US20050150404A1 - Hardened nano-imprinting stamp - Google Patents
Hardened nano-imprinting stamp Download PDFInfo
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- US20050150404A1 US20050150404A1 US11/065,171 US6517105A US2005150404A1 US 20050150404 A1 US20050150404 A1 US 20050150404A1 US 6517105 A US6517105 A US 6517105A US 2005150404 A1 US2005150404 A1 US 2005150404A1
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- nano
- hardened
- silicon
- sized features
- imprinting stamp
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C99/00—Subject matter not provided for in other groups of this subclass
- B81C99/0075—Manufacture of substrate-free structures
- B81C99/009—Manufacturing the stamps or the moulds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0017—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor for the production of embossing, cutting or similar devices; for the production of casting means
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the present invention relates generally to a structure and method of hardening a nano-imprinting stamp. More specifically, the present invention relates to a structure and method of hardening a nano-imprinting stamp using a plasma carburization and/or nitridation process.
- Nano-imprinting lithography is a promising technique for obtaining nano-size (as small as a few tens of nanometers) patterns.
- a key step in forming the nano-size patterns is to first form an imprinting stamp that includes a pattern that complements the nano-sized patterns that are to be imprinted by the stamp.
- a prior nano-imprint lithography process includes an imprinting stamp 200 having a plurality of imprint patterns 202 formed thereon.
- the imprint patterns 202 consists of a simple line and space pattern having a plurality of lines 204 separate by a plurality of spaces 206 between adjacent lines 204 .
- the imprint patterns 202 are carried by a substrate 211 .
- a thickness of the mask layer 203 is modulated with respect to the imprint patterns 202 (see FIG. 1 a ) such that the imprint patterns 202 are replicated in the mask layer 203 .
- the mask layer 203 is made from a material such as a polymer.
- a photoresist material can be used for the mask layer 203 .
- the mask layer 203 is deposited on a supporting substrate 205 .
- the imprinting stamp 200 is pressed repeatedly onto the mask layer 203 to replicate the imprint patterns 202 in the mask layer 203 and to cover the whole area of the mask layer 203 .
- the mask layer 203 includes a plurality of nano-size impressions 207 that complement the shape of the imprint patterns 202 .
- the mask layer 203 is anisotropically etched (i.e. a highly directional etch) to form nano-sized patterns 209 in the mask layer 203 .
- the supporting substrate 205 or another layer (not shown) positioned between the mask layer 203 and the supporting substrate 205 serves as an etch stop for the anisotropic etch.
- each line 204 includes opposed side surfaces 204 s , a top surface 204 t , opposed face surfaces 204 f , and edges 204 e .
- a space 206 separates each line 204 .
- the imprint stamp 200 is made from a material such as silicon (Si).
- the substrate 211 can be a silicon wafer and the line and space features ( 204 , 206 ) can be made from silicon (Si) or polysilicon ( ⁇ -Si). Silicon is the material of choice for nano-imprint stamps because there are well established microelectronics processes for manufacturing silicon based structures and circuits and silicon is readily available at a reasonable cost.
- one of the disadvantages of the prior imprint stamp 200 is that silicon is a soft material and is subject to breakage, damage, and wear from repeated pressing steps into the mask layer 203 .
- a section E-E of the line feature 204 is particularly subject to wear, damage, and breakage due to repeated pressing steps.
- an enlarged view of the section E-E of FIG. 4 illustrates that the edges 204 e , the top surface 204 t , the side surfaces 204 s , and the face surfaces 204 f are particularly susceptible to wear W from only a few pressing with the mask layer 203 .
- the imprint stamp 200 is pressed 201 into the mask layer 203 so that the line features 204 are disposed in the mask layer 203 .
- Repeated pressing steps cause wear, damage, and breakage denoted as W at the edges 204 e and the top surface 204 t of the line features 204 . Only ten or fewer pressing steps can result in the imprint stamp 200 wearing to the point where it can no longer be used to form consistent, repeatable, and accurate imprint patterns 209 .
- FIGS. 7 a and 7 b a more detailed view of the wear to the line features 204 illustrates that the wear is most severe along the edges 204 e and top surface 204 t as those portions of the line features 204 contact the mask layer 203 first and have surface features that are substantially normal to the direction of pressing 201 . Accordingly, as illustrated in FIGS. 8 a and 8 b , the line feature 204 quickly deteriorates from the ideal line feature 204 of FIG. 8 a to the wom out line features 204 of FIG. 8 b after only a few pressing cycles with the mask layer 203 .
- Fabrication of the imprint stamp 200 is one of the most crucial and most expensive steps in the entire imprinting lithography process.
- Another disadvantage of the prior imprint stamp 200 is that a cost of manufacturing the imprint stamp 200 is not recouped because the imprint stamp 200 is damaged and/or wears out before an adequate number of pressing steps required to justify the manufacturing cost of the imprint stamp 200 can occur. Accordingly, the prior imprint stamp 200 is not economical to manufacture.
- nano-size imprinting stamp that is resistant to wear, damage, and breakage.
- nano-size imprinting stamp that can retain consistent, repeatable, and accurate imprint patterns over multiple pressing cycles so that the cost of manufacturing the nano-size imprinting stamp is recovered.
- the hardened nano-imprinting stamp of the present invention solves the aforementioned disadvantages and limitations of the prior nano-imprinting stamps.
- the silicon-based hardened nano-imprinting stamp of the present invention is made stronger and tougher by a plasma carburization and/or nitridation process that forms a hardened shell of silicon carbide (SiC), silicon nitride (SiN), or silicon carbide nitride (SiCN) along the outer surface of the hardened nano-imprinting stamp.
- the plasma carburization and/or nitridation process easily converts the reactive silicon (Si) material of the hardened nano-imprinting stamp into silicon carbide (SiC), silicon nitride (SiN), or silicon carbide nitride (SiCN) resulting in a hardened nano-size imprinting stamp that is much stronger than prior imprinting stamps made only of silicon.
- the hardened nano-imprinting stamp has an increased lifetime and therefore the cost of manufacturing the hardened nano-imprinting stamp of the present invention can be recovered because the hardened nano-imprinting stamp can endure several more additional pressing cycles without wearing out, breaking, or being damaged, unlike the prior nano-imprinting stamps.
- FIGS. 1 a and 1 b are profile and top plan views respectively of a prior imprint stamp and prior imprint patterns.
- FIG. 2 is a profile view of a prior mask layer with nano-size impression formed therein by the prior imprint stamp of FIG. 1 a.
- FIG. 3 is a profile view of the prior mask layer of FIG. 2 after an anisotropic etch step.
- FIGS. 4 and 5 are a cross-sectional and profile views respectively that depict portions of a prior imprint stamp that are most susceptible to wear, breakage, or damage.
- FIG. 6 is a cross-sectional view depicting a prior imprint stamp pressed into a mask layer.
- FIGS. 7 a and 7 b depict wear to the prior imprint stamp resulting from the pressing step of FIG. 6 .
- FIGS. 8 a and 8 b depict the rapid progression of wear to the prior imprint stamp after only a few pressing cycles.
- FIG. 9 is a profile view of a nano-imprinting stamp including a plurality of nano-sized features before a hardening process according to the present invention.
- FIG. 10 a is a profile view depicting exposed edges and surfaces of the nano-sized features of FIG. 9 .
- FIG. 10 b is a cross-sectional view depicting a plasma hardening process for hardening the exposed edges and surfaces of FIG. 10 a according to the present invention.
- FIG. 11 is a cross-sectional view of a hardened shell of a hardened nano-imprinting stamp according to the present invention.
- FIGS. 12 a and 12 b are schematic views depicting a plasma carburization process for forming a hardened shell according to the present invention.
- FIGS. 13 a and 13 b are schematic views depicting a plasma nitridation process for forming a hardened shell according to the present invention.
- FIG. 14 is a cross-sectional view depicting a hardened nano-imprinting stamp pressed into contact with a mask layer according to the present invention.
- FIGS. 15 a and 15 b are schematic views depicting a plasma carburization process and a plasma nitridation process for forming a hardened shell according to the present invention.
- FIG. 16 is a profile view of a hardened nano-imprinting stamp including a plurality of hardened nano-sized features according to the present invention.
- the present invention is embodied in a hardened nano-imprinting stamp and a method of making a hardened nano-imprinting stamp.
- the hardened nano-imprinting stamp comprises a plurality of silicon based nano-sized features that include a hardened shell formed by a plasma carburization and/or a plasma nitridation process.
- a plasma with a gas comprising carbon and/or nitrogen bombards exposed surfaces of the nano-sized features and penetrates those surfaces to react with the silicon to form a silicon carbide, a silicon nitride, or a silicon carbide nitride material.
- the nano-sized features have a hardened outer shell (i.e. a hardened crust) that makes the nano-sized features more resilient to wear and damage due to repeated pressing cycles with a media to be imprinted by the nano-imprinting stamp.
- the hardened nano-imprinting stamp of the present invention is cost effective because the hardened nano-sized features are durable and therefore have a longer service life that allows for the cost of manufacturing the hardened nano-imprinting stamp to be recovered before the service life has ended.
- the hardened nano-imprinting stamp of the present invention is more accurate than the prior nano-imprinting stamps because the hardened nano-sized features are more durable and maintain their imprint profiles over repeated pressing cycles with the media to be imprinted.
- a substrate 11 includes a base surface 13 and a plurality of nano-sized features 12 that are in contact with the substrate 11 and extend outward of the base surface 13 .
- the substrate 11 can be made from a material including but not limited to silicon (Si), single crystal silicon, polysilicon ( ⁇ -Si), silicon oxide (SiO 2 ), and silicon nitride (SiN x ).
- the substrate 11 can be a wafer of single crystal silicon such as the type commonly used for the fabrication of microelectronic devices and structures.
- the nano-sized features 12 have dimensions (i.e. a width W and a height h) that are typically in a range of about 1.0 ⁇ m or less.
- a length L of the nano-sized features 12 may also be about 1.0 ⁇ m or less. Dimensions of a few hundred nanometers or less are desirable.
- the nano-sized features 12 can be made from a silicon-based material including but not limited to silicon (Si) and polysilicon ( ⁇ -Si).
- the nano-sized features 12 can be formed by depositing a layer of polysilicon (not shown) on the base surface 13 of the substrate 11 followed by lithographically patterning the layer of polysilicon with a mask layer and then etching through the mask layer to form the nano-sized features 12 of polysilicon.
- the nano-sized features 12 include an outer surface that defines an imprint profile.
- the nano-sized features 12 have an outer surface that defines a rectangular imprint profile. Accordingly, when the substrate 11 is pressed into contact with a media to be imprinted (not shown) the imprint profile of the nano-sized features 12 is transferred to the media.
- the imprint profile of the nano-sized features 12 will be application dependent and the present invention is not limited by the imprint profiles of the nano-sized features 12 as illustrated herein.
- the outer surfaces of the nano-sized features 12 includes opposed side surfaces 128 , a top surface 12 t , a front surface 12 f , a back surface 12 b , edge surfaces 12 e , and the base surface 13 . All of the aforementioned surfaces can be exposed surfaces that are subject to wear, damage, or breakage resulting from one or more pressing cycles in a nano-imprint lithography process.
- the edge surfaces 12 e are particularly susceptible to wear and damage.
- the nano-sized features 12 are spaced apart from one another by a spacing S that can vary among the nano-sized features 12 . That spacing S is also transferred to the media in which the nano-sized features 12 are imprinted. Accordingly, wear to the side surfaces 12 s will cause the spacing S to increase thereby reducing the accuracy of the imprint. Wear or damage to the base surface 13 can also result in a reduction in accuracy of the imprint.
- the imprint profile and the accuracy of the imprint made by the nano-sized features 12 depends on the mechanical stability (i.e. toughness) of the exposed surfaces and edges.
- the aforementioned outer surfaces ( 12 s , 12 e , 12 t , 12 ′, 12 b ) of the nano-sized features 12 and the base surface 13 are exposed to a plasma P.
- the plasma P bombards those surfaces and atoms of a material in the plasma P penetrates those surfaces to a predetermined depth d.
- the atoms of carbon (C) and/or nitrogen (N 2 ) can penetrate the exposed surfaces through a mechanism such a diffusion, for example.
- the plasma P comprises a gas that includes carbon (C) for a plasma carburization process, nitrogen (N 2 ) for a plasma nitridation process, and carbon (C) and nitrogen (N 2 ) for a plasma carburization and nitridation process.
- the predetermined depth d can vary along the aforementioned surfaces and need not be equal along all of the surfaces.
- the predetermined depth d may be greater (i.e deeper) on the top surface 12 t and base surface 13 than it is on the side surfaces 12 s.
- a hardened nano-imprinting stamp 10 results from the plasma carburization process, plasma nitridation process, or plasma carburization and nitridation processes.
- the nano-sized features 12 include a hardened shell 20 that extends inward of the outer surface to the predetermined depth d.
- the hardened shell 20 comprises silicon carbide (SiC) when the plasma process is the plasma carburization process.
- the hardened shell 20 comprises silicon nitride (SiN) when the plasma process is the plasma nitridation process. If both the plasma earburization process and the plasma nitridation process are used, then the hardened shell 20 comprises silicon carbide nitride (SiCN).
- the resulting silicon carbide hardened shell 20 , silicon nitride hardened shell 20 , or silicon carbide nitride hardened shell 20 is harder and more resilient to wear, damage, and breakage than an underlying core of softer silicon-based material that lies beneath the hardened shell 20 of the nano-sized features 12 .
- the hardened shell 20 forms an outrer hardened crust of SiC, SiN, or SiCN that surrounds an underlying core of the softer silicon (Si) based material. Consequently, the imprint profile of the nano-sized features 12 is maintained after repeated engagements of the hardened nano-imprinting stamp 10 with a media that is to be imprinted by the hardened nano-imprinting stamp 10 .
- the predetermined depth d will be application dependent and can be determined by factors that include processing time and temperature, just to name a few.
- the predetermined depth d is small relative to the dimensions of the nano-sized features 12 .
- a width dimension of the nano-sized features 12 can be on the order of a few hundred nanometers.
- the predetermined depth d can be on the order of a few hundred angstroms ( ⁇ ).
- the predetermined depth d of the hardened shell 20 can be in a range from about 10.0 ⁇ to about 300.0 ⁇ .
- the predetermined depth d is not to be construed as being limited to that range, and as was stated above, the predetermined depth d is application specific.
- the hardened nano-imprinting stamp 10 is pressed into contact with an imprint target 50 that includes a support substrate 51 and an imprint media 53 .
- the imprint media 53 can be made from a variety of materials.
- the imprint media 53 can be a polymer such as a photoresist material used for photolithography.
- the nano-sized features 12 of the hardened nano-imprinting stamp 10 are pressed into the imprint media 53 to form an imprint that complements the imprint profiles of the nano-sized features 12 .
- the aforementioned exposed surfaces are in contact C P with the imprint media 53 and those points of contact C P are resistant to wear and damage due to the hardened shell 20 .
- the surfaces of the hardened nano-imprinting stamp 10 that will come into contact with the imprint media 53 are hardened against wear and damage, as is illustrated in FIG. 16 , where the exposed surfaces ( 12 s , 12 e , 12 t , 12 f , 12 b shown in cross-hatched line) of the nano-sized features 12 and the base surface 13 include the hardened shell 20 . Because wearing out of the nano-sized features 12 is closely related with a hardness of the material for the nano-sized features 12 , a useful lifetime of the hardened nano-imprinting stamp 10 of the present invention can be increased by a factor of ten or more.
- FIGS. 12 a and 12 b illustrate a method of hardening a nano-imprinting stamp 10 using a plasm carburization process.
- the nano-imprinting stamp 10 includes a plurality of silicon-based nano-sized features 12 that are carried by a substrate 11 .
- the nano-sized features 12 include a plurality of exposed surfaces (see 12 s , 12 e , 12 t , 12 f , 12 b , and 13 in FIGS. 10 a and 10 b ).
- the nano-sized features 12 can be made from a material including but not limited to silicon (Si) and polysilicon ( ⁇ -Si).
- the nano-sized features 12 are carburized in a plasma that includes a carbon (C) containing gas (denoted as an encircled C in FIG. 12 a ).
- a carbon (C) containing gas denoted as an encircled C in FIG. 12 a ).
- atoms of the carbon C bombard the exposed surfaces and penetrate into those surfaces.
- the atoms of the carbon C chemically react with the silicon of the nano-sized features 12 to form silicon carbide (SiC).
- the carburizing continues until a hardened shell 20 of silicon carbide (SiC) forms on the exposed surfaces and extends inward of those surfaces to the predetermined depth d. Resulting is the hardened nano-imprinting stamp 10 described above in reference to FIGS. 11, 14 , and 16 .
- SiC silicon carbide
- the carbon containing gas can be a hydrocarbon including but not limited to methane (CH 4 ) and ethane (C 2 H 6 ).
- the plasma carburization process can occur at a temperature in a range from about 300° C. to about 900° C.
- FIGS. 13 a and 13 b illustrate a method of hardening a nano-imprinting stamp 10 using a plasma nitridation process.
- the nano-imprinting stamp 10 includes a plurality of silicon-based nano-sized features 12 that are carried by a substrate 11 .
- the nano-sized features 12 include a plurality of exposed surfaces (see 12 s , 12 e , 12 t , 12 f , 12 b , and 13 in FIGS. 10 a and 10 b ).
- the nano-sized features 12 can be made from a material including but not limited to silicon (Si) and polysilicon ( ⁇ -Si).
- the nano-sized features 12 are nitridized in a plasma that includes a nitrogen (N 2 ) containing gas (denoted as an encircled N in FIG. 13 a ).
- a nitrogen (N 2 ) containing gas denoted as an encircled N in FIG. 13 a ).
- atoms of the nitrogen N bombard the exposed surfaces and penetrate into those surfaces.
- the atoms of the nitrogen N chemically react with the silicon of the nano-sized features 12 to form silicon nitride (SiN).
- nitridizing continues until a hardened shell 20 of silicon nitride forms on the exposed surfaces and extends inward of those surfaces to the predetermined depth d. Resulting is the hardened nano-imprinting stamp 10 described above in reference to FIGS. 11, 14 , and 16 .
- the nitrogen containing gas can be a material including but not limited to nitrogen (N 2 ) or ammonia (NH 3 ).
- the plasma nitridation process can occur at a temperature including but not limited to room temperature (i.e. 25° C.) or a temperature that is above room temperature.
- FIGS. 15 a and 15 b illustrate a method of hardening a nano-imprinting stamp 10 using a plasma carburization process and a plasma nitridation process.
- the nano-imprinting stamp 10 includes a plurality of silicon-based nano-sized features 12 that are carried by a substrate 11 .
- the nano-sized features 12 include a plurality of exposed surfaces (see 12 s , 12 e , 12 t , 12 f , 12 b , and 13 in FIGS. 10 a and 10 b ).
- the nano-sized features 12 can be made from a material including but not limited to silicon (Si) and polysilicon ( ⁇ -Si).
- the nano-sized features 12 are carburized in a plasma that includes a carbon (C) containing gas (denoted as an encircled C in FIG. 15 a ) and nitridized in a plasma that includes a nitrogen (N 2 ) containing gas (denoted as an encircled N in FIG. 15 a ).
- a carbon (C) containing gas denoted as an encircled C in FIG. 15 a
- N 2 nitrogen
- FIG. 15 b atoms of the carbon C and the nitrogen N bombard the exposed surfaces and penetrate into those surfaces.
- the atoms of the carbon C and nitrogen N chemically react with the silicon of the nano-sized features 12 to form silicon carbide nitride (SiCN).
- the carburizing and nitridizing continues until a hardened shell 20 of silicon carbide nitride (SiCN) forms on the exposed surfaces and extends inward of those surfaces to the predetermined depth d. Resulting is the hardened nano-imprinting stamp 10 described above in reference to FIGS. 11, 14 , and 16 .
- SiCN silicon carbide nitride
- the carbon containing gas can be a hydrocarbon including but not limited to methane (CH 4 ) and ethane (C 2 H 6 ).
- the plasma carburization process can occur at an elevated temperature in a range from about 300° C. to about 900° C.
- the nitrogen containing gas can be a material including but not limited to nitrogen (N 2 ) or ammonia (NH 3 ).
- the plasma nitridation process can occur at a temperature including but not limited to room temperature (i.e. 25° C.) or a temperature that is above room temperature.
- the plasma carburization process can occur first followed by the plasma nitridation process or vice-versa.
- the plasma carburization process and the plasma nitridation process can occur substantially at the same time in a plasma that includes a carbon (C) containing gas and a nitrogen (N 2 ) containing gas.
- Those gasses (C, N 2 ) can be mixed together (i.e. premixed) before introduction into a chamber in which the plasma carburization and plasma nitridation will occur.
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Abstract
A hardened nano-imprinting stamp and a method of forming a hardened nano-imprinting stamp are disclosed. The hardened nano-imprinting stamp includes a plurality of silicon-based nano-sized features that have an hardened shell of silicon carbide, silicon nitride, or silicon carbide nitride. The hardened shell is made harder than the underlying silicon by a plasma carburization and/or a plasma nitridation process. During the plasma process atoms of carbon and/or nitrogen bombard and penetrate a plurality of exposed surfaces of the nano-sized features and chemically react with the silicon to form the hardened shell of silicon carbide, silicon nitride, or silicon carbide nitride. The lifetime, durability, economy, and accuracy of the resulting hardened nano-imprinting stamp are improved.
Description
- The present invention relates generally to a structure and method of hardening a nano-imprinting stamp. More specifically, the present invention relates to a structure and method of hardening a nano-imprinting stamp using a plasma carburization and/or nitridation process.
- Nano-imprinting lithography is a promising technique for obtaining nano-size (as small as a few tens of nanometers) patterns. A key step in forming the nano-size patterns is to first form an imprinting stamp that includes a pattern that complements the nano-sized patterns that are to be imprinted by the stamp.
- In
FIG. 1 a, a prior nano-imprint lithography process includes animprinting stamp 200 having a plurality ofimprint patterns 202 formed thereon. InFIG. 1 b, theimprint patterns 202 consists of a simple line and space pattern having a plurality oflines 204 separate by a plurality ofspaces 206 betweenadjacent lines 204. Theimprint patterns 202 are carried by asubstrate 211. By pressing (see dashed arrow 201) theimprinting stamp 200 into a specially designedmask layer 203, a thickness of themask layer 203 is modulated with respect to the imprint patterns 202 (seeFIG. 1 a) such that theimprint patterns 202 are replicated in themask layer 203. - Typically, the
mask layer 203 is made from a material such as a polymer. For instance, a photoresist material can be used for themask layer 203. Themask layer 203 is deposited on a supportingsubstrate 205. Using a step and repeat process, theimprinting stamp 200 is pressed repeatedly onto themask layer 203 to replicate theimprint patterns 202 in themask layer 203 and to cover the whole area of themask layer 203. - In
FIG. 2 , after the step and repeat process, themask layer 203 includes a plurality of nano-size impressions 207 that complement the shape of theimprint patterns 202. Next, inFIG. 3 , themask layer 203 is anisotropically etched (i.e. a highly directional etch) to form nano-sized patterns 209 in themask layer 203. Typically, the supportingsubstrate 205 or another layer (not shown) positioned between themask layer 203 and the supportingsubstrate 205 serves as an etch stop for the anisotropic etch. - In
FIG. 4 , eachline 204 includesopposed side surfaces 204 s, atop surface 204 t, opposedface surfaces 204 f, andedges 204 e. Aspace 206 separates eachline 204. Typically, theimprint stamp 200 is made from a material such as silicon (Si). For example, thesubstrate 211 can be a silicon wafer and the line and space features (204, 206) can be made from silicon (Si) or polysilicon (α-Si). Silicon is the material of choice for nano-imprint stamps because there are well established microelectronics processes for manufacturing silicon based structures and circuits and silicon is readily available at a reasonable cost. - However, one of the disadvantages of the
prior imprint stamp 200 is that silicon is a soft material and is subject to breakage, damage, and wear from repeated pressing steps into themask layer 203. InFIG. 4 , a section E-E of theline feature 204 is particularly subject to wear, damage, and breakage due to repeated pressing steps. InFIG. 5 , an enlarged view of the section E-E ofFIG. 4 illustrates that theedges 204 e, thetop surface 204 t, theside surfaces 204 s, and theface surfaces 204 f are particularly susceptible to wear W from only a few pressing with themask layer 203. - In
FIG. 6 , theimprint stamp 200 is pressed 201 into themask layer 203 so that theline features 204 are disposed in themask layer 203. Repeated pressing steps cause wear, damage, and breakage denoted as W at theedges 204 e and thetop surface 204 t of the line features 204. Only ten or fewer pressing steps can result in theimprint stamp 200 wearing to the point where it can no longer be used to form consistent, repeatable, andaccurate imprint patterns 209. - In
FIGS. 7 a and 7 b, a more detailed view of the wear to theline features 204 illustrates that the wear is most severe along theedges 204 e andtop surface 204 t as those portions of the line features 204 contact themask layer 203 first and have surface features that are substantially normal to the direction of pressing 201. Accordingly, as illustrated inFIGS. 8 a and 8 b, theline feature 204 quickly deteriorates from theideal line feature 204 ofFIG. 8 a to the wom out line features 204 ofFIG. 8 b after only a few pressing cycles with themask layer 203. - Fabrication of the
imprint stamp 200 is one of the most crucial and most expensive steps in the entire imprinting lithography process. Another disadvantage of theprior imprint stamp 200 is that a cost of manufacturing theimprint stamp 200 is not recouped because theimprint stamp 200 is damaged and/or wears out before an adequate number of pressing steps required to justify the manufacturing cost of theimprint stamp 200 can occur. Accordingly, theprior imprint stamp 200 is not economical to manufacture. - Consequently, there exists a need for a nano-size imprinting stamp that is resistant to wear, damage, and breakage. There is also an unmet need for a nano-size imprinting stamp that can retain consistent, repeatable, and accurate imprint patterns over multiple pressing cycles so that the cost of manufacturing the nano-size imprinting stamp is recovered.
- The hardened nano-imprinting stamp of the present invention solves the aforementioned disadvantages and limitations of the prior nano-imprinting stamps. The silicon-based hardened nano-imprinting stamp of the present invention is made stronger and tougher by a plasma carburization and/or nitridation process that forms a hardened shell of silicon carbide (SiC), silicon nitride (SiN), or silicon carbide nitride (SiCN) along the outer surface of the hardened nano-imprinting stamp. The plasma carburization and/or nitridation process easily converts the reactive silicon (Si) material of the hardened nano-imprinting stamp into silicon carbide (SiC), silicon nitride (SiN), or silicon carbide nitride (SiCN) resulting in a hardened nano-size imprinting stamp that is much stronger than prior imprinting stamps made only of silicon.
- The hardened nano-imprinting stamp has an increased lifetime and therefore the cost of manufacturing the hardened nano-imprinting stamp of the present invention can be recovered because the hardened nano-imprinting stamp can endure several more additional pressing cycles without wearing out, breaking, or being damaged, unlike the prior nano-imprinting stamps.
- Other aspects and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, illustrating by way of example the principles of the present invention.
-
FIGS. 1 a and 1 b are profile and top plan views respectively of a prior imprint stamp and prior imprint patterns. -
FIG. 2 is a profile view of a prior mask layer with nano-size impression formed therein by the prior imprint stamp ofFIG. 1 a. -
FIG. 3 is a profile view of the prior mask layer ofFIG. 2 after an anisotropic etch step. -
FIGS. 4 and 5 are a cross-sectional and profile views respectively that depict portions of a prior imprint stamp that are most susceptible to wear, breakage, or damage. -
FIG. 6 is a cross-sectional view depicting a prior imprint stamp pressed into a mask layer. -
FIGS. 7 a and 7 b depict wear to the prior imprint stamp resulting from the pressing step ofFIG. 6 . -
FIGS. 8 a and 8 b depict the rapid progression of wear to the prior imprint stamp after only a few pressing cycles. -
FIG. 9 is a profile view of a nano-imprinting stamp including a plurality of nano-sized features before a hardening process according to the present invention. -
FIG. 10 a is a profile view depicting exposed edges and surfaces of the nano-sized features ofFIG. 9 . -
FIG. 10 b is a cross-sectional view depicting a plasma hardening process for hardening the exposed edges and surfaces ofFIG. 10 a according to the present invention. -
FIG. 11 is a cross-sectional view of a hardened shell of a hardened nano-imprinting stamp according to the present invention. -
FIGS. 12 a and 12 b are schematic views depicting a plasma carburization process for forming a hardened shell according to the present invention. -
FIGS. 13 a and 13 b are schematic views depicting a plasma nitridation process for forming a hardened shell according to the present invention. -
FIG. 14 is a cross-sectional view depicting a hardened nano-imprinting stamp pressed into contact with a mask layer according to the present invention. -
FIGS. 15 a and 15 b are schematic views depicting a plasma carburization process and a plasma nitridation process for forming a hardened shell according to the present invention. -
FIG. 16 is a profile view of a hardened nano-imprinting stamp including a plurality of hardened nano-sized features according to the present invention. - In the following detailed description and in the several figures of the drawings, like elements are identified with like reference numerals.
- As shown in the drawings for purpose of illustration, the present invention is embodied in a hardened nano-imprinting stamp and a method of making a hardened nano-imprinting stamp. The hardened nano-imprinting stamp comprises a plurality of silicon based nano-sized features that include a hardened shell formed by a plasma carburization and/or a plasma nitridation process. A plasma with a gas comprising carbon and/or nitrogen bombards exposed surfaces of the nano-sized features and penetrates those surfaces to react with the silicon to form a silicon carbide, a silicon nitride, or a silicon carbide nitride material. The atoms of carbon and/or nitrogen only penetrate the exposed surfaces to a finite depth so that only a portion of the silicon along the exposed surfaces is converted into an outer shell of the silicon carbide, silicon nitride, or the silicon carbide nitride material. As a result, the nano-sized features have a hardened outer shell (i.e. a hardened crust) that makes the nano-sized features more resilient to wear and damage due to repeated pressing cycles with a media to be imprinted by the nano-imprinting stamp.
- The hardened nano-imprinting stamp of the present invention is cost effective because the hardened nano-sized features are durable and therefore have a longer service life that allows for the cost of manufacturing the hardened nano-imprinting stamp to be recovered before the service life has ended.
- Additionally, the hardened nano-imprinting stamp of the present invention is more accurate than the prior nano-imprinting stamps because the hardened nano-sized features are more durable and maintain their imprint profiles over repeated pressing cycles with the media to be imprinted.
- In
FIG. 9 , prior to a hardening process that will be described below, asubstrate 11 includes abase surface 13 and a plurality of nano-sized features 12 that are in contact with thesubstrate 11 and extend outward of thebase surface 13. Thesubstrate 11 can be made from a material including but not limited to silicon (Si), single crystal silicon, polysilicon (α-Si), silicon oxide (SiO2), and silicon nitride (SiNx). For example, thesubstrate 11 can be a wafer of single crystal silicon such as the type commonly used for the fabrication of microelectronic devices and structures. - The nano-
sized features 12 have dimensions (i.e. a width W and a height h) that are typically in a range of about 1.0 μm or less. A length L of the nano-sized features 12 may also be about 1.0 μm or less. Dimensions of a few hundred nanometers or less are desirable. The nano-sized features 12 can be made from a silicon-based material including but not limited to silicon (Si) and polysilicon (α-Si). For example, using well understood microelectronics processing techniques, the nano-sized features 12 can be formed by depositing a layer of polysilicon (not shown) on thebase surface 13 of thesubstrate 11 followed by lithographically patterning the layer of polysilicon with a mask layer and then etching through the mask layer to form the nano-sized features 12 of polysilicon. - The nano-
sized features 12 include an outer surface that defines an imprint profile. For instance, inFIG. 9 , the nano-sized features 12 have an outer surface that defines a rectangular imprint profile. Accordingly, when thesubstrate 11 is pressed into contact with a media to be imprinted (not shown) the imprint profile of the nano-sized features 12 is transferred to the media. The imprint profile of the nano-sized features 12 will be application dependent and the present invention is not limited by the imprint profiles of the nano-sized features 12 as illustrated herein. - In
FIG. 10 a, the outer surfaces of the nano-sized features 12 includes opposed side surfaces 128, atop surface 12 t, afront surface 12 f, aback surface 12 b, edge surfaces 12 e, and thebase surface 13. All of the aforementioned surfaces can be exposed surfaces that are subject to wear, damage, or breakage resulting from one or more pressing cycles in a nano-imprint lithography process. - The edge surfaces 12 e are particularly susceptible to wear and damage. Moreover, the nano-
sized features 12 are spaced apart from one another by a spacing S that can vary among the nano-sized features 12. That spacing S is also transferred to the media in which the nano-sized features 12 are imprinted. Accordingly, wear to the side surfaces 12 s will cause the spacing S to increase thereby reducing the accuracy of the imprint. Wear or damage to thebase surface 13 can also result in a reduction in accuracy of the imprint. Essentially, the imprint profile and the accuracy of the imprint made by the nano-sized features 12 depends on the mechanical stability (i.e. toughness) of the exposed surfaces and edges. - In
FIG. 10 b, the aforementioned outer surfaces (12 s, 12 e, 12 t, 12′, 12 b) of the nano-sized features 12 and thebase surface 13 are exposed to a plasma P. The plasma P bombards those surfaces and atoms of a material in the plasma P penetrates those surfaces to a predetermined depth d. The atoms of carbon (C) and/or nitrogen (N2) can penetrate the exposed surfaces through a mechanism such a diffusion, for example. The plasma P comprises a gas that includes carbon (C) for a plasma carburization process, nitrogen (N2) for a plasma nitridation process, and carbon (C) and nitrogen (N2) for a plasma carburization and nitridation process. Accordingly, either carbon atoms and/or nitrogen atoms penetrate those surfaces to the predetermined depth d and chemically react with the material of the nano-sized features 12. The predetermined depth d can vary along the aforementioned surfaces and need not be equal along all of the surfaces. For example, the predetermined depth d may be greater (i.e deeper) on thetop surface 12 t andbase surface 13 than it is on the side surfaces 12 s. - In
FIG. 11 , a hardened nano-imprinting stamp 10 results from the plasma carburization process, plasma nitridation process, or plasma carburization and nitridation processes. As a result of those plasma processes, the nano-sized features 12 include ahardened shell 20 that extends inward of the outer surface to the predetermined depth d. Thehardened shell 20 comprises silicon carbide (SiC) when the plasma process is the plasma carburization process. Conversely, thehardened shell 20 comprises silicon nitride (SiN) when the plasma process is the plasma nitridation process. If both the plasma earburization process and the plasma nitridation process are used, then thehardened shell 20 comprises silicon carbide nitride (SiCN). The resulting silicon carbide hardenedshell 20, silicon nitride hardenedshell 20, or silicon carbide nitride hardenedshell 20 is harder and more resilient to wear, damage, and breakage than an underlying core of softer silicon-based material that lies beneath thehardened shell 20 of the nano-sized features 12. Essentially, thehardened shell 20 forms an outrer hardened crust of SiC, SiN, or SiCN that surrounds an underlying core of the softer silicon (Si) based material. Consequently, the imprint profile of the nano-sized features 12 is maintained after repeated engagements of the hardened nano-imprinting stamp 10 with a media that is to be imprinted by the hardened nano-imprinting stamp 10. - The predetermined depth d will be application dependent and can be determined by factors that include processing time and temperature, just to name a few. The predetermined depth d is small relative to the dimensions of the nano-
sized features 12. For example, a width dimension of the nano-sized features 12 (see D1 and D2 inFIG. 11 ) can be on the order of a few hundred nanometers. On the other hand, the predetermined depth d can be on the order of a few hundred angstroms (Å). The predetermined depth d of thehardened shell 20 can be in a range from about 10.0 Å to about 300.0 Å. However, for the embodiments described herein, the predetermined depth d is not to be construed as being limited to that range, and as was stated above, the predetermined depth d is application specific. - In
FIG. 14 , the hardened nano-imprinting stamp 10 is pressed into contact with animprint target 50 that includes asupport substrate 51 and animprint media 53. Theimprint media 53 can be made from a variety of materials. For example, theimprint media 53 can be a polymer such as a photoresist material used for photolithography. The nano-sized features 12 of the hardened nano-imprinting stamp 10 are pressed into theimprint media 53 to form an imprint that complements the imprint profiles of the nano-sized features 12. The aforementioned exposed surfaces are in contact CP with theimprint media 53 and those points of contact CP are resistant to wear and damage due to thehardened shell 20. - Accordingly, the surfaces of the hardened nano-
imprinting stamp 10 that will come into contact with theimprint media 53 are hardened against wear and damage, as is illustrated inFIG. 16 , where the exposed surfaces (12 s, 12 e, 12 t, 12 f, 12 b shown in cross-hatched line) of the nano-sized features 12 and thebase surface 13 include thehardened shell 20. Because wearing out of the nano-sized features 12 is closely related with a hardness of the material for the nano-sized features 12, a useful lifetime of the hardened nano-imprinting stamp 10 of the present invention can be increased by a factor of ten or more. -
FIGS. 12 a and 12 b illustrate a method of hardening a nano-imprinting stamp 10 using a plasm carburization process. InFIG. 12 a, the nano-imprinting stamp 10 includes a plurality of silicon-based nano-sized features 12 that are carried by asubstrate 11. The nano-sized features 12 include a plurality of exposed surfaces (see 12 s, 12 e, 12 t, 12 f, 12 b, and 13 inFIGS. 10 a and 10 b). The nano-sized features 12 can be made from a material including but not limited to silicon (Si) and polysilicon (α-Si). - The nano-
sized features 12 are carburized in a plasma that includes a carbon (C) containing gas (denoted as an encircled C inFIG. 12 a). InFIG. 12 b, atoms of the carbon C bombard the exposed surfaces and penetrate into those surfaces. The atoms of the carbon C chemically react with the silicon of the nano-sized features 12 to form silicon carbide (SiC). - The carburizing continues until a
hardened shell 20 of silicon carbide (SiC) forms on the exposed surfaces and extends inward of those surfaces to the predetermined depth d. Resulting is the hardened nano-imprinting stamp 10 described above in reference toFIGS. 11, 14 , and 16. - The carbon containing gas can be a hydrocarbon including but not limited to methane (CH4) and ethane (C2H6). The plasma carburization process can occur at a temperature in a range from about 300° C. to about 900° C.
- Similarly,
FIGS. 13 a and 13 b illustrate a method of hardening a nano-imprinting stamp 10 using a plasma nitridation process. InFIG. 13 a, the nano-imprinting stamp 10 includes a plurality of silicon-based nano-sized features 12 that are carried by asubstrate 11. The nano-sized features 12 include a plurality of exposed surfaces (see 12 s, 12 e, 12 t, 12 f, 12 b, and 13 inFIGS. 10 a and 10 b). The nano-sized features 12 can be made from a material including but not limited to silicon (Si) and polysilicon (α-Si). - The nano-
sized features 12 are nitridized in a plasma that includes a nitrogen (N2) containing gas (denoted as an encircled N inFIG. 13 a). InFIG. 13 b, atoms of the nitrogen N bombard the exposed surfaces and penetrate into those surfaces. The atoms of the nitrogen N chemically react with the silicon of the nano-sized features 12 to form silicon nitride (SiN). - The nitridizing continues until a
hardened shell 20 of silicon nitride forms on the exposed surfaces and extends inward of those surfaces to the predetermined depth d. Resulting is the hardened nano-imprinting stamp 10 described above in reference toFIGS. 11, 14 , and 16. - The nitrogen containing gas can be a material including but not limited to nitrogen (N2) or ammonia (NH3). The plasma nitridation process can occur at a temperature including but not limited to room temperature (i.e. 25° C.) or a temperature that is above room temperature.
-
FIGS. 15 a and 15 b illustrate a method of hardening a nano-imprinting stamp 10 using a plasma carburization process and a plasma nitridation process. In FIG. 15 a, the nano-imprinting stamp 10 includes a plurality of silicon-based nano-sized features 12 that are carried by asubstrate 11. The nano-sized features 12 include a plurality of exposed surfaces (see 12 s, 12 e, 12 t, 12 f, 12 b, and 13 inFIGS. 10 a and 10 b). The nano-sized features 12 can be made from a material including but not limited to silicon (Si) and polysilicon (α-Si). - The nano-
sized features 12 are carburized in a plasma that includes a carbon (C) containing gas (denoted as an encircled C inFIG. 15 a) and nitridized in a plasma that includes a nitrogen (N2) containing gas (denoted as an encircled N inFIG. 15 a). InFIG. 15 b, atoms of the carbon C and the nitrogen N bombard the exposed surfaces and penetrate into those surfaces. The atoms of the carbon C and nitrogen N chemically react with the silicon of the nano-sized features 12 to form silicon carbide nitride (SiCN). The carburizing and nitridizing continues until ahardened shell 20 of silicon carbide nitride (SiCN) forms on the exposed surfaces and extends inward of those surfaces to the predetermined depth d. Resulting is the hardened nano-imprinting stamp 10 described above in reference toFIGS. 11, 14 , and 16. - The carbon containing gas can be a hydrocarbon including but not limited to methane (CH4) and ethane (C2H6). The plasma carburization process can occur at an elevated temperature in a range from about 300° C. to about 900° C. The nitrogen containing gas can be a material including but not limited to nitrogen (N2) or ammonia (NH3). The plasma nitridation process can occur at a temperature including but not limited to room temperature (i.e. 25° C.) or a temperature that is above room temperature. The plasma carburization process can occur first followed by the plasma nitridation process or vice-versa. The plasma carburization process and the plasma nitridation process can occur substantially at the same time in a plasma that includes a carbon (C) containing gas and a nitrogen (N2) containing gas. Those gasses (C, N2) can be mixed together (i.e. premixed) before introduction into a chamber in which the plasma carburization and plasma nitridation will occur.
- Although several embodiments of the present invention have been disclosed and illustrated, the invention is not limited to the specific forms or arrangements of parts so described and illustrated. The invention is only limited by the claims.
Claims (4)
1. A hardened nano-imprinting stamp, comprising:
a substrate including a base surface;
a plurality of nano-sized features connected with the substrate and extending outward of the base surface, the nano-sized features including an outer surface defining an imprint profile, and the nano-sized features are made from a material selected from the group consisting of silicon and polysilicon; and
a hardened shell extending inward of the outer surface by a predetermined depth, the hardened shell is made from a material selected from the group consisting of silicon carbide, silicon nitride, and silicon carbide nitride, and
the hardened shell is operative to maintain the imprint profile of the nano-sized features over repeated engagements of the nano-imprinting stamp with a media to be imprinted.
2. The hardened nano-imprinting stamp as set forth in claim 1 , wherein the substrate comprises silicon.
3. The hardened nano-imprinting stamp as set forth in claim 1 , wherein the predetermined depth is in a range from about 10.0 angstroms to about 300.0 angstroms.
4-20. (canceled)
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KR20180105433A (en) * | 2017-03-15 | 2018-09-28 | 주식회사 기가레인 | Apparatus and method for imprinting |
KR102206492B1 (en) * | 2019-11-04 | 2021-01-22 | 주식회사 기가레인 | Transfer apparatus and method of manufacturing a transferred wafer using the same |
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- 2003-06-24 CN CNA031487513A patent/CN1498776A/en active Pending
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US20080094621A1 (en) * | 2006-10-20 | 2008-04-24 | Zhiyong Li | Nanoscale structures, systems, and methods for use in nano-enhanced raman spectroscopy (ners) |
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US20090274874A1 (en) * | 2008-04-30 | 2009-11-05 | Zhiyong Li | Photonic Device And Method For Forming Nano-Structures |
US20100288543A1 (en) * | 2009-04-14 | 2010-11-18 | Nanoink, Inc. | Conducting lines, nanoparticles, inks, and patterning |
Also Published As
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TW200406808A (en) | 2004-05-01 |
EP1424309A3 (en) | 2006-01-25 |
EP1424309A2 (en) | 2004-06-02 |
US6916511B2 (en) | 2005-07-12 |
US20040081798A1 (en) | 2004-04-29 |
TWI300237B (en) | 2008-08-21 |
JP2004148494A (en) | 2004-05-27 |
CN1498776A (en) | 2004-05-26 |
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