jp:

[0〇53] Table 2 suggests that increasing the thickness of the porous layer alone can result in a higher permeability than the permeability of the porous layer alone. That is to say, for the thickness of the nano-porous layer and the thickness of the meter - covering 18 200931174 5 ❹ 10 15 20 cap layer, the permeability of the porous layer is from 1〇〇p to 1〇〇〇. A tenfold increase in Ρι increases the effective permeability from 23.8P! to SO.lPt. For a composite embossed stack having a porous layer of 100 nm, 200 nm and 3 Å nanometers and a cover layer having a thickness of 1 〇 nanometer, the thickness of the porous layer is increased by 2 〇〇 The meter can increase the effective permeability by 2 times, from 1.5P! to 2.8P! to 30.1P! [0054] In another embodiment, the protrusion 31A can be extended by the cover layer 3〇6. In one example, the template 300B can deposit a 500 nm thick porous layer (eg, an organic bismuth low-k film) on a substrate layer (eg, quartz) and grow on top of the porous layer. A cover layer having a thickness of 1 nanometer (for example, SiOx) is formed. The cover layer is etched back to form a protrusion having a height of 90 nm. As regards the thickness of a cover layer used herein, it is considered to be independent of the height of the protrusion 310. Thus, the cover layer is considered to be 10 nanometers thick in this example, and the protrusions extend from the cover layer by a height of 9 nanometers. The templating surface of at least about 50°/° has a SiOx covering a thickness of 10 nm (i.e., about 5% of the templating surface area is covered by the protrusions) and has a 5 Å thick layer of porous layer underneath. Helium may diffuse more rapidly through the cover layer without a portion of the canine, achieving an overall increase in helium permeability that depends, at least in part, on the thickness of the porous layer, the thickness of the cover layer, and the surface area of the template without protrusions. Part depends. [0055] A template is capable of forming a uniform configuration that is capable of diffusing a porosity of one gas and an average pore size. The template is made of, for example, an organic polymer, an inorganic material (e.g., carbonized; gadoline, doped vermiculite, VYC〇R(g)) and the like, or any combination thereof, capable of having a lower packing density. And therefore has a higher gas permeability than the vitreous fused vermiculite (Example 19 200931174 such as helium). Figure 3 shows the template 300C. Template 300C consists essentially of a single porous layer 302. The porous layer 302 does not adhere to a base layer. The porous layer can have an average pore size of at least about 0.4 nanometers and a porosity of at least about 10%. Luudo j 10 15 20 〇 vp ^ 1 text m / hundred jvu ~ 7 Zha is 302. Cover layer 306 can be, for example, si〇x. Like the template 3〇〇c, the porous ^ does not adhere to the base layer. The cover layer 3G6_ inhibits the polymerizable material and enters the porous material. The cover layer 306 can also impart the desired surface properties, mechanical properties, and the like to the template. [0057] The embossed stack can comprise a substrate and a layer of the substrate. Multi-laminated (four) stack ships include one or more additional self-layers adhered to form a multi-layer composite. The substrate can be, for example, a lithographic wafer. The layer of the substrate can comprise, for example, an organic polymeric material, an inorganic polymeric material, in any combination thereof. Pure, layer or; any combination of cranes: ruler cuts and holes __ to choose to allow the gas to diffuse through the imprinted (four) body, thereby helping to reduce the in-imprint (four) process of the body, And it is full of features in the board. The diagram of the door is shown in the template 18 and the imprint stack ·=Γ:Γ4. The arrow symbol indicates that the gas is transported into the pressure _ increasing pressure _ body - thickness can be changed; ==:: force, and down 1 wash _ produce (four) fine = body and atmosphere [_] in some embodiments, like pressure Imprint J

❹ 20 200931174 5 Ο 10 15 ❹ The cross-sectional view shows that the embossed stack can include a porous layer 402 formed on the substrate 12. The porous layer 402 can have pores 408 and can be, for example, an organic bismuth low-k film. A cover layer 4〇6 can be formed on the porous layer 402. One of the porous layers 402 can range in thickness from about 50 nanometers to a few micrometers, depending on the intended use. The pore size in the porous layer can be well controlled (e.g., substantially uniform or with a known distribution). [0060] In certain embodiments, one of the porous layers 4'2 has a pore size or average pore size of less than about 1 nanometer, less than about 3 nanometers, or less than about 1 nanometer. In some cases, the pore size or average pore size is at least about 0.4 nanometers, at least about ο” nanometers or more. That is, the pore size or average pore size can be large enough to provide a sufficient amount of solubles for the gas (e.g., mash) so that the gas trapped between the substrate 丨2 and a template 18 can diffuse. It enters the porous layer 4〇2 of the imprint stack 4〇〇. In some embodiments, the porosity of the porous layer is at least about hops or at least 20%. 20 . [0G61] In some cases, the strain from the substrate layer of the porous template or the substrate of the porous imprinted stack can be transmitted through the porous layer to the cover layer. The porous layer can have a Young's modulus that is lower than the base layer or substrate. In some implementations, Qian Zhiwei Wei-embeds the porous material in the substrate and adds low. For example, a plurality of recesses or grooves can be inserted into the substrate-substrate or substrate layer into which the porous material can be deposited. In some cases, the porous material can be substantially filled or recessed. Next, the m-domain is overlaid on the substrate or substrate to substantially cover the substrate or substrate and the porous material such that the cover layer contacts the substrate or substrate and reduces strain transfer. The area and space of the recess or groove, as well as the volume of the porous material, can be sufficient to dissipate the gas into the porous material during the embossing lithography procedure. [0062] Figure 5 shows an exploded perspective view of layer 500 having a recess 502. Layer 500 can be, for example, a substrate. The recess 502 can include, for example, any regular or irregular, uniform or non-uniform shape or size of grooves or depressions. In some embodiments, the recess 502 can form a grid pattern with uniform or non-uniform spacing. The grid spacing a can be, for example, about 0.25 microns. The recess 502 can be substantially filled with a porous material 504. A cover layer 506 can be formed over the layer 500 and the porous material 504 located in the recess 502 such that strain can be transferred directly from the layer 500 to the cover layer. 506, while still increasing the diffusion of gas through the template 500. The cover layer 506 can be formed by, for example, chemical vapor deposition and the like. [0063] For an embossing lithography procedure with a porous template, when the pores of the second template are less than the porous template, or have a lower porosity (for example, when the second When the template is made of molten vermiculite, quartz or a common templating material, the time required for a droplet of polymerizable material to form a substantially continuous layer between the embossed stack® substrate/template and the template may The time required for droplets of the same polymerizable material to form a substantially continuous layer between 2 Å and a second template in a similar embossed stack/substrate, up to about 50%, up to about 50%, or up to about It is 20%. For an embossing lithography procedure with a porous embossed stack/substrate, when the second embossed stack/substrate has less porosity than the porous embossed stack/substrate, or has a lower At the time of porosity (for example, when the second embossed stack/substrate is essentially composed of 22 200931174 on one of the adhesion layers on a wafer), a droplet of polymerizable material is in the embossed stack/substrate The time required to form a substantially continuous layer with the template may be the same arrangement of droplets of the same polymerizable material to form a substantial 5 Ο 10 15 between a second embossed stack/substrate and a similar template. ❹ 20 The time required for the continuous layer is up to about 80%, up to about 5%, or up to about 20%. [0064] As shown in Figure 6, in some embodiments, a porous template and a porous imprint stack can be used together. For example, a porous layer 302 can be included in the template 3, and the porous layer 4 can be included in an imprint stack 400. If, for example, the cover layer is thin enough, the introduction of a porous layer into the template and the imprinted stack can increase the amount of gas (e.g., helium, nitrogen, or helium) that is dissipated through the porous layer. In some embodiments, as shown in Figure 7, a uniform porous template 3 〇〇 and an embossed stack with a porous layer can be used together. EXAMPLES [0065] Preparation of a porous imprint stack. S〇g (Rotary coated glass sold by Honeywell Electronic Materials, ACCUGLASS® 512B) is rotated on a pre-cleaned 8 吋 double-sided polished 矽 wafer substrate. The wafers are then at 80 ° C, 150 ° C and Bake at temperatures of 250 ° C for 60 to 120 seconds. The SOG coated wafer is then cured in a nitrogen atmosphere of 425 ° C to 45 (TC for 1 hour. The SOG layer is about 1.7 μm thick, and the resulting hydrophobic SOG surface is treated with oxygen electricity through 5 to 20 Seconds to produce a hydrophobic surface. [0066] One component is about 77 grams of IsoRad 501 (a multi- 23 200931174 functional reactive compound sold by Schenectady, Schenectady, NY), 22 grams of Cymel 303ULF (New Jersey,

A cross-linker comprising hexamethoxymercapto melamine (HMMM) sold by Cytec Industries Ltd., West Patterson, and 1 gram of Cycat 4040 (a catalyst sold by Cytec Industries Ltd.), There is also about 5 39.9 kg of PM acetate (a solvent including 2-(l-meth〇xy)pr〇pyl acetate) sold by Eastman Chemical Company, Kingsport, Tennessee. A layer is formed on the surface of the SOG. The composition was spin-coated on the s〇G layer and cured at i6 (TC for 60 seconds to form an adhesion layer of approximately 7 nm thickness. ® 1〇 [0067] Porous template preparation. s〇G (Honeywell) The spin-on glass sold by Electronic Materials, ACCUGLASS® 512B) is rotated on a pre-cleaned molten vermiculite template, which is then baked at 8 (rc, 150 ° C and 250 ° C). Bake 6 〇~120 sec. The s〇G coated wafer is then cured at 425 ° C ~ 450. (: nitrogen curing for 1 hour. The 15 layers are about 650 microns thick. The template is cleaned with standard wet The process is cleaned. A cerium oxide coating is then deposited using plasma enhanced chemical vapor deposition (PEVCD). The overlay is approximately 8 nanometers thick. [0068] Similar to US Patent No. 7, 3, 7118 (which An imprinting resist (e.g., viscous 20 of about 10 CP) of the block A8 described herein, incorporated herein by reference, is used to test a porous embossing made as described above. Filling speed of the stack. As shown in Figure 8, the imprinting resist is distributed in a grid pattern. The stack is printed on the stack, and the center of the droplet 800 of the imprinting resist is separated by 340 micrometers, and a droplet volume is about 12 picoliters (PL). The interstitial region 8〇2 is visible between the droplets 800. A 氦气清24 200931174 Wash to substantially replace the air between the embossed stack and the stencil with helium. The residual layer thickness of each of the cured curing resists is about 9 〇. 5 ❹ 10 15 20 [0069] Comparative Example: The porous imprinted stack was not used and was spread using an imprinting resist of a blank fused vermiculite template. Figure 9a is an embossing resist for an imprinted stack and a fused template. The droplet 900 is in the photo when the template is in contact with the imprinting resist. The interstitial region 902 covers more surface area than the droplet 9GG. The 9Bg is taken after 1 second of exposure of the imprinting resist to the template. ―Photo. The camera's field of view has been adjusted so that you can see the four inter-f regions. The 9c picture is a photo taken after the material impedance display is _7 seconds off, and you can see two interstitials. Area 9〇2. The first map shows the template and imprint impedance After 8 seconds, the embossing resistor (4) is completely spread to form a substantially continuous layer 9〇4 between the stencil and the embossed stack. [0070] Example: Using a embossed stack and using a blank fused gravel template The embossing resist is dispersed. The first GA_ is a droplet 1_ of the imprinting resist between the "porous! embossed stack" and the empty self-reinforcing stencil template when the template is in contact with the imprinting resist - Photographs. As previously described, the porous imprinted stack comprises a SOG layer coated with a thickness of about 17 microns and a fine layer of 8 nanometers on the object G. The first rigid frame is a photograph taken after the embossing resist is in contact with the template for 0.5 second. The field of view of the camera has been adjusted so that four interstitial areas can be seen. The 1GC image shows that the embossed impedance is difficult to contact with the photo taken after 0.75 seconds, and the interstitial area can be seen. The first impressions of the stacking of the stacks of the stencils after the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ [0071] Thus, comparing the embossing resist dispersion to achieve a complete fill or forming a substantially continuous layer between a blank fused vermiculite template and an embossed stack (ie, no visible trapped gas or It is the interstitial region. The time required 'shows that the porous imprint stack has a dramatic effect on the shortening of the filling time of the conventional imprint stack. In this case, the time to complete the fill was reduced by more than 75%. Therefore, the embossing resist is dispersed to form a substantially continuous layer 10 on a embossed stack having a porous material to form a substantially continuous embossed resist on an embossed stack having no porous material. The time required for the layer is reduced by about 20%. Comparing the porous template with the template without a porous material, a similar increase in filling speed can be obtained for the porous template. This reduction in fill time can result in more rapid productivity and reduce the likelihood of defects in the imprint lithography procedure. The embodiment of the present invention described above is exemplary, and the above disclosure can be changed and modified without departing from the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a simplified side view of a lithography system; Fig. 2 shows a simplified side view of the substrate shown in Fig. 1, on which a pattern layer is arranged. Figure 3 shows the porous template. Figure 4 shows a porous imprint stack. 26 200931174 Figure 5 shows a portion of a layer having a porous material in a plurality of recesses. Figure 6 shows an imprint lithography procedure using a porous template and a porous imprint stack. Figure 7 shows an imprint lithography procedure using a uniform porous template and a porous imprint stack. Figure 8 is a photograph of an embossed resist droplet dispensed on a substrate. Figures 9A through D are photographs of the embossed resist droplets sprayed onto an embossed stack. Figures 10A-D are photographs of embossed 10 resist droplets sprayed onto a porous embossed stack. [Description of main component symbols] 10...System 38...Energy source 12...Substrate 40...Energy 14...Substrate clip 42...Path 16...Platform 44...Surface 18...Template 46...Pattern forming layer 20...Module 48...Retained layer 22...surface 50...protrusion 24.·recess 52...recess 26...projection 54...processor 28...clip 56...memory 30...imprint head 300...template 32...fluid distribution system 300A...template 34 ...polymerizable material 300B...template 27 200931174 300C...template 502...recess 300D...template 504...porous material 302·porous layer 506...covering layer 304...base layer 800...imprinting resist droplets 306···covering Layer 802...interstitial region 308...pore 900...imprinted resist droplet 310···overtapping 902...interstitial region 400··imprint stack 904...continuous layer 402···porous layer 1000...imprint Impedance droplets 406...cover layer 1002···interstitial region 408...porosity 1004...continuous layer 500···layer 28

Claims (1)

200931174 VII. Patent application scope: 1. An imprint lithography template comprising a porous material defining a plurality of pores having an average pore size of at least about 0.4 nm, wherein the porosity of the porous material is At least about 10%. 5 10 15 ❹ 20 2. The template of claim 1 wherein the average pore size is at least about 0.5 nm. 3. The template of claim 1 wherein the average pore size is at least about 1.0 nm. 4. The template of claim 1, wherein the porous material has a porosity of at least about 20%. 5. The template of claim 1 wherein the porous material is an organic bismuth low-k material. 6. The template of claim 5, wherein the porous material has a relative porosity of at least about 20% for one of the fused vermiculite. 7. The template of claim 1, wherein the porous material has a Young's modulus of at least about 2 GPa. 8. The template of claim 1, wherein the porous material has a Young's modulus of at least about 5 GPa. 9. The template of claim 1, wherein the porous material has a Young's modulus of at least about 10 GPa. 10. The template of claim 1, wherein the porous material is disposed between a substrate layer and a cover layer. 11. The template of claim 10, wherein the substrate layer comprises molten vermiculite. 29 200931174 12. The template of claim 10, wherein the substrate layer comprises a plurality of recesses, and wherein the porous material is placed in the recesses. 13. The template of claim 10, wherein the cover layer comprises SiOx, and wherein l$xS2. 5 14. The template of claim 10, wherein one of the cover layers has a thickness of less than about 100 nanometers. 15. The template of claim 14, wherein one of the cover layers has a thickness of less than about 50 nanometers. 16. The template of claim 15 wherein one of the cover layers has a thickness of 10 less than about 20 nanometers. 17. The template of claim 10, further comprising a protrusion extending from the cover layer. 18. An embossed lithography embossed stack comprising a porous material defining a plurality of pores 15 having an average pore size of at least about 0.4 nm, wherein the porosity of the porous material is at least About 10%. 19. The embossed stack of claim 18, wherein the average pore size is at least about 0.5 nanometers. 20. The embossed stack of claim 18, wherein the average pore size is at least about 1.0 nanometer. The embossed stack of claim 18, wherein the porous material has a porosity of at least about 20%. 22. The template of claim 18, wherein the porous material is an organic acid salt low-k material. 23. The template of claim 22, wherein the porous material has a relative porosity of at least about 20% for one of the melted 200931174 molten vermiculite. 24. The embossed stack of claim 18, wherein the porous material has a Young's modulus of at least about 2 GPa. 25. The template of claim 18, wherein the porous material has a Young's modulus of less than about 5 GPa. 26. The template of claim 18, wherein the porous material has a Young's modulus of at least about 10 GPa. 27. The template of claim 18, wherein the porous material is disposed between a substrate layer and a cover layer. 10 28. A method of forming an imprint lithography template, the method comprising: forming a porous layer on a substrate layer, wherein the porous layer defines a plurality of pores having an average pore size of about 0.4 nm, And wherein one of the porous layers has a porosity of at least about 10%; and a cover layer is formed on the porous layer. 15 29. A method of forming an embossed lithography stack, the method comprising: forming a plurality of recesses in a substrate layer; depositing a porous material in the recesses, wherein the porous material defines A plurality of pores having an average pore size of at least about 0.4 nanometers, and wherein one of the porous materials has a porosity of at least about 10%; and 20 forming a coating layer on the substrate layer. 30. A method of forming an imprinted lithography stack, the method comprising: forming a porous layer on a substrate, wherein the porous layer defines a plurality of pores having an average pore size of at least about 0.4 nm, and Wherein one of the porous layers has a porosity of at least about 10%; and 31 200931174 forms a cover layer on the porous layer. 31. A lithography method comprising: applying a polymerizable material to an embossed stack; contacting the polymerizable material with a template, wherein the template comprises 5 a porous material defining a plurality of An aperture having an average pore size of at least about 0.4 nanometers, and wherein one of the porous materials has a porosity of at least about 10%; curing the polymerizable material; and separating the template from the cured material. 32. An embossing lithography method comprising: 10 applying a droplet of a polymerizable material to an embossed stack, wherein the embossed stack comprises a porous material defining a plurality of average pore sizes a pore of at least about 0.4 nm, and wherein one of the porous materials has a porosity of at least about 10%; contacting the polymerizable material with a template; 15 curing the polymerizable material; and subjecting the template to the template The solidified material is separated. 33. An embossing lithography method comprising: dispensing a droplet of a polymerizable material onto a surface of a porous embossed stack, wherein the porous embossed stack comprises a porous material 20, which defines a plurality of pores having an average pore size of at least about 0.4 nm, and wherein one of the porous materials has a porosity of at least about 10%; contacting the polymerizable material with a template; and the polymerizable material Dispersing to form a substantially continuous layer on the surface of the porous embossed stack, dispersing the polymerizable material to form a substantially continuous layer in the form of 200931174, similarly dispersing a similar polymerizable material for use in a second template as well 80% or less of the time required to form a substantially continuous layer between a second embossed stack, wherein the second stencil and the second embossed stack have an average pore size of less than about 0.4 nanometers. 5 34. An embossing lithography method comprising: applying a droplet of a polymerizable material to a surface of an embossed stack; contacting the polymerizable material with a template, wherein the template comprises a porous material defining a plurality of pores having an average pore size of at least about 0.4 nm, and wherein one of the porous materials has a porosity of at least about 10%; and enabling the polymerizable material to be dispersed so as to be at the pressure Forming a substantially continuous layer on the surface of the print stack, dispersing the polymerizable material to form a substantially continuous layer occurs by similarly spreading a similar polymerizable material to form a bond between a second template and a second stamp stack 80% or less of the time required to substantially continuate the layer, wherein the second template and the second embossed stack have an average pore size of less than about 0.4 nm. 33