TW201409164A - Cylindrical polymer mask and manufacturing method - Google Patents

Abstract

A cylindrical mask may be fabricated using a hollow casting cylinder and a mask cylinder. The casting cylinder has an inner diameter that is larger than the outer diameter of the mask cylinder. The casting and mask cylinders are coaxially assembled and a liquid polymer inserted in a space surrounding the mask cylinder between the inner surface of the casting cylinder and the outer surface of the mask cylinder. After curing the liquid polymer, the casting cylinder is removed. A surface of the cured polymer can be patterned. It is emphasized that this abstract is provided to comply with the rules requiring an abstract that will allow a searcher or other reader to quickly ascertain the subject matter of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims.

Description

Cylindrical polymer mask and manufacturing method Priority claims and references to related applications

This case advocates the US temporary application pending the simultaneous transfer of the "CYLINDRICAL POLYMER MASK AND METHOD OF FABRICATION" filed by Boris Kobrin et al. on March 15, 2013. The priority of the case number 61/798,629 (Attorney Docket No. RO-020-PR), the entire disclosure of which is hereby incorporated by reference.

The case of the United States provisional application number pending by Boris Kobrin et al. on May 2, 2012, entitled "SEAMLESS MASK AND METHOD OF MANUFACTURING" The priority of 61/641,711 (Attorney Docket No. RO-013-PR), the entire disclosure of which is hereby incorporated by reference.

In this case, the US temporary application number number pending by Boris Kobrin et al. on May 2, 2012, entitled "LARGE AREA MASKS AND METHOD OF MANUFACTURING" Priority of 61/641, 650 (Agent Case No. RO-014-PR), within the entire disclosure of the case It is incorporated by reference.

This case advocates the US non-provisional application pending the simultaneous transfer of the CYLINDRICAL MASTER MOLD AND METHOD OF FABRICATION, which was applied for by Boris Kobrin et al. on January 31, 2013. The priority of Serial No. 13/756,348 (Attorney Docket No. RO-018-US), the entire disclosure of which is hereby incorporated by reference.

This case advocates the simultaneous transfer of the CYLINDRICAL PATTERNED COMPONENT FOR CASTING CYLINDRICAL MASKS, which was applied for by Boris Kobrin et al. on January 31, 2013. The priority of the pending US Non-Provisional Application Serial No. 13/756,370 (Attorney Docket No. RO-019-US), the entire disclosure of which is hereby incorporated by reference.

The present invention is also related to the co-transfer of the International Patent Application Publication No. WO2009094009, the entire disclosure of which is incorporated herein by reference.

The present disclosure is related to the lithography method. More specifically, aspects of the present disclosure relate to rotatable masks, including cylindrical polymer masks and methods of making the same.

Photolithography manufacturing methods have been used in a wide variety of different technical applications, including solar cells, LEDs, integrated circuits, MEMS devices, architectural glass, information Micro-scale and nano-scale manufacturing of displays and the like.

Continuous roll or roll-to-roll and roll-to-plate lithography methods typically use a cylindrical shaped mask (eg, mold, stamp) (stamp), photomask, etc., to transfer the desired pattern onto a rigid or flexible substrate. The desired pattern can be, for example, an imprinting method (e.g., nano transfer lithography), selective transfer of material (e.g., micro-or nano-contact printing). , transfer transfer lithography, etc., or exposure methods (eg, optical contact lithography, near field lithography, etc.) are transferred to the substrate. Some advanced types of such cylindrical masks use a soft polymer to form a patterned layer that conforms to the outer surface of the cylinder. Unfortunately, the lamination of the laminate on the cylindrical surface creates a seam line where the edges of the laminate meet. This may create unwanted image features at the seams when the pattern is reproducibly transferred to the substrate using a cylindrical mask.

In addition to making a mask with a seamless polymer layer, it is desirable to make a polymer layer having a thick and uniform smooth surface, For subsequent rolling lithography manufacturing methods.

Patterned substrates and structured coatings are attractive for a variety of applications, including architectural glass, information displays, solar panels, and more. For example, nanostructured coatings can provide the desired anti-reflective properties for architectural glass. At present, methods for patterning substrates include methods such as electron beam lithography, photolithography, interference lithography, and the like, and are used for practical use in applications requiring a large area. For substrates or structured coatings, especially for applications having an area of 200 cm ² (cm 2 ) or greater, the cost is typically too high.

Therefore, there is a need in the art for large-area patterned layers and their low cost manufacturing methods. The need for the present invention is generated in this regard.

The nanostructure is necessary for many current applications and industries as well as for new technologies and future advanced products. By way of example and not limitation, an increase in efficiency can be achieved for current applications in, for example, the field of solar cells and LEDs (light-emitting diodes) and the next generation of data storage devices.

The nanostructured substrate can be exemplified by, for example, e-beam direct writing, deep ultraviolet lithography, nanosphere lithography, nano transfer lithography. Near-field phase shift lithography, and plasma It is manufactured by techniques such as plasmonic lithography.

The use of near-field optical lithography as described in the International Patent Application Publication No. WO2009094009 and U.S. Patent No. 8,182,982, the entire disclosure of which is incorporated herein by reference in its entirety, is incorporated by reference. The method of material nanographing. According to such methods, a rotatable mask is used to image a radiation-sensitive material. Typically, the rotatable mask comprises a cylinder or cone having a mask pattern formed on its surface. The mask rolls relative to the radiation-sensitive material (eg, photoresist) as the radiation passes through the mask pattern to the radiation-sensitive material. Therefore, this technique is sometimes referred to as "rolling mask" lithography. This nanopatterning technique utilizes near-field photolithography in which a mask system that is used to pattern a substrate is placed in contact with a substrate. The near-field photolithography implementation of this method may utilize an elastomeric phase shift mask or a surface plasmon technique in which the rotating mask surface contains metal nanopores or Nano particles. In one embodiment, such a mask can be a near field phase shifting mask. Near-field phase shift lithography involves exposing a radiation-sensitive material to ultraviolet (UV) light that is phase-shielded through an elastomer while the mask is in conformal contact with the radiation-sensitive material. Bringing the elastomeric phase mask into contact with a thin layer of radiation-sensitive material causes the radiation-sensitive material to "wet" the surface of the contact surface of the mask. Passing UV light through the mask while the mask is in contact with the radiation-sensitive material exposes the radiation-sensitive material to light intensity developed at the surface of the mask. distributed.

In some implementations, a phase mask can be formed with a depth of relief that is designed to modulate the phase of the transmitted light by radians. As a result of the phase modulation, a local null in the intensity occurs at the step edge in the release pattern formed on the mask. When a positive radiation sensitive material is used, exposure through such a mask and subsequent development produces a line of radiation sensitive material having a width equal to the characteristic width of the zero in the intensity. For a combination of 365 nm (nano) (near UV) light and conventional radiation sensitive materials, the width of the zero in the intensity is approximately 100 nm. A polydimethylsiloxane (PDMS) mask can be used to form a conformal atomic scale contact with the layer of radiation-sensitive material. This contact is spontaneously established upon contact without applying pressure. A generalized adhesion force directs this process and provides a simple and convenient way to align the mask at an angle and position orthogonal to the surface of the radiation-sensitive material to establish a perfect contact. There is no physical gap here relative to the radiation sensitive material. PDMS is transparent to UV light having a wavelength greater than 300 nm. Passing light from a mercury lamp (where the main spectral line is at 355 nm to 365 nm) through the PDMS exposes the radiation-sensitive material to the intensity formed at the mask while the PDMS is in angular contact with the radiation-sensitive material layer. distributed.

Another embodiment of the rotating mask can include surface plasma Sub-technology in which a metal layer or film is applied or deposited on the outer surface of a rotatable mask. The metal layer or film has a specific series of nano-through holes. In another embodiment of the surface plasmonics technique, a layer of metal nanoparticles is deposited on the outer surface of the transparent rotatable mask to achieve surface plasmonics by enhanced nanopatterning.

Each of the above applications can use a rotatable mask. The rotatable mask can be assisted by a master mold (manufactured using one of known nanolithography techniques such as electron beam, deep UV, interference, and nano transfer lithography) Made. The rotatable mask can be made by molding a polymeric material, curing the polymer to form a replica film, and finally attaching the replica film to the surface of the cylinder. Unfortunately, this method inevitably creates some "macro" sutures between the individual polymer films (even if the main mold is very large and only one polymer film is needed to cover the entire cylinder) The surface still inevitably produces a stitch). The present invention has been made in this connection.

According to some aspects of the present disclosure, a cylindrical mask can be formed by patterning a master mold, forming a patterned polymer mask by casting a liquid polymer onto the master mold, and curing the liquid polymer. Made. A portion of one end of the patterned polymeric mask can be truncated or the liquid polymer can be cast on a strip at the end of the main mold. The master mold and the patterned polymer mask can be rolled up to form a laminated cylinder A gap is formed on the patterned polymer mask. The laminated cylinder can be inserted into the casting cylinder, wherein the substrate of the master mold is in contact with the casting cylinder and the gap is filled with additional liquid polymer, and the additional liquid polymer can be solidified by removing the casting circle The cartridge and the main mold are separated from the laminate to form a free standing polymer.

According to other aspects of the present disclosure, a cylindrical mask can be fabricated using a hollow casting cylinder and a mask cylinder. The casting cylinder can have an inner diameter that is greater than the outer diameter of the mask cylinder. The casting cylinder and the mask cylinder can be assembled coaxially, and the liquid polymer is injected into the space surrounding the mask cylinder between the inner surface of the casting cylinder and the outer surface of the mask cylinder. After curing the liquid polymer, the casting cylinder can be removed.

According to other aspects, the substrate can be patterned by successively repeating the transfer of the substrate with a master mask having a pattern, wherein the pattern has a smaller area than the substrate, and the transfer system is repeated until the substrate The desired area is patterned. Each successive transfer may overlap a portion of the previously transferred portion of the substrate. The primary mask transfer substrate can comprise (i) depositing a polymer precursor liquid; (ii) applying pressure to the polymer precursor liquid between the main mask and the substrate; and (iii) curing the polymer precursor liquid. The resulting substrate can have a patterned layer with a plurality of imprints, and each border between the imprints contains an imprint that overlaps a portion of another imprint.

A further aspect of the present disclosure describes a cylindrical mold that can be used to create a cylindrical mask for lithography. The structured porous layer can be deposited on the inner surface of the cylinder. Radiation sensitive material can be deposited over the porous layer Above is filled with a pore formed in the porous layer. The radiation sensitive material in the hole can be cured by exposing the cylinder with a light source. The uncured resist and porous layer can be removed leaving a post on the inner surface of the cylinder.

A further aspect of the present disclosure includes a cylindrical master mold assembly having a cylindrical patterned assembly having a first diameter and a sacrificial casting component having a second diameter ). A component having a smaller radius can be coaxially inserted into the interior of a component having a larger radius. The patterned features can be formed on the inner surface of the cylindrical patterned assembly facing the sacrificial casting assembly. Once the cast polymer has been cured, the sacrificial casting assembly can be removed to allow the polymer to be released.

200‧‧‧assembly

202‧‧‧mask cylinder, first casting cylinder

204‧‧‧casting cylinder, main mode

206‧‧‧ axis

208‧‧‧Cylindrical area, space

300‧‧‧ method

302‧‧‧Steps

304‧‧‧Steps

306‧‧‧Steps

308‧‧‧Steps

400‧‧‧Assembled device

402a‧‧‧First board

402b‧‧‧second board

406‧‧ sales

408‧‧‧ hole

410a‧‧‧first trench

410b‧‧‧Second trench

412‧‧‧mask cylinder

414‧‧‧casting cylinder

416‧‧‧ Polymer precursor

502‧‧‧mask cylinder

504‧‧‧casting cylinder

506‧‧‧assembly

508a‧‧‧ first board

508b‧‧‧second board

510‧‧ sales

512‧‧‧Liquid polymer, polymer precursor

514‧‧‧ openings

516‧‧‧ curing means

518‧‧‧cured polymer, external compliant layer

520‧‧‧Cylindrical mask

602‧‧‧ casting cylinder

604‧‧‧ release coating

606‧‧‧Liquid polymer material, outer polymer layer

608a‧‧‧ curing means

608b‧‧‧ curing means

610‧‧‧mask cylinder

612a‧‧‧plate

612b‧‧‧plate

614‧‧ sales

616‧‧‧assembly

618‧‧‧Liquid polymer, inner polymer layer

620‧‧‧ holes or openings

622‧‧‧Cylindrical mask

711‧‧‧Cylinder

712‧‧‧Light source

713‧‧‧ Elastomeric film, elastomeric cylindrical rolling mask, cylindrical mask

714‧‧‧Nylon pattern

715‧‧‧Substrate

716‧‧‧Light sensitive materials, radiation sensitive materials

800‧‧‧ main mold assembly

820‧‧‧Cylindrographic components

825‧‧‧ pattern

830‧‧‧ Sacrificial casting components

840‧‧‧ space

900‧‧‧Process

960‧‧‧Steps

961‧‧‧Steps

962‧‧‧Steps

963‧‧‧Steps

1000‧‧‧ main mold assembly

1013‧‧‧Cylindrical rolling mask, cylindrical mask

1014‧‧‧Nylon pattern

1020‧‧‧Cylindrographic components

1025‧‧‧ pattern

1030‧‧‧ Sacrificial casting components

1040‧‧‧ Space

1100‧‧‧Process

1160‧‧ steps

1161‧‧‧Steps

1162‧‧‧Steps

1163‧‧‧Steps

1164‧‧ steps

1200‧‧‧Cylindrical mask

1201‧‧‧Cylindrical rolling mask

1202‧‧‧Cylindrical rolling mask

1211‧‧‧ hollow cylinder

1212‧‧‧Light source

1213‧‧‧ Elastomeric rolling mask, elastomeric mask

1214‧‧‧Shaped surface

1217‧‧‧ gas

1218‧‧‧ gas holder

1218 _B ‧‧‧Airbag

1218 _S ‧‧‧Seal

1302‧‧‧Main mask

1304‧‧‧Graph, main pattern

1306‧‧‧Substrate

1308‧‧‧Previous transfer part, imprint

1310‧‧‧ polymer precursor liquid

1312‧‧‧Contact line

1314‧‧‧ Direction of pressure

1402‧‧‧Main mask

1404‧‧‧Substrate

1406‧‧‧Main pattern

1408‧‧‧ polymer precursor liquid

1410‧‧‧ curing means

1412‧‧‧Previous transfer and curing part, graphic part

1502a‧‧‧Substrate

1502b‧‧‧Substrate

1502c‧‧‧Substrate

1504a‧‧ mark

1504b‧‧·mark

1504c‧‧·mark

1506a‧‧‧ seam line

1506c‧‧‧ seam line

1600‧‧‧ main mode

1620‧‧‧Cylinder

1621‧‧‧ outer surface

1622‧‧‧ inner surface

1633‧‧‧Protruding

1720‧‧‧Cylinder

1721‧‧‧Unexposed radiation sensitive materials

1722‧‧‧ inner surface

1723‧‧‧radiation

1729‧‧‧ holes

1730‧‧‧structured porous layer, nanostructured porous layer, anodized aluminum (AAO) layer

1731‧‧‧radiation sensitive materials

1732‧‧‧cured materials

1733‧‧‧glass material

1800‧‧‧ main mode

1820‧‧‧Cylinder

1821‧‧‧ outer surface

1822‧‧‧ inner surface

1824‧‧‧ Epitaxial seed layer

1829‧‧‧ hole

1830‧‧‧Structural porous layer

1833‧‧‧Protruding

1900‧‧‧ main mode

1922‧‧‧ inner surface

1923‧‧‧radiation

1931‧‧‧radiation sensitive materials

1932‧‧‧Unexposed portions of radiation-sensitive materials (Fig. 19B)

1932‧‧‧ Cured radiation-sensitive materials (Fig. 19B’)

1933‧‧‧Protruding

1940‧‧‧Self-Organized Single Layer (SAM)

2020‧‧‧Cylinder

2021‧‧‧ outer surface

2023‧‧‧radiation

2031‧‧‧radiation sensitive materials

2033‧‧‧Protruding

2040‧‧‧Self-Organized Single Layer (SAM)

2100‧‧‧ method

2105‧‧‧Substrate

2110‧‧‧ pattern

2112‧‧‧patterned master/mask, first main mask, sub-main mask, sub-master

2115‧‧‧ Elastomeric materials, cured polymers, cast polymers, polymer masks

2120‧‧‧Strip, gap

2125‧‧‧Strip section

2130‧‧‧ casting cylinder

2140‧‧‧ pattern

2230‧‧‧Cylindrical master assembly

2232‧‧‧casting cylinder

2234‧‧‧Master mode

2236‧‧‧ patterned polymer mask

2237‧‧‧ gap, lost strip

2239‧‧‧Striped section, lost strip section

2300‧‧‧Process

2310‧‧‧Steps

2320‧‧‧Steps

2330‧‧‧Steps

2340‧‧‧Steps

2342‧‧‧Steps

2350‧‧‧Steps

2400‧‧‧Cylindrical master assembly

2401‧‧‧Cylindrical master assembly

2410‧‧‧Cylindrical master, master/mask

2420‧‧‧First casting cylinder

2430‧‧‧polymer mask, outer layer

2432‧‧‧Protective film, protective layer

2440‧‧‧Second casting assembly

2450‧‧‧mask cylinder

2460‧‧‧ Buffer layer, polymer

2500‧‧‧Process, method

2510‧‧‧Steps

2520‧‧‧Steps

2530‧‧‧Steps

2540‧‧‧Steps

2550‧‧‧Steps

2560‧‧‧Steps

2570‧‧‧Steps

2580‧‧‧Steps

2590‧‧‧Steps

R ₁ ‧‧‧first radius

R ₂ ‧‧‧second radius

Figures 1A through 1C show a general cylinder that is labeled to help clarify the description language used in the description of the present invention and the claims in the claims.

Figure 2 shows a mask cylinder assembled inside the casting cylinder in accordance with an embodiment of the present invention.

3 is a flow chart of a method of making a cylindrical mask in accordance with an embodiment of the present invention.

4A through 4D show an assembly device in accordance with an embodiment of the present invention.

5A to 5D are diagrams showing the system according to an embodiment of the present invention. Schematic diagram of the process flow for the method of making a cylindrical mask.

6A through 6I are process flow diagrams showing a method of fabricating a cylindrical mask having a plurality of polymer layers that become external compliant layers, in accordance with an embodiment of the present invention.

7 is a schematic diagram showing an example of printing a pattern using a cylindrical mask manufactured in accordance with an embodiment of the present invention using rolling mask nanolithography.

8A is a top plan view of a cylindrical master mold assembly including a cylindrical patterning assembly in which a sacrificial casting assembly is coaxially inserted into the interior of a cylindrical patterning assembly, in accordance with an aspect of the present disclosure.

Figure 8B is a perspective view of the cylindrical main mold assembly shown in Figure 8A.

9 is a block diagram depicting instructions of a method of forming a cylindrical mask with a cylindrical master mold assembly in accordance with aspects of the present disclosure.

10A is a top plan view of a cylindrical master mold assembly including a sacrificial casting assembly in which a cylindrical patterning assembly is coaxially inserted into the interior of a sacrificial casting assembly, in accordance with an aspect of the present disclosure.

Figure 10B is a perspective view of the cylindrical main mold assembly shown in Figure 10A.

Figures 10C through 10E show how a cylindrical mask can be removed from a cylindrical patterning assembly in accordance with aspects of the present disclosure.

11 is a block diagram depicting instructions for a method of forming a cylindrical mask with a cylindrical master mold assembly in accordance with aspects of the present disclosure.

12A through 12C show aspects in accordance with aspects of the present disclosure. A cylindrical mask in which a gas holder is formed between the elastomer cylinder and the rigid transparent cylinder.

Figure 13A shows a primary mask in accordance with an embodiment of the present invention.

Figure 13B shows a main mask being used to pattern a larger area of substrate in accordance with an embodiment of the present invention.

Figure 13C shows an individual imprint of a larger area substrate using a primary mask in accordance with an embodiment of the present invention.

Figures 13D and 13E show photomicrographs of patterned substrates obtained in accordance with embodiments of the present invention.

14A to 14G show a process flow of transferring a large-area substrate according to an embodiment of the present invention.

15A through 15C show examples of patterned large area substrates in accordance with an embodiment of the present invention.

16 is a top plan view of a cylindrical master mold having a projection extending from an inner surface in accordance with an aspect of the present disclosure.

17A-17G are schematic diagrams showing a process of forming a master mold in accordance with aspects of the present disclosure.

18A to 18D are schematic views showing a process of forming a master mold according to another aspect of the present disclosure using an epitaxial seed layer.

19A, 19B, 19B', and 19C are schematic views showing a process of forming a master mold according to another aspect of the present disclosure using a self-assembled monomer formed on an inner surface of a master mold.

20A, 20B, 20B', and 20C are displayed according to use A schematic diagram of a process of forming a master mold of a further aspect of the present disclosure that forms a self-assembled monomer on the outer surface of the master mold.

21A-21G are schematic diagrams showing a process flow for creating a self-contained mask using a rolled stack in accordance with various aspects of the present disclosure.

22A is a top plan view of a cylindrical master mold assembly having a rolled stack used to form a cylindrical mask in accordance with various aspects of the present disclosure.

Figure 22B is a perspective view of the cylindrical main mold assembly shown in Figure 22A.

23 is a process flow diagram showing a method of making a cylindrical polymer mask using a rolled stack in accordance with various aspects of the present disclosure.

24A is a top plan view of a cylindrical master mold assembly used to form a multi-layered cylindrical mask in accordance with various aspects of the present disclosure.

Figure 24B is a plan view of the cylindrical main mold assembly shown in Figure 24A.

25 is a process flow diagram showing a method of making a multi-layered cylindrical polymer mask in accordance with various aspects of the present disclosure.

The following definitions of terms help to clarify and assist the narrative technical terms used in the description of this disclosure and in the claims of the patent application. Understanding.

As used herein, the "opposing ends" of a component refer to two opposite end faces of a cylinder or other axially symmetrical shape as shown in Figure 1A.

The "outer surface" of the component refers to the outer surface on the side of the cylinder or other axially symmetrical shape as shown in Figures 1A and 1B.

The "inner surface" of the assembly refers to the inner surface on the inside of a hollow cylinder or other axially symmetrical shape as shown in Figure 1B.

The "outer radius/diameter" of the assembly refers to the radius/diameter of the outer surface of the cylinder or other axially symmetrical shape as shown in Figures 1A and 1B. Where the outer surface of the component is of a shape having a non-fixed radius/diameter, such as in the case of a cone or other axially symmetrical shape, the outer radius/diameter may refer to any such radius/diameter as long as it Corresponding to the outer surface.

The "internal radius/diameter" of the component refers to the radius/diameter of the inner surface of the cylinder or other axially symmetric shape as shown in Figure 1B. Where the inner surface of the component is a shape having a radius/diameter that is not fixed, such as in the case of a cone or other axially symmetrical shape, the inner radius/diameter may refer to any such radius/diameter as long as it Corresponds to the inner surface.

The "coaxially assembled" assembly means that the assembly is assembled such that the assembly has the same axis of symmetry as shown in Figure 1C.

"mask cylinder" or "masking cylinder" There is a cylindrical substrate for a cylindrical mask, and a compolant layer is formed on the outer surface of the cylindrical substrate.

A "cast cylinder" or a "cast cylinder" refers to a cylindrical mold.

I. Casting using coaxial components

Aspects disclosed in this Section I include methods and apparatus for making a rotatable mask. A variety of other methods and devices are also included in this section. The casting/molding process and the coaxial casting assembly can be used to cast a compliant layer of rotatable mask that provides a number of benefits, including minimizing or eliminating the occurrence of seams of the rotatable mask. The implementation aspects of this chapter may also have a variety of other advantages.

It should also be noted that this section I can be applied to the various aspects of the remaining sections II to VI described herein and can be readily implemented in these aspects, including but not limited to any that may involve the use of coaxial casting assemblies and assemblies. To make these chapters of the rotatable mask. By way of example and not limitation, the various aspects disclosed in this section I can be readily applied to the section described herein that relates to the manufacture of a rotatable mask using a sacrificial casting assembly and a coaxial assembly assembly. The implementation of II.

To make a cylindrical mask, the polymeric material can be used as an external compliant layer of a cylindrical mask. In an embodiment of the invention, a casting process can be used to form an outer compliant layer by casting a polymer onto the outer surface of the mask cylinder to create a seamless outer layer. In an embodiment of the invention The casting process can involve assembling the casting cylinder coaxially with the mask cylinder and injecting the liquid polymer into the space surrounding the mold of the mask cylinder. The polymer is then cured and the casting cylinder is removed to create a seamless cylindrical mask that can be used to make a variety of different devices. The polymeric layer of the cylindrical mask can be patterned to produce a mask pattern that can be repeatedly transferred to the substrate, such as by roll-to-roll lithography, roll-to-plate lithography, and the like.

In an embodiment of the invention, a method of making a cylindrical mask may comprise assembling a casting cylinder coaxially with a mask cylinder, injecting a liquid polymer into a space between the casting cylinder and the mask cylinder Internal, solidified polymer, and removed casting cylinder. The method may additionally comprise patterning the polymer, which may be an additional step after removal of the casting cylinder, or it may be incorporated into the manufacturing process by using a cylinder having a pattern on the surface, such that When the polymer is in contact with the surface of the cylinder, the pattern is transferred to the polymer.

In an embodiment of the invention, assembling the casting cylinder around the shroud cylinder may involve the use of an assembly apparatus that holds the shroud cylinder and the casting cylinder in position during manufacture of the cylindrical shroud. The assembly device can be designed to maintain coaxial alignment of the cylinder during the casting process to create a cylindrical space of uniform thickness around the mask cylinder corresponding to the outer compliant layer of the cylindrical mask. The fixture can be designed to allow liquid polymer material to be injected into the space with the cylinder and the mount assembled.

In an embodiment of the invention, the assembly device used to maintain the coaxial alignment of the cylinder during the manufacturing process may comprise a set of plates, wherein the plates are held at opposite ends of the cylinder by pins Together. Plate A groove or other mechanism may be included that is aligned with the sides of the cylinder to keep the cylinder aligned for positioning. One of the panels may have holes or other mechanisms to allow liquid polymer to be cast through the apertures into the space corresponding to the outer compliant layer of the cylindrical mask.

The casting fixture can be removed by disassembly. For example, after the polymer between the cylinders has been cured, the casting cylinder can be longitudinally oriented from its outer surface without significantly damaging the polymer or leaving a small amount of cast cylinder material The cured polymer is cut down to the tubular shape and divided into two or more than two sections. The above cutting can be performed by sawing, chemical etching, or laser. The sections of the casting cylinder can then be separated from the cured polymer and relative to each other.

Embodiments of the present invention can produce a patterned cylindrical mask having a uniform and seamless outer layer, while the outer layer has a desired thickness and smoothness for reproducibly transferring the pattern of the mask to the substrate Used to make a variety of different devices.

Turning now to Figure 2, an assembly 200 having a shroud cylinder 202 surrounded by a cast cylinder 204 is shown in accordance with an embodiment of the present invention. The mask cylinder 202 is assembled coaxially with the casting cylinder 204 such that the axes 206 of the two are aligned with each other, thereby creating a cylindrical region 208 having a uniform thickness around the mask cylinder, which can define a cylindrical cover The shape of the outer polymer layer of the cover. The cylinders 202 and 204 can be held in position by the use of an assembly device (not shown) that aligns the axes of the cylinders 202 and 204 and allows liquid polymer to be injected into the cylindrical region 208 of the assembly 200. Inside, for example, by pouring a liquid polymer through the opening of the assembly device Or hole. The polymer precursor can be injected into the space 208 between the mask cylinder 202 and the casting cylinder 204. The polymer precursor can be in the form of a monomer, a polymer, a partially cross-linked polymer, or any mixture of the above, in a liquid or semi-liquid form. The polymer precursor can be cured to form an outer polymeric layer of a cylindrical mask. The polymer can be patterned into a mask pattern in a variety of different ways. For example, the inner surface of the casting cylinder 204 can include a mask pattern such that the outer surface of the polymeric material fits over the pattern on the inner surface of the casting cylinder 204. As another example, the outer surface of the mask cylinder 202 may contain a mask pattern such that the pattern is transferred to the inner surface of the polymer after the polymer is formed on the mask cylinder. As another example, the polymeric material can be patterned after subsequent manufacturing steps and removal of the casting cylinder 204 by patterning the outer surface of the polymer using a variety of different lithography methods. As another example, the pattern can also be patterned by a combination of the above.

Turning to Figure 3, there is shown a flow chart for making a seamless cylindrical mask in accordance with an embodiment of the present invention. The method 300 of making a cylindrical mask can include coaxially assembling the cylinder as shown at step 302, which may involve assembling the casting cylinder with the mask cylinder such that the casting cylinder and the mask cylinder are The axes are the same. The casting cylinder can be a hollow cylinder having an inner diameter that is larger than the outer diameter of the shroud cylinder such that the space is left between the two cylinders. This difference in diameter may define the thickness of the outer compliant layer of the mask such that in the case where D _cast is the inner diameter of the casting cylinder and D _mask is the outer diameter of the mask cylinder, the compliant layer of the cylindrical mask The thickness T will be T = (D _{cast -} D _mask )/2, which is half the difference in diameter. The thickness T can be selected by the use of a cylinder having a diameter corresponding to the above equation, depending on the particular requirements for the various applications. Manufacturing method 300 can also include injecting a polymer precursor into the space surrounding the outer surface of the mask cylinder as shown at step 304. Injection of the polymer precursor can be carried out, for example, by casting a liquid or semi-liquid polymer precursor material through the top of the assembled cylinder into the space between the cylinders. The injected polymer precursor can also be implemented in other ways as long as the polymer precursor material is introduced into the space between the cylinders. Preferably, the polymer should substantially fill this space. The method 300 of making a cylindrical mask can also include curing the polymer precursor as shown at step 306 to form a polymer layer. Curing the polymer precursor may involve applying UV radiation, heat application, or other curing treatment to the assembled assembly to harden the polymer. Once the polymer is cured, the method 300 can further include removing the casting cylinder as shown at step 308, thereby leaving a cylindrical mask having an outer compliant layer corresponding to the cured polymer. The method 300 can also include patterning the polymer, which can be polymerized, for example, by patterning the outer surface of the compliant layer after removal of the mold or by using a patterned cylinder during the manufacturing process. The patterning is achieved by being combined with other manufacturing steps.

It should be noted that although the casting cylinder is shown to be assembled outside of the mask cylinder and around the mask cylinder, it may be the reverse configuration. In such an embodiment, the outer surface of the casting cylinder can be patterned, and when the casting cylinder is removed, the negative of the pattern on the outer surface of the casting cylinder is transferred to On the inner surface of the mask cylinder Polymer material.

It should be noted that the removal of the casting cylinder can be carried out in a variety of different ways. By way of example and not limitation, the casting cylinder can be cut by using a saw, laser, wet or dry etch, or other means. When cutting the casting cylinder, care must be taken not to damage the polymer layer below. If a laser is used to cut the casting cylinder, a special layer of material can be deposited on the inner surface of the casting cylinder to act as an etch stop layer, and this layer should be reflective to the light used to cut the casting cylinder material. Cutting can be performed by using one or more cut lines to facilitate subsequent stripping of the casting cylinder from the polymer surface. Once the casting cylinder is cut, the casting cylinder can be mechanically stripped from the polymer surface. By way of example and not limitation, the casting cylinder can be chemically etched by using an etch chemistry that does not etch away the polymer or mask cylinder therein. go with. By way of example and not limitation, the casting cylinder can be treated with a low friction coating or other release coating prior to assembly such that after curing, the casting cylinder can slide away from the polymer surface. By way of example and not limitation, if the coefficient of thermal expansion of the casting cylinder is greater than the coefficient of thermal expansion of the polymer, the casting cylinder can be heated to expand the casting cylinder and slide it away (if polymer Can withstand this temperature). By way of example and not limitation, the casting cylinder can be treated with a uniform coating which can be dissolved after curing the polymer and the casting cylinder can be slid away from the polymer surface. The casting cylinder can also be removed by other means, and such other removal means are also within the scope of the invention. Therefore, the present invention The scope should not be limited to any particular method of removal unless explicitly recited in the claims of the patent application.

Turning to Figures 4A through 4D, details of an example of an assembly apparatus in accordance with an embodiment of the present invention are shown. In FIG. 4A, an entire assembly apparatus 400 that can be used to make a seamless cylindrical mask in accordance with an embodiment of the present invention is shown. Assembly device 400 can include plates 402a and 402b that are held together by pin 406. The plates 402a and 402b can be held together at opposite ends of the cylinder (not shown) and the pins 406 are preferably aligned with the axis of the cylinder. For example, the first panel 402a can be oriented into a top panel during assembly and the second panel 402b can be oriented into a bottom panel. The first panel 402a may additionally include apertures to allow the polymer to be cast through the apertures into the space between the cylinders. The panel may also include grooves 410a and 410b that align with the arrangement of the mask cylinder and the sidewalls of the casting cylinder to facilitate positioning of the cylinder.

4C shows a top view of a first panel 402a in accordance with an embodiment of the present invention. The arrangement of the holes 408 may correspond to the space surrounding the mask cylinder inside the casting cylinder. As shown in FIG. 4C, in an embodiment of the invention, during fabrication of the cylindrical mask, the first trench 410a can be aligned with the mask cylinder 412, and the second trench 410b can be coupled to the casting cylinder. 414 alignment. In the embodiment illustrated in Figures 4B and 4C, it can be seen that the aperture 408 is positioned between the groove 410a where the surface of the mask cylinder 412 is aligned and the groove 410b where the surface of the casting cylinder 414 is aligned. To better facilitate the pouring of the polymer precursor 416 into the space between the two cylinders. It should be noted that the aperture 408 can be designed to allow the polymer precursor 416 to be injected through the assembly Any of a variety of different hole shapes, hole setting patterns, number of holes, and the like are provided, and the holes shown in Fig. 4C are provided for illustrative purposes only. It should also be noted that although circular panels are shown generally in the figures, other shapes may be used and the panels shown in the figures are for illustrative purposes only.

Figure 4D shows a side view of a panel 402a in accordance with an embodiment of the present invention. The plate 402a can include grooves 410a and 410b to enable the assembly device to hold the cylinder in position during manufacture of the cylindrical mask. In an embodiment of the invention, the plate 402a can include a first groove 410a that is aligned with the mask cylinder during manufacture of the cylindrical mask, and a second groove 410b that is aligned with the casting cylinder. It should be noted that the grooves 410a and 410b can be designed into any of various shapes and setting patterns depending on the cylinder used to manufacture the cylindrical mask, and the grooves shown in the drawings are only provided. For the purpose of the narrative. It should also be noted that both the first plate member 402a and the second plate member 402b may have grooves for maintaining the alignment of the cylinder in alignment, as shown in Figures 4A through 4D.

Turning to Figures 5A through 5D, there is shown a process flow for fabricating a cylindrical mask in accordance with an embodiment of the present invention. In FIG. 5A, casting cylinder 504 is coaxially assembled around mask cylinder 502 by use of an assembly device to produce assembly 506, wherein the assembly device holds the cylinder in position and aligns the central axis of the cylinder. In FIG. 5A, the holder includes a first plate member 508a, a second plate member 508b, and attachable to the first and second plates 508a and 508b to place the two plates at opposite ends of the cylinders 502 and 504. A pin 510 that is held together. Cylinders 502 and 504 can be packaged in a variety of different materials Included in, for example, glass, metal, polymer, or other materials.

The mask cylinder 502 is preferably made of a material that is transparent to UV or other radiation used in the photolithography process using a cylindrical mask. Examples of materials for the mask cylinder 502 include fused silica. The casting cylinder 504 is preferably made of a material that is dimensionally stable for successful casting and that is also conformable to the removal process such as described above. The casting cylinder can be transparent to UV or other radiation, but does not have to be constructed as such in all embodiments.

The inner surface of the casting cylinder 504 may include a mask pattern corresponding to the pattern of the outer surface of the compliant layer desired for the cylindrical mask such that the polymer is during the casting process illustrated in Figures 5A through 5D. It is patterned. Likewise, the outer surface of the mask cylinder 502 can include a mask pattern for the inner surface of the compliant layer of the cylindrical mask. Alternatively, the surfaces of the cylinders 502 and 504 may not have any pattern, and the outer surface of the polymer may be patterned by various lithographic methods after formation of the compliant layer. In FIG. 5B, a liquid polymer or polymer precursor 512 is injected between the cylinders in the space between the inner surface of the casting cylinder 504 and the outer surface of the mask cylinder 502. For example, the injected polymer precursor 512 can be passed through the holder by casting it onto the top of the assembly 506, by the opening 514 remaining in the top panel 508a, and surrounding the mask circle to the interior of the casting cylinder. It is achieved within the space of the barrel. In FIG. 5C, the polymer is cured, for example, by applying UV radiation, temperature treatment, or other curing means 516 to the assembly 506. In Figure 5D, the casting cylinder 504 is removed from the cured polymer 518 leaving a cylindrical mask having a cured polymer 518 that becomes an external compliant layer. 520. If the patterned cylinder is not used in the manufacturing process, the process of Figures 5A through 5D may additionally include patterning the outer surface of the outer compliant layer 518 to have the desired shape after removal of the casting cylinder 504. Mask pattern.

It is noted that the pattern should be formed on the surface of the polymer, preferably on the outer surface for contact lithography, such that a cylindrical mask can be used to transfer the pattern onto the substrate. In embodiments of the invention, the outer surface of the polymer can be patterned by a variety of different means. In an embodiment of the invention, the mask pattern can be applied to the inner surface of the casting cylinder prior to filling the mold with the liquid polymer such that the mask pattern is transferred during casting of the polymer on the mask cylinder To the outer surface of the polymer. In other embodiments, the outer surface of the polymer can be patterned after removal of the casting cylinder. Regardless of the chosen patterning method, care must be taken to avoid stitching errors when forming the mask pattern, making this pattern seamless. Accordingly, it is preferred that the cylindrical mask of the embodiment of the present invention includes not only a seam-free compliant layer, but also a seamless pattern on the surface of the compliant layer.

It is noted that the patterning of the inner surface of the casting cylinder or the outer surface of the mask cylinder can be implemented using a variety of different techniques in accordance with embodiments of the present invention. For example, the inner or outer surface of the cylinder can be patterned by successively transferring it with a smaller primary mask, as described in Section III of the present description and by reference in its entirety. Application No. 61/641,650 (Attorney Docket No. RO-014-PR) of the co-transfer application filed on May 2, 2012. As another example, the surface of the cylinder can be used by using nano transfer lithography, Nano is patterned by any of a variety of different known techniques of printing, photolithography, and the like. As another example, the surface of the cylinder can be patterned by using an anodization process. This can be achieved, for example, by using a casting cylinder made of aluminum. The aluminum surface for anodization may alternatively be provided, for example, by depositing an aluminum layer on the surface of the cylinder. At that time, the nanoporous surface can be produced on the aluminum surface by using anodization. As another example, the inner surface patterning can be implemented by self-assembly of nanoparticle or nanosphere. The nanoparticle or nanosphere can be deposited from the suspension by using a dipping method, a spraying method, or the like. Upon drying, the cylindrical material can be etched by using these nanoparticles or nanospheres as an etch mask, and then the etch mask is removed or etched away.

According to an embodiment of the invention, patterning the polymer on the outer surface of the cylindrical mask after removal of the casting cylinder can be carried out by using a variety of different techniques. For example, the outer surface of the polymer can be patterned by successively transferring it with a smaller primary mask, as described in Section III of the present description and the co-examination of the above-mentioned co-transfer application. The case number is described in No. 61/641,650 (Attorney's Case No. RO-014-PR). As another example, the outer surface of the polymer can be used by using nano transfer lithography, nanocontact printing, photolithography, nanosphere lithography, self-assembly, interference lithography, anodized aluminum Any of a variety of different known techniques of anodic aluminum oxidation, and the like, is patterned.

It should also be noted that the compliant layer of the cylindrical mask is not limited to a single polymer layer, but may comprise a plurality of polymer layers having different properties. Embodiments of the invention may include forming an outer compliant layer of a bilayer polymer for use in a cylindrical mask. The outermost layer of the two-layer polymer can be a harder layer having a higher durability than the softer innermost polymer layer, and thus can be tolerated higher than a soft polymer layer only. Resolution or patterning of higher aspect ratio nanostructures. The inner surface of the casting cylinder may be pretreated with a release coating to facilitate removal of the casting cylinder from the outermost polymer layer at the end of manufacture. Forming a bilayer polymer may involve depositing the outermost liquid polymer on the patterned inner surface of the casting cylinder. For a two-layer polymer, the outer surface can be patterned after the removal of the casting cylinder in the same manner as a single layer of cushioning material (rather than patterning the inside of the casting cylinder). The hard polymer layer can then be cured, for example, by temperature treatment, UV radiation, or other means. After curing, the inner surface of the rigid polymer layer can withstand surface treatment to promote adhesion to another, softer innermost polymer layer. The surface treatment can be carried out, for example, by plasma treatment, corona discharge, deposition of an adhesive coating, or other means. The softer innermost polymer layer can then be formed in the same manner as described above for the single layer polymer. It should also be noted that a multi-layered cylindrical mask can be formed by successively repeating the casting process described herein to cast a new polymer layer on the outer surface of a previously fabricated polymer layer. In this case, each time the previous casting cylinder is removed, a larger casting cylinder should be used to the new surface of the previously manufactured polymer layer with the new one. A space for the new polymer layer is left between the inner surfaces of the casting cylinder.

In embodiments where two or more polymer layers are used, it is desirable to have an index of the optical index covering both the material of the previous pattern and the previous pattern. Also, it is desirable that the photolithography tool using the resulting mask be constructed to conform to a mask having an increasing diameter.

Turning to Figures 6A through 6I, there is shown a more detailed process flow for forming a cylindrical mask having a two-layer polymer as an outer compliant layer in accordance with an embodiment of the present invention. For example, fabricating a cylindrical mask having an outer compliant layer that is a two-layer polymer can include patterning the inner surface of the casting cylinder 602 as shown in FIG. 6A. The patterned inner surface can then be treated with a release coating 604 as shown in Figure 6B to facilitate subsequent release of the casting cylinder from the outer surface of the outermost polymer layer. In Figure 6C, a liquid polymer material 606 is deposited on the inner surface of the casting cylinder to form the outermost layer of the multilayered outer compliant laminate.

The polymer can be deposited according to any of several known methods. By way of example and not limitation, the polymer may be impregnated, ultrasonically sprayed, microjet or inkjet type dispensing, and possibly combined with spin impregnation. Deposited.

The polymeric material 606 may preferably be a relatively rigid polymer such as h-PDMS as described in Truong, TT et al., Soft Lithography Using Acryloxy Perfluoropolyether Composite Stamps. Langmuir 2007 , 23, (5), 2898-2905. The disclosure is hereby incorporated by reference. The use of a longer lasting outer layer allows for the patterning of higher resolution or higher aspect ratio nanostructures than can be achieved with an outer laminate that has a single polymer layer that becomes a cylindrical mask. In Figure 6D, the outer polymer layer 606 is cured by UV radiation, temperature treatment, or other curing means 608a. In FIG. 6E, the inner surface of outer polymer layer 606 may be surface treated after curing, such as by plasma treatment, corona discharge, deposition of an adhesive coating, or other means to promote interpolymer layers. Sticky. In FIG. 6F, a casting cylinder 602 having an outer polymer layer 606 on the inner surface is assembled around the mask cylinder 610 by use of an assembly device having cylinders 602 and 610 by pins 614. The plates 612a and 612b are held together on opposite ends. In Figure 6G, liquid polymer 618 is injected into the casting cylinder by being cast through a hole or opening 620 in the top plate 612a of the device. The liquid polymer 618 can correspond to the inner polymer layer, which can be softer than the outer polymer layer, and the liquid polymer 618 is injected into the space between the inner surface of the casting cylinder 602 and the outer surface of the mask cylinder 610. And more specifically, it is injected into the space between the inner surface of the outer polymer layer and the outer surface of the mask cylinder 610. In FIG. 6H, the inner polymer layer 618 is cured by applying a curing means 608b to the assembly 616 that can be UV radiation, heat, or other means. In FIG. 6I, the casting cylinder 602 is removed leaving a cylindrical mask 622 having an outer compliant layer comprising an inner polymer layer 618 and an outer polymer layer 606 on the outer surface of the mask cylinder 610. . The cylindrical shroud 622 has a patterned outer surface corresponding to the mask pattern applied to the inner surface of the casting cylinder 602 in the step of FIG. 6A.

It is also noted that the thickness of the polymer layer can vary depending on the particular requirements of the various applications. The thickness of the polymer layer may preferably, but not necessarily, be in the range of from about 0.5 mm (millimeters) to 5 mm. In the case where a two-layer polymer is used, the softer innermost layer may be relatively thick, for example in the range of 0.5 mm to 5 mm, while the harder outermost patterned layer may be relatively thin, for example in It is in the range of about 0.5 μm (micrometer) to 10 μm.

It is also noted that the polymer used to make the cylindrical mask can be, for example, a polydimethylsiloxane (PDMS) material such as Dow Corning ^® Sylgard ^® 184, h-PDMS (" Hard "PDMS", soft PDMS gel (gel), and the like. In the case where two polymer layers are used, for example, the soft inner polymer may be a soft PDMS gel and the outer layer may be Sylgard ^® 184. As another example, the inner layer can be Sylgard ^® 184 and the outer layer can be h-PDMS. It is noted that a variety of other elastomeric and polymeric materials can also be used to make the cylindrical mask and are within the scope of the present invention. Other possible polymers that can be used include, for example, melcapto-ester based adhesives (some of which are available from Norland products of Cranbury, New Jersey), all Perfluoropolyether, or other UV curable or heat curable polymer.

It should also be noted that the means for curing the polymer in embodiments of the invention may depend on the type of polymer being cured, the cylindrical material used, and other factors. For example, curing can use heat, UV Radiation, or other means to implement.

It is further noted that those of ordinary skill in the art can appreciate various modifications to the design of the assembly apparatus or method that maintains the cylinder aligned to the positioning without departing from the teachings of the present invention.

It should also be noted that the present invention can be used to form a variety of different patterns for a variety of different substrates and devices. The pattern may comprise features having different sized dimensions, and may preferably comprise microscale or nanoscale features, and more preferably have nanoscale features.

Embodiments of the invention may be used with a type of lithography technology known as "rolling mask" nanolithography. An example of a "rolling mask" near-field nano-lithography system is described in the International Patent Application Publication No. WO2009094009, the entire disclosure of which is incorporated herein by reference. An example of such a system is shown in Figure 7. The "rolling mask" may be in the form of a glass (e.g., quartz) frame, wherein the glass frame is in the shape of a hollow cylinder 711 that houses the light source 712. The elastomer film 713 formed on the outer surface of the cylinder 711 as described above may have a nano pattern 714 fabricated in accordance with a desired pattern to be formed on the substrate 715. The nanopattern 714 can be designed to perform phase shift exposure, and in this case is fabricated as an array of nanotrucks, struts, or cylinders, and can include features of any shape.

By way of example and not limitation, the nanopattern 714 on the cylinder 711 can have features in the form of parallel lines, wherein the parallel lines have a line width of about 50 nanometers and about 200 nanometers or Larger pitch. In general, the line width can range from about 1 nm to about 500. Within the range of nanometers, the pitch can range from about 10 nanometers to about 10 micrometers. Although an example in which the nanopattern 714 is in the form of a regular parallel line is described herein, the nanopattern may alternatively be a regularly repeated two-dimensional pattern having regular intervals and a fixed point of an arbitrary shape. (spot). Additionally, pattern features (lines or any shape) may be irregularly spaced apart.

The nanopattern 714 on the cylinder 711 is brought into contact with a photosensitive material 716, such as a photoresist applied to the substrate 715. Light sensitive material 716 is exposed to radiation from source 712, and nanopattern 714 on cylinder 711 is transferred to photosensitive material 716 at a location where the nanopattern contacts the photosensitive material. The substrate 715 is translated as the cylinder rotates such that the nanopattern 714 remains in contact with the photosensitive material. Depending on the nature of the light sensitive material, portions of the pattern exposed to the radiation may react with the radiation such that the portions become removable or non-removable.

For example, if the light sensitive material is of the type of photoresist known as positive resist, the portion of the material that is exposed to light becomes soluble to the developer and is not exposed. The portion remains insoluble to the developer. In the opposite case, if the light sensitive material is of the type of photoresist known as a negative photoresist, the portion of the material exposed to light becomes insoluble to the developer and the material is not The exposed portion is dissolved by the photoresist.

In certain embodiments of the invention, the light sensitive material 716 can be exposed by passing the substrate through the cylinder 711 two or more times. For a sufficiently small pitch value and line width value, from a pass The linear patterns of exposure are less likely to align with each other. As a result, the line from one sweep may eventually become between the lines obtained from the previous sweep. By carefully selecting the pitch, line width, and number of sweeps, a line pattern having a pitch that is less than the pitch of the lines in the pattern 714 on the cylinder 711 can ultimately be achieved at the light sensitive material 716.

When patterning the polymer, care must be taken to avoid splicing errors in the pattern. Preferably, the manufacture of the cylindrical mask in embodiments of the present invention also involves patterning a seamless pattern on the seamless polymer layer. This prevents the seam from being transferred to the substrate when the cylindrical mask is used to reproducibly map the substrate, because the outer compliant layer itself is seamless and because the surface of the compliant layer contains The pattern is also seamless.

It is further noted that embodiments of the present invention can be applied to make an axisymmetric but not cylindrical rolling mask, such as a frusto-conical shaped mask. In this case, the masking element and the mold element can be coaxially aligned with a panel that is held together by one or more pins. When assembled coaxially, the mutually facing surfaces of the mask element and the mold element can have similar shapes and the same aspect ratio such that a space having a substantially uniform thickness is defined therebetween.

II. Casting using sacrificial components

Aspects disclosed in this Section II include methods and apparatus for making a rotatable mask using a sacrificial casting assembly. A variety of other methods and devices are also included in this section. Sacrifice according to aspects of this chapter The casting assembly can be used with a patterned casting assembly to cast a compliant layer for a rotatable mask that can provide a variety of benefits, including under a pattern that does not damage the surface of the patterned casting assembly. Save the patterned cast components for future use. The implementation aspects of this chapter may also have a variety of other advantages.

It should also be noted that this Section II can be applied to the various aspects of the remaining sections I and III to VI described herein and can be readily implemented in such aspects, including but not limited to any that may involve the use of coaxial cast components and The assembly is made into the sections of the rotatable mask. By way of example and not limitation, the various aspects disclosed in this section II can be readily described in the section relating to the manufacture of a multi-layered rotatable mask using coaxially assembled components as described herein. Implemented in VI.

Aspects disclosed herein describe various different patterned component assemblies and methods for fabricating near field optical lithography masks for "rolling mask" lithography using patterned component assemblies. In rolling mask lithography, the cylindrical mask is coated with a polymer and the polymer is patterned to have the desired characteristics for phase shift lithography or plasmonic printing. The mask. Features that are patterned into polymers can be patterned using the composition of the patterned components described herein. The pattern component can comprise patterned features ranging in size from about 1 nanometer to about 100 micrometers, preferably in the range of from about 10 nanometers to about 1 micrometer, and more preferably in the range of from about 10 nanometers to about 1 micrometer. It is in the range of about 50 nm to about 500 nm. Cylindrical masks can be used to print sizes from about 1 nanometer The characteristic in the range of meters to about 1000 nm is preferably in the range of from about 10 nm to about 500 nm, and more preferably in the range of from about 50 nm to about 200 nm. .

The first aspect disclosed herein describes a cylindrical master mold assembly comprising a cylindrical patterning assembly having a first diameter and a sacrificial casting assembly having a second diameter. The second diameter can be smaller than the first diameter. A patterned feature can be formed on the inner surface of the cylindrical patterning assembly, and the sacrificial casting assembly can be coaxially embedded into the interior of the cylindrical patterning assembly. The polymeric material can then be filled into the gap between the patterned component and the sacrificial casting component to form a cylindrical mask. Once the polymer has been cured, the sacrificial casting assembly can be removed. According to certain aspects of the present disclosure, the sacrificial casting assembly can be broken to allow the cylindrical mask to be removed. Additionally, certain aspects of the present disclosure also result in deformation of the sacrificial casting assembly to allow the cylindrical mask to be removed.

In accordance with further aspects disclosed herein, the cylindrical master mold can have a cylindrical patterned assembly having a first diameter and a sacrificial cast assembly having a second diameter. The second diameter can be greater than the first diameter. The patterned assembly can have patterned features formed on its outer surface. The patterning assembly can be coaxially embedded into the sacrificial casting assembly. The polymer can then be filled into the gap between the patterned component and the sacrificial casting component. Once the polymer has cured, the sacrificial casting assembly can be disengaged leaving a cylindrical mask on the patterned assembly. The cylindrical mask can then be peeled off from the patterned assembly.

According to a further aspect, the cylindrical mask can comprise a cylindrical elastomer component having an inner radius and a rigid transparency having an outer radius Cylindrical component. A gas retainer can be constructed to hold a volume of gas between the inner surface of the elastomeric component and the outer surface of the rigid transparent cylindrical component. The elastomeric component has a major surface and the nanopattern is formed on this major surface. The outer radius of the rigid transparent cylindrical assembly is sized to fit within the cylindrical elastomer assembly.

In some embodiments, the gas holder can comprise two seals. Each seal seals a respective end of the volume of gas. Such a seal can be in the form of an O-ring or a leak-proof gasket.

In some embodiments, the volume of gas can be retained by a bladder disposed between the major surface of the elastomeric component and the major surface of the rigid transparent cylindrical component.

In some embodiments, the major surface of the cylindrical elastomer assembly having the nanopattern formed thereon is a cylindrical outer surface.

A "rolling mask" near field nanolithography system is described in the International Patent Application Publication No. WO2009094009, which is hereby incorporated by reference. One of the embodiments is shown in FIG. The "rolling mask" includes a glass (for example, a molten vermiculite) frame that becomes a shape of a hollow cylinder 711 in which a hollow cylinder 711 houses a light source 712. An elastomeric cylindrical rolling mask 713 that fits over the outer surface of the cylinder 711 has a nanopattern 714 that is fabricated in accordance with the desired pattern. Rolling mask 713 is brought into contact with substrate 715 coated with radiation sensitive material 716.

The nanopattern 714 can be designed to implement phase shift exposure Light, and in this case, is fabricated as an array of nanotrucks, struts, or cylinders, or may comprise features of any shape. Alternatively, the nanopattern can be fabricated into an array or pattern of nanometallic islands for plasmonic printing. The nanopattern on the rolling mask can have features ranging from about 1 nanometer to about 100 micrometers, preferably in the range of from about 10 nanometers to about 1 micrometer, and more preferably. It is in the range of from about 50 nanometers to about 500 nanometers. Rolling masks can be used to print features ranging in size from about 1 nanometer to about 1000 nanometers, preferably in the range of from about 10 nanometers to about 500 nanometers, and more preferably In the range from about 50 nm to about 200 nm.

The nanopattern 714 on the rolling mask 713 can be fabricated using a cylindrical master mold assembly. The aspects disclosed herein describe a cylindrical master mold assembly and method for forming a nanopattern on a rolling mask 713.

FIG. 8A is a top plan view of the main mold assembly 800. The master mold assembly 800 includes a cylindrical patterning assembly 820 and a sacrificial casting assembly 830. The cylindrical patterned assembly 820 can have a first radius R ₁ and the sacrificial casting assembly 830 can have a second radius R ₂ . In accordance with the first aspect disclosed herein, R ₁ can be greater than R ₂ to allow the sacrificial casting assembly 830 to be coaxially embedded into the interior of the cylindrical patterning assembly 820 with a space 840 therebetween.

Patterning component 820 can be made of a material that is transparent to optical radiation, such as infrared, visible, and/or ultraviolet wavelengths. By way of example and not limitation, the cylinder may be glass, such as molten vermiculite. Note It is meant that molten vermiculite is often referred to as "quartz" by semiconductor manufacturers. Although quartz is a common term, "melted vermiculite" is a preferred term. Technically, quartz is crystalline and molten vermiculite is amorphous. As can be seen in Figure 8B, the inner surface of the patterning assembly 820 can be patterned to have the desired pattern that will be used to form the nanopattern 714 on the cylindrical mask 713. 825. By way of example and not limitation, FIG. 825 may be applied to the cylinder as described in the section IV, which is incorporated herein by reference in its entirety herein by reference. The use of structured porous masks or self-organizing together with the photolithography techniques described in co-owned U.S. Patent Application Serial No. 13/756,348 (Attorney Docket No. RO-018-US). A single-layered (self-assembled monolayer (SAM)) mask is formed.

The sacrificial casting assembly 830 should be removable without damaging the nanopattern 714 after the cylindrical rolling mask 713 has been cured. In accordance with aspects of the present disclosure, the sacrificial casting assembly 830 can be a thin-walled cylinder formed from a material that is susceptible to cracking. By way of example and not by way of limitation, the material may be a glass, a sugar (Sugar), or aromatic hydrocarbons (aromatic hydrocarbon) resin, e.g. Piccotex ^TM, styrene or aromatic hydrocarbons ( aromatic styrene hydrocarbon) resins such as Piccolastic ^TM. Piccotex ^TM and Piccolastic ^TM is a trademark of Kingsport, Tennessee, Eastman Chemical Company of. By way of example and not limitation, the sacrificial casting assembly 830 can be approximately 1 to 10 mm (millimeters) thick, or within any thickness range encompassed by this range, such as 2 to 4 mm thick. The nanopattern 714 of the cylindrical mask 713 is not located on the surface of the sacrificial casting assembly 830, so the nanopattern 714 is less susceptible to damage during the removal of the sacrificial casting assembly. In accordance with additional aspects disclosed herein, the sacrificial casting assembly 830 can be made of a material that can be dissolved by a solvent that does not damage the patterning assembly 820 or the cylindrical mask 713. For example, a suitable soluble material can be a sugar based material and the solvent can be water. Dissolving the sacrificial casting assembly 830, rather than breaking it, provides additional protection to the nanopattern 714.

In accordance with additional aspects disclosed herein, the casting assembly 830 can be a thin walled sealing cylinder made of a malleable material such as plastic or aluminum. Instead of rupturing the sacrificial casting assembly 830, the sealed assembly can be removed by evacuating air from the interior of the cylinder to collapse the assembly. According to another aspect disclosed herein, the sacrificial casting assembly 830 can be a pneumatic cylinder made of an elastomeric material. Suitable elastomeric materials for the pneumatic cylinder examples include, but are not limited plastic, polyethylene (Polyethylene), PTFE (polytetrafluoroethylene (PTFE)), in which the PTFE-based name Teflon ^® sold, and Teflon ^® for the German Registered trademark of EI du Pont de Nemours and Company, Wilmington, Latvia. During the molding process, the sacrificial casting assembly 830 can be inflated to expand to form a cylinder, and once the cylindrical mask 713 has cured, the casting assembly 830 can be deflated to not damage the cylindrical mask. Was removed. In some embodiments, such a pneumatic cylinder can be reused or discarded depending on, for example, whether its manufacture is relatively inexpensive and easy to clean.

In FIG. 9, aspects of the disclosure describe a process 900 in which a cylindrical master mold assembly 800 can be used to form a cylindrical mask 713. First, at step 960, the sacrificial casting assembly 830 can be coaxially embedded into the cylindrical patterning assembly 820. Then, at step 961, the space 840 between the sacrificial casting assembly 830 and the cylindrical patterning assembly 820 is filled with a liquid precursor that forms an elastomeric material upon curing. By way of example and not limitation, the material may be poly bis methoxy oxane (PDMS).

Next, at step 962, the liquid precursor is cured to form an elastomeric material that will act as a cylindrical mask 713. For example, the curing process may need to be exposed to light radiation. The radiation source can be placed coaxially within the master mold assembly 800 when the wavelength of the radiation required by the sacrificial casting assembly 830 to cure the liquid precursor is transparent. Alternatively, a source of radiation can be placed outside of the master mold assembly 800, and exposure can be performed by the cylindrical patterning assembly 820. Once the cylindrical mask 713 has cured, the sacrificial casting assembly 830 can be removed at step 963. By way of example and not limitation, casting assembly 830 can be removed by rupture, dissolution, deflation, or collapse.

FIG. 10A is a top plan view of a cylindrical master mold assembly 1000 in accordance with additional aspects of the present disclosure. As shown, the cylindrical patterned assembly 1020 can have a first radius R ₁ and the sacrificial casting assembly 1030 can have a second radius R ₂ greater than R ₁ . The cylindrical master mold assembly 1000 is formed by coaxially embedding the cylindrical patterning assembly 1020 into the interior of the sacrificial casting assembly 1030 with a clearance space 1040 between the two components.

Patterning component 1020 can be made of a material that is transparent to optical radiation, such as infrared, visible, and/or ultraviolet wavelengths. By way of example and not limitation, the cylinder may be glass, such as quartz. As shown in the perspective view in FIG. 10B, a pattern 1025 is formed on the outer surface of the cylindrical patterning assembly 1020. By way of example and not limitation, pattern 1025 may be formed using nanolithography techniques such as, but not limited to, e-beam direct writing, deep ultraviolet (deep UV) Micro-image, nanosphere lithography, nanoimprint lithography, near-field phase shift lithography, and plasmonic lithography .

The sacrificial casting assembly 1030 can be removed without damaging the nanopattern 1014 after the cylindrical rolling mask 1013 has been cured. In accordance with aspects of the present disclosure, the sacrificial casting assembly 1030 can be a thin-walled cylinder formed from a material that is susceptible to cracking. By way of example and not limitation, the material may be glass. The nanopattern 1014 of the cylindrical mask 1013 is not located on the surface of the sacrificial casting assembly 1030, so the nanopattern 1014 is less susceptible to damage during the removal of the sacrificial casting assembly. In accordance with additional aspects disclosed herein, the sacrificial casting assembly 1030 can be made of a material that can be dissolved by a solvent that does not damage the patterning assembly 1020 or the cylindrical mask 1013. For example, a suitable soluble material can be a sugar based material and the solvent can be water. Dissolving the sacrificial casting assembly 1030 rather than breaking it provides additional protection to the nanopattern 1014.

After the sacrificial casting assembly 1030 has been removed, the cylindrical mask 1013 is maintained on the patterning assembly 1020 as shown in Figure 10C. To remove the cylindrical mask 1013 from the patterned assembly 1020, the cylindrical mask 1013 can be peeled back relative to itself. Starting from one end of the patterning assembly 1020, the cylindrical mask is pulled back over itself in a direction parallel to the axis of the patterning assembly 1020 such that the interior of the nanopattern 1014 is formed. The surface is revealed. Fig. 10D shows the case where the cylindrical mask 1013 has been partially removed during the removal process. In order to fold back onto itself during the removal process, the cylindrical mask 1013 should be relatively thin, such as 4 mm thick or thinner. Therefore, the difference between the first radius and the second radius should preferably be 4 mm or less. Once the entire cylindrical mask 1013 has been removed from the patterned assembly 1020, the cylindrical mask 1013 has been completely inverted to the inside and outside, thereby revealing the nanopattern 1014 on the outer surface as shown in Figure 10E. .

In FIG. 11, aspects of the present disclosure describe a process 1100 in which a cylindrical master mold assembly 1000 can be used to form a cylindrical mask 1013. First, at step 1160, the cylindrical patterning assembly 1020 is coaxially embedded within the sacrificial casting assembly 1030. Then, at step 1161, the space 1040 between the sacrificial casting assembly 1030 and the cylindrical patterning assembly 1020 is filled with a liquid precursor that forms an elastomeric material upon curing. By way of example and not limitation, the material may be poly bis methoxy oxane (PDMS).

Next, at step 1162, the liquid precursor is cured to form an elastomeric material that will act as a cylindrical mask 1013. For example In other words, the curing process may need to be exposed to light radiation. The radiation source can be placed coaxially within the master mold assembly 1000. Alternatively, if the wavelength of the radiation required by the casting assembly 1030 to cure the liquid precursor is transparent, the radiation source can be placed outside of the master mold assembly 1000, and exposure can be performed by sacrificing the casting assembly 1030. Once the cylindrical mask 1013 has cured, the sacrificial casting assembly 1030 can be removed at step 1163. By way of example and not limitation, the sacrificial casting assembly 1030 can be removed by rupturing and/or dissolving. Finally, at step 1164, the cylindrical mask is pulled back over itself in a direction parallel to the axis of the patterning assembly 1020 such that the inner surface of the nanopattern 1014 is exposed.

Figure 12A shows a cylindrical mask 1200 in accordance with additional aspects disclosed herein. The cylindrical mask 1200 is substantially similar to the cylindrical mask shown in Figure 7, with the addition of a gas retaining member 1218 positioned between the elastomeric rolling mask 1213 and the rigid hollow cylinder 1211. By way of example and not limitation, the elastomeric rolling mask 1213 can have a patterned surface 1214 and can be made in substantially the same manner as those described in the process 900 or 1100. . The rigid hollow cylinder can also be transparent to light radiation. By way of example and not limitation, the hollow cylinder can be glass, such as molten vermiculite. The light source 1212 can be placed inside the hollow cylinder 1211. The gas holder 1218 holds a volume of gas 1217 between the outer surface of the cylinder 1211 and the inner surface of the elastomeric shroud 1213. The gas retainer 1218 can be pressurized to provide an additional adjustable source of compliance for the elastomeric rolling mask 1213. By way of example and not limitation, the gas holder 1218 can be borrowed A pair of seals are formed or formed by an inflatable bladder.

FIG. 12B along line 6-6 of FIG. 12A taken sectional view showing a cylindrical rolling shield 1201, disclosed herein showing the gas holder member 1218 is a pair of seals aspect of _S 1218 is formed. Each seal 1218 _S can be a hollow cylinder, a ring, or a torus-like shape such as, but not limited to, an O-ring or a leak-proof gasket. Seal 1218 _S can be made of a suitable elastomeric material. At that time, the elastomeric mask 1213 can be spaced apart from the rigid hollow cylinder 1211 by a seal 1218 _S at each end. The inner radius of the elastomeric mask 1213 can be selected such that the volume of gas 1217 bounded by the inner surface of the elastomeric mask 1213, the seal 1218 _S , and the rigid outer surface of the rigid hollow cylinder 1211 can be pressurized . When the volume of gas 1217 is pressurized, the elastomeric mask 1213 will be rigid with the pressure of the volume of gas 1217 held between the inner surface of the elastomeric shroud 1213 and the outer surface of the cylinder 1211. The outer surfaces of the hollow cylinders 1211 are spaced apart. The cylinder 1211 can optionally include a groove that is sized and shaped to receive the seal 1218 _S and facilitates gripping the seal 1218 _S when the volume of gas is pressurized.

FIG 12C along line 6-6 in FIG. 12A taken sectional view of a cylindrical rolling shield 1202, which displays disclosed herein is the aspect of the gas holder 1218 1218 _B by the balloon member is formed. The bladder 1218 _B can be cylindrical in shape and positioned between the rigid hollow cylinder 1211 and the elastomeric shroud 1213. When the volume of the gas in the airbag 1218 _B 1217 is pressurized, the elastomeric bladder mask 1218 _B 1213 supported above an outer surface of a rigid hollow cylinder 1211.

III. Use successive transfer to map larger areas of the substrate

Aspects disclosed in this Section III include methods and apparatus for patterning a larger area of the main mask using a smaller area of the master mask using a successive imprinting scheme. A variety of other methods and devices are also included in this section. Successive transfer can be used to pattern relatively large area substrates for a variety of different purposes, which can provide a variety of benefits, including the ability to minimize or eliminate the visibility or effects of seams between the indicia. The various other advantages of this chapter will be apparent when reading this chapter.

It should also be noted that this Section III is applicable to the various aspects of the remaining sections I, II, and IV to VI described herein and can be readily implemented in such aspects, including but not limited to any that may involve a pattern These chapters on the use of components. By way of example and not limitation, the various aspects disclosed in this section III can be readily described herein as being described in the context of the use of a rolled laminate having a pattern to be made rotatable. The mask of the chapter V is implemented.

In an embodiment of the invention, a small main mask having a desired pattern can be used to inexpensively map a large area substrate. The small primary mask can be successively transferred onto a large area substrate using a polymeric or cured polymeric precursor liquid. The array of imprints is formed by a sequential transfer scheme in which each successive transfer overlaps a portion of the previous transfer so that there is no gap space that is not patterned. In this way, the desired pattern of the main mask is copied to produce a continuous pattern on the giant view, the size of which It is only limited by the size of the substrate. The sequential transfer scheme results in a large-area substrate with a patterned layer or structured coating having a boundary between individual marks or copies of the main mask that is hardly visible.

In an embodiment of the invention, a method of patterning a large area substrate may include transferring the substrate in a pattern having a main mask, wherein the pattern has an area that is smaller than the area of the substrate to be patterned. This method may additionally include repeating the transfer process one by one until the desired substrate area is patterned. Each successive transfer may comprise depositing a polymer precursor liquid, applying a pressure to the polymer precursor liquid between the main mask and the substrate, and polymerizing or curing the polymer precursor liquid such that the polymer precursor liquid becomes a solid material.

It is noted that in embodiments of the invention, the substrate to be patterned may be of a variety of different shapes, sizes, materials, etc., but should generally be larger than the primary mask used to transfer the substrates one by one. The primary mask can also be of a variety of different shapes, sizes, materials, etc., and can have a variety of shapes and sizes, but should be generally smaller than the substrate to be patterned. In embodiments of the invention, the substrate to be patterned may have a variety of different characteristics and may be, for example, a flexible, rigid, flat, or curved substrate. Likewise, the primary mask can have a variety of different characteristics and can be, for example, a flexible or rigid mask.

In embodiments of the invention, the desired pattern may include features having a variety of different different sizes, shapes, and configurations. The substrate can be given a variety of different physical or other properties by using patterns having a variety of different characteristics depending on the characteristics of the application.

Turning to Figures 13A to 13C, there is shown in accordance with the present invention. The main mask of the embodiment and the method of manufacturing a larger area substrate using the main mask.

In FIG. 13A, a main mask 1302 having a pattern 1304 is shown, wherein the pattern 1304 can be used to transfer to a larger area of the substrate by repeatedly transferring a larger area of the substrate with the main mask 1302. Although the main mask 1302 shown in FIG. 13A has a circular shape, and its pattern 1304 covers a rectangular area of the mask, it should be noted that both the main mask 1302 and the main pattern 1304 are in the embodiment of the present invention. The various shapes and sizes can be varied, and the main pattern 1304 can cover all or part of the main mask 1302. The primary pattern 1304 should correspond to the pattern desired for a large area substrate and can vary depending on the particular requirements of the various applications. For example, the primary pattern 1304 can comprise a uniform array or uniform array of ribs as used in many structured coating applications. It is noted that in the structured coating embodiment of the present invention, the array of struts is better than the array of holes because experiments have shown that the main pattern of the struts results in lower seam visibility at successive boundaries of the imprint. For example, Figures 13D and 13E provide photomicrographs of a strut array formed on a photoresist by exposure to UV light through a pattern of a cylindrical mask and developing the exposed resist.

FIG. 13B shows the main mask 1302 used to transfer a larger area of the substrate 1306. The primary mask 1302 can be used to repeatedly transfer a portion of the substrate 1306 until the desired area of the substrate is patterned. Each successive transfer of the main mask 1302 may overlap a portion of the previous transfer portion (imprint) 1308 of the substrate 1306 and remain on the substrate 1306. The pattern of imprint 1308 corresponds to main pattern 1304.

Figure 13C shows individual imprints during successive transfer of the transfer scheme in accordance with an embodiment of the present invention. In Figure 13C, it can be seen that the polymer precursor liquid 1310 is propagated as the liquid is pressed between the main mask 1302 and the substrate 1306. By way of example and not limitation, the polymeric precursor liquid 1310 can be a monomer, a polymer, a partially crosslinked polymer, or any mixture of the foregoing. The transfer scheme shown in Figures 13A to 13C according to an embodiment of the present invention should preferably include a method of controlling the propagation of the polymer precursor liquid to minimize the presence of bubbles to fill the characteristics of the main pattern. And preventing the liquid from flowing to the outside of the boundary of the mask pattern contained on the main mask and to the open area of the previously cured stamp. There are a variety of different methods that can be used to control the propagation of the polymer precursor liquid during each transfer. In the example shown in FIG. 13C, controlling the propagation of the polymer precursor liquid 1310 includes maintaining a continuous line of pressure along the line of contact 1312 between the main mask 1302 and the substrate 1306. Mechanical pressure may be applied along contact line 1312 to force the propagation of polymer precursor liquid 1310 toward the open area of substrate 1306 in the direction of pressure 1314 and to maintain liquid 1310 within the boundaries of main pattern 1304. In some embodiments, it may be preferable to maintain a continuous pressure line by using a flexible substrate on the substrate 1306 because a more clearly defined contact may be created between the main mask 1302 and the substrate 1306 using the flexible substrate. Line 1312. In other embodiments, a continuous pressure line can be conveniently maintained by using a flexible mask to the main mask 1302. In still other embodiments, by using a curved mask or The curved substrate can conveniently maintain a continuous pressure line at the mask 1302 or the substrate 1306. In still other embodiments, the propagation of the polymer precursor liquid 1310 can be controlled by other means.

Turning to Figures 14A through 14G, there is shown a process flow for a method of patterning a substrate in accordance with an embodiment of the present invention. In FIGS. 14A through 14G, a primary mask 1402 is used to pattern the substrate 1404, and the primary mask 1402 should be smaller than the substrate 1404. More specifically, the area of the main pattern 1406 of the main mask 1402 should be smaller than the area on the substrate 1404 to be patterned, and the main pattern 1406 should correspond to the desired pattern of the larger area of the substrate 1404. type. The main mask 1402 is used to pattern the substrate by successively transferring the substrate 1404 until the substrate 1404 is fully patterned or at least until the desired area of the substrate 1404 is patterned.

In FIG. 14A, a polymer precursor liquid 1408 is deposited on a substrate 1404, and a polymer precursor liquid 1408 corresponds to a patterned layer or structured coating of a larger area substrate 1404. It is noted that the polymer precursor liquid 1408 can be deposited in a variety of different ways. For example, in the embodiment illustrated in Figures 14A through 14G, polymer precursor liquid 1408 is deposited on substrate 1404 as a discrete drop for each successive transfer. In other embodiments, a polymer precursor liquid 1408 can be deposited on the primary mask 1402. In still other embodiments, the polymer precursor liquid 1408 can be deposited continuously throughout the patterning process as opposed to being discrete droplets prior to each transfer. It is noted that the materials used for the polymer precursor liquid 1408 can vary depending on the characteristics of the various applications. Deposited polymer precursor liquid 1408 The amount can vary depending on the particular requirements of the various applications including, for example, the thickness of the desired layer, the size of the desired transfer area, and the characteristics of the desired pattern to be formed. Depth and pitch.

In FIG. 14B, polymer precursor liquid 1408 is pressurized between main mask 1402 and substrate 1404 to transfer main pattern 1406 to polymer precursor liquid 1408. Pressing the polymer precursor liquid 1408 as shown in Figure 14B should preferably be carried out carefully and using a method of controlling the propagation of the polymer precursor liquid to minimize air bubbles during the transfer process, filling the main The features of pattern 1406 and the retention of polymer precursor liquid 1408 are maintained within the area of main pattern 1406. Controlling the propagation of the polymer precursor liquid can include, for example, maintaining a continuous pressure line as shown in Figure 13C and described above. In FIGS. 14A through 14G, pressing the polymer precursor liquid 1408 between the main mask 1402 and the substrate 1404 is shown pressing the main mask 1402 against the substrate 1404, but it should be noted that the present invention is not limited Such an embodiment. In an embodiment of the invention, applying pressure to the polymer precursor liquid between the main mask 1402 and the substrate 1404 may involve pressing the substrate 1404 against the main mask 1402. In other embodiments, the application of the polymer precursor liquid 1408 between the main mask 1402 and the substrate 1404 can be performed by other means, such as by simultaneously applying both the main mask 1402 and the substrate 1404. Apply pressure to press the two against each other.

In FIG. 14C, a curing means 1410 is used to cure or polymerize the patterned polymer precursor liquid, wherein the curing means 1410 can be a UV radiation source, a heat source, or other equivalent depending on the nature of the polymer precursor liquid. Means, and the nature of the substance is more specifically a polymer precursor liquid The mechanism by which curing or polymerization can be based. After the polymer precursor liquid is cured or polymerized, the primary mask 1402 can be removed and successive imprints can be formed.

In FIG. 14D, by depositing the polymer precursor liquid 1408 again, successive imprints can be formed to overlap a portion of the previously transferred and cured portion 1412. To minimize the visibility of the boundaries between successive imprints, a portion of the polymer precursor liquid should be deposited on the previously transferred portion 1412 of the substrate 1404. The main pattern 1406 will be previously transferred. A portion of the partially overlapping area is shown in Figure 14D.

In FIG. 14E, the polymer precursor liquid 1408 is again pressed between the main mask 1402 and the substrate 1404 to transfer the main pattern 1406 to the polymer precursor liquid and transfer the other portion of the substrate 1404. Share. It is to be noted that the flow of the polymer precursor liquid 1408 is controlled and prevented from flowing to the portion of the previously cured portion 1412 of the substrate that exceeds the boundary of the main pattern 1406.

In Figure 14F, curing means 1410 is again used to cure the polymer precursor liquid, and after curing, the main mask 1402 can be removed leaving a larger footprint on substrate 1404 as shown in Figure 14G. The patterning portion 1412. This process can be repeated sequentially until the substrate 1404 is fully mapped or until the desired area of the substrate 1404 is patterned.

After each portion of the substrate is transferred, the unpatterned regions of the substrate 1404 can be cleaned as desired by a wet or dry cleaning process. For example, the wet cleaning process can include the use of chemicals such as See organic solvents such as acetone, physical removal of particles, and/or plasma cleaning. The selective cleaning process of the unpatterned areas may require the use of a shadow mask (not shown) to prevent any damage to the patterned areas. To prevent any contamination or damage to the patterned area, the patterned area can optionally be selectively treated with hydrophobic silane. In other words, the patterned region can be rendered hydrophobic and the unpatterned region rendered hydrophilic. For example, the cleaning process may include a hydrophobic surface treatment (both of the patterned regions and the unpatterned regions), followed by plasma treatment of the unpatterned regions and the patterned regions will be during the next transfer. Overlapping area parts.

In a further embodiment, the patterned and unpatterned regions that become the checkerboard pattern are created on the substrate and treated with hydrophobic decane. The substrate is then plasma treated, wherein a shield mask is used such that only the unpatterned surface of the substrate and the surface to which the new imprint is to be overlapped are exposed to the plasma. Then, in the second step, all of the unpatterned areas of the substrate are transferred.

In Figures 15A through 15C, various different patterned substrates that are transferred in accordance with the methods described herein are shown. It is noted that embodiments of the present invention include a main mask and a main pattern having a variety of different shapes and sizes, and the successive prints can be configured in a variety of different different arrays and configurations. Likewise, larger substrates that are patterned with a main mask can be of various shapes, sizes, and the like.

The embodiment shown in Figures 15A through 15C shows a two-dimensional array and Configuration aspects, but it should be noted that the invention is not limited to such an embodiment. Embodiments of the invention may include various transfer schemes involving two-dimensional arrays of successive imprints in a transfer scheme, one-dimensional arrays of successive imprints, or other configurations that are formed by successive imprints. However, it should be noted that the two dimensional array and configuration aspects are preferred in some embodiments of the present invention because they minimize the visibility of seams between successive imprints.

In FIG. 15A, a substrate 1502a that is patterned into a two-dimensional rectangular array of successive imprints 1504a is shown. The pattern on substrate 1502a can be substantially continuous and uniform at the macro-level because the visibility of seam line 1506a at the boundary between successive imprints is minimal. In various applications of the invention, the appearance of the seam line has little or no effect on the desired functional properties of the patterned or structured substrate.

In FIG. 15B, a substrate 1502b having a two-dimensional hexagonal array of successive imprints 1504b is shown in accordance with an embodiment of the present invention.

In Figure 15C, the substrate 1502c is shown having a randomized two-dimensional configuration consisting of successive imprints 1504c, wherein randomized seam lines 1506c are created between successive imprints. Randomizing the imprint can provide certain benefits in some applications of the present invention, and the visibility of the seam line 1506c can be minimized at the macro level by setting a randomized pattern rather than a regular array. In Figure 15C, the substrate 1502c is shown to be fully patterned from edge to edge in accordance with some embodiments of the present invention, and the surface area that can be patterned is only It is limited by the size of the substrate selected.

It should be noted that increasing the amount of seam line to a certain limit minimizes the visibility of the seam lines while at the same time imparting the desired properties resulting from the pattern or structure being transferred to the substrate. There will be only minimal or no deductions. For example, in an architectural glass embodiment of an embodiment of the invention, a nanostructured coating can be applied by using a transfer scheme as described herein to provide anti-reflective properties on the glass. Increasing the number of seam lines minimizes the visibility of the seam line at the macroscopic level while still providing the desired anti-reflective properties provided by the nanostructure. This is a significant contrast to the known methods of attempting to minimize seam lines by drawing the entire large area into a single uniform layer at very high cost.

In embodiments of the invention, the substrates to be patterned may be of various shapes and sizes, but should generally be larger than the primary mask used to transfer the substrates one by one. In some embodiments, the substrate to be patterned may have a square shape, a rectangular shape, or other shape. In some embodiments, the substrate can be flat, curved, or have other three-dimensional surfaces. In some embodiments, the substrate can have a size of 150 mm x 150 mm or greater. In some embodiments, the substrate to be patterned may have a size of 400 mm x 1000 mm and may be larger. Embodiments of the invention may also include substrates having a smaller area than those described above, but it is believed that embodiments of the invention are directed to substrates having a larger area, such as substrates having an area of 200 cm ² (cm 2 ) or greater. The examples have particular applicability.

In embodiments of the invention, the primary mask can be of a variety of different shapes and sizes, and can have a variety of different shapes and sizes of graphics, but should be generally smaller than the area of the substrate to be patterned. In some embodiments, the mask may have a main dimension of 10mm to 50mm and 100mm ² to 2500mm ² in area. In other embodiments, the primary mask can have dimensions and areas outside of the ranges described above, but it is noted that the preferred embodiment includes a square mask having dimensions of 10 mm x 10 mm to 50 mm x 50 mm. In some embodiments, the primary mask can have a circular shape, a rectangular shape, or other shape. In some embodiments, the main pattern may cover the entire surface of the main mask or a portion of the surface of the main mask.

In an embodiment of the invention, the desired pattern may comprise a variety of different features of different sizes, shapes, and configurations. In some embodiments, the desired pattern may comprise microscale features, nanoscale features, or other scale features. In some embodiments, the features can include features having dimensions in the range of 100 nm to 400 nm. In some embodiments, the features can be shaped as holes, struts, or other shapes. In some embodiments, the features can be configured as a regular array or a randomized array.

It should be noted that the figures shown are primarily related to a flat substrate and the flat surface is patterned, but the invention is not so limited. Embodiments of the invention may be used to pattern curved surfaces or substrates having a variety of other shapes, but are primarily transferred by a primary mask having a smaller area than those described herein. surface.

It should be noted that embodiments of the present invention can be used to map a very large substrate to a pattern having a small feature size having a microscale or nanoscale. More specifically, embodiments of the invention can be used to A nanostructured coating having a nanoscale feature size is provided on the surface region. More specifically, embodiments of the present invention can be used to provide nanostructured coatings having an array of features such as pillars or holes, wherein the array of features has a characteristic dimension of 1 nanometer (nm) to 1000 nm (characteristic dimension ( CD)), 1.1 times the CD to 10 times the pitch of the CD, and a depth of 10 nm to 10000 nm. A preferred embodiment of the invention comprises a CD of between 50 nm and 400 nm, a 2x pitch of CD, and a depth in the range from 100 nm to 1000 nm. A CD is generally a dimension of a feature along a direction perpendicular to the depth. Examples of CDs include the width or diameter of a circular or nearly circular feature.

In an embodiment of the invention, the main mask pattern can be generated by a variety of different methods. For example, the main mask can be by electron beam lithography, photolithography, interference lithography, nanosphere lithography, nano transfer lithography, self-assembly, anode aluminum oxidation, or other The means are patterned.

It is noted that the substrates in the embodiments of the present invention can be of various different types of materials and various types of substrates. For example, the substrate can be made of plastic film, glass, semiconductor, metal, other smooth substrates, or other materials.

It is noted that substrates that are patterned in accordance with embodiments of the present invention include surfaces for a variety of different applications. For example, embodiments of the invention may be used in solar panels, information displays, architectural glass, and a variety of other applications. For example, embodiments of the present invention can be used for nanostructured solar cells, light absorbing enhancement layers, anti-reflective coatings Layer, self-cleaning coating, TCO for solar cells and displays, transparent electric cells, low-E glass Anti-icing coating, anti-glare coating, color filter for high efficiency displays, wire grid polarizer for FPD (flat panel display), LED ( Light-emitting diode) light-harvesting layer, nano-patterned magnetic media, nano-patterned water filtration media, nanoparticle for drug delivery, Ultra-sensitive sensors, nano electrodes for batteries, and other applications. It should also be noted that the patterned substrate in accordance with embodiments of the present invention can be used as a large mask that is itself used to pattern other large surfaces such as those described above.

It should be noted that a uniform pattern is typically used in a variety of different structured coating applications. Although the use of successive transfer as described herein may result in non-uniformities at the boundaries between the imprints, the entire area that is patterned may appear continuous on a macroscopic view and is desired by the pattern. The nature of the boundary will not be affected by the boundary, or it will be minimally affected by the boundary.

It should also be noted that although embodiments of the invention are primarily described in relation to two-dimensional imprint arrays, the invention is not limited to such embodiments. For example, embodiments of the invention may include a one-dimensional array of imprints, and other transfer schemes involving imprints that are repeated in only one dimension. However, it should be noted that the two-dimensional array and transfer scheme are repeated in two dimensions. Good because it minimizes the visibility of the boundaries between the imprints.

IV. Patterning the surface of the cast component

Aspects disclosed in this Section IV include methods and apparatus for patterning the surface of a cast component, including a variety of different exposure and epitaxial techniques. A variety of other methods and devices are also included in this section. Patterning the cast surface in accordance with aspects of this section can be used with a compliant layer casting process for a rotatable mask that can provide a variety of benefits, including any of the patterns that can be rotated. Seams are minimized or eliminated. The various other advantages of this chapter will be apparent when reading this chapter.

It should also be noted that this Section IV can be applied to various aspects of the remaining sections I through III, V, and VI described herein and can be readily implemented in such aspects, including but not limited to any that may involve a pattern These sections of the use of the casting assembly. By way of example and not limitation, the various aspects disclosed in this section IV can be readily applied to the rotary masks described herein that are used to form a multi-layered shape using a patterned casting assembly. The implementation of Chapter VI.

Aspects disclosed herein describe a mold and method of making a mold that can be used to fabricate a lithography mask, such as a near-field optical lithography mask for "rolling mask" lithography, or for nano-transfer. The mask of the lithography. In rolling mask lithography, a cylindrical mask is coated with a polymer that is patterned to have the desired features to obtain a mask for phase shift lithography or plasmonic printing. Features that are patterned into the polymer can be used The model described in this case is patterned. The mold may comprise patterned features protruding from an inner surface of an optically transparent cylinder (optical transparent cylinder). The features of the protruding features may range from about 1 nanometer to about 100 microns, preferably from about 10 nanometers to about 1 micrometer, and more preferably from about 50 nanometers to about 500 nanometers. The mask can be used to print features ranging in size from about 1 nanometer to about 1000 nanometers, preferably from about 10 nanometers to about 500 nanometers, and more preferably from about 50 nanometers to about 50 nanometers. About 200 nm.

Aspects disclosed herein describe molds that can be made with a porous mask. The structured porous material layer can be deposited or grown on the inner surface of the optically transparent cylinder. An example of the grown porous material is porous alumina (anodized aluminum oxide (AAO)) manufactured by anodization of an aluminum layer. The interior of the cylinder can then be coated with a radiation sensitive material. The radiation sensitive material will be filled in the pores formed in the structured porous material. The radiation sensitive material can then be developed by exposing the exterior of the cylinder with a light source. Exposure from the outside allows the radiation-sensitive material that has filled the voids to be cured without curing the remaining resist. The uncured resist and the porous mask material can be removed, thereby forming a mold having struts protruding from the inner surface thereof.

According to additional aspects disclosed herein, an epitaxial layer can be grown on the inner surface of the cylinder. The structured porous material can then be deposited or otherwise formed on the epitaxial layer. Then, the epitaxial layer can be grown using a hole in the porous layer as a guide. The epitaxial layer can be grown to a thickness greater than the thickness of the structured porous layer, or the structured porous layer can be deeply etched Etching back leaving the epitaxial pillars. According to certain aspects disclosed herein, the epitaxial material can be a semiconductor material. Each of the epitaxial pillars can be constructed as a light emitting diode (LED). The LED struts can be further constructed to be individually addressable such that radiation can be selectively generated by individual struts.

According to additional aspects disclosed herein, the mold can be formed from a self-assembled monolayer of nanospheres. A single layer can be formed overlying the layer of radiation-sensitive material that has been formed on the inner surface of the cylinder. The radiation sensitive material can then be exposed by a light source located inside the cylinder. The self-assembled monolayer masks portions of the radiation-sensitive material during exposure. The exposed area can then be removed by the developer. The radiation-sensitive material that is shielded by the self-assembled monolayer can then be cured to form pillars made of glassy material.

According to additional aspects disclosed herein, the self-assembled monolayer of formed nanospheres can comprise quantum dots. The quantum dots can be formed to overlie a layer of radiation-sensitive material that has been formed on the inner surface of the cylinder. Quantum dots can be used to expose radiation sensitive materials just below each point. As such, there is no need for an external light source. The developer can then remove the unexposed portions of the radiation sensitive material. The exposed portion of the radiation-sensitive material can then be cured to form a glassy substance.

In accordance with additional aspects disclosed herein, a self-assembled monolayer of nanospheres can be formed on the outer surface of the cylinder, and a radiation-sensitive material can be formed on the inner surface of the cylinder. A light source located outside of the cylinder can be used to generate radiation that exposes the radiation sensitive material. Nanosphere can shield the spoke The portion of the sensitive material is isolated from the radiation. The exposed portion can be removed with a developer, thus leaving a pillar. The struts can be cured to produce a glassy material.

According to further embodiments of the invention, the self-assembled monolayer may comprise quantum dots. Quantum dots can be formed on the outer surface of the cylinder. Quantum dots can be used to expose portions of the radiation-sensitive material that have been formed on the inner surface of the cylinder. As such, there is no need for an external light source. The developer can then remove the unexposed portions of the radiation sensitive material. The exposed portion of the radiation-sensitive material can then be cured to form a glassy substance. Radiation sensitive materials have been formed on the inner surface of the cylinder.

The "rolling mask" near-field nano-lithography system is described in International Patent Application Publication No. WO2009094009, which is incorporated herein by reference. One of the embodiments is shown in FIG. The "rolling mask" is composed of a glass (for example, a molten vermiculite) frame that is in the shape of a hollow cylinder 711, and the hollow cylinder 711 accommodates the light source 712. The elastomer film 713 attached to the outer surface of the cylinder 711 has a nano pattern 714 which is manufactured according to a desired pattern. The rolling mask is brought into contact with the substrate 715 coated with the radiation sensitive material 716.

The nanopattern 714 can be designed to perform phase shift exposure, and in this case is fabricated as an array of nanotrucks, struts, or cylinders, and can include features of any shape. Alternatively, the nanopattern can be fabricated into an array or pattern of nanometal islands for plasmonic printing. The nanopattern on the rolling mask can have features ranging in size from about 1 nanometer to about 100 micrometers, preferably from about 10 nanometers to about Within the range of 1 micron, and more preferably in the range of from about 50 nanometers to about 500 nanometers. Rolling masks can be used to print features ranging in size from about 1 nanometer to about 1000 nanometers, preferably in the range of from about 10 nanometers to about 500 nanometers, and more preferably In the range from about 50 nm to about 200 nm.

The nanopattern 714 on the cylinder 711 can be fabricated using the master mold. The aspects disclosed herein describe a master mold and a method for forming a master mold wherein the master mold has features that form a nanopattern 714 having holes or depressions. To form a hole or depression in the rolling mask, the master mold can have a protrusion, such as a post.

16 is a top plan view of a master mold 1600 in accordance with aspects disclosed herein. The master mold 1600 is a hollow cylinder 1620 having an outer surface 1621 and an inner surface 1622. Cylinder 1620 can be made of a material that is transparent to radiation at visible and/or ultraviolet wavelengths. By way of example and not limitation, the cylinder may be glass, such as molten vermiculite. The master mold 1600 has a protrusion 1633 that extends outwardly from the inner surface 1622.

17A to 17G are cross-sectional views of the main mold 1600 seen along line 3-3 shown in Fig. 16. Each view shows the processing steps used in the fabrication of the master mold 1600 in accordance with aspects disclosed herein.

FIG. 17A shows the master mold after the structured porous layer 1730 is formed on the inner surface of the cylinder 1720. By way of example and not limitation, the cylinder 1720 can be made of a transparent material such as molten vermiculite. Note that molten vermiculite is often referred to as "quartz" by semiconductor manufacturers. Although quartz is a common term, "melted vermiculite" is preferred. terms of. Technically, quartz is crystalline and molten vermiculite is amorphous. The structured porous layer 1730 contains high density cylindrical pores 1729 that are oriented perpendicular to the surface on which the structured porous layer is disposed. The size and density of the holes 1729 can be within any range of desirable features suitable for a mask pattern such as those discussed above with respect to FIG. By way of example and not limitation, nanostructured porous layer 1730 can be an anodized aluminum (AAO) layer that has been formed on inner surface 1722 of cylinder 1720. AAO is a self-organized nanostructured material containing a high density of cylindrical pores, wherein the pore system is oriented perpendicular to the surface on which the AAO layer is disposed. The AAO can be formed by depositing an aluminum layer on the inner surface 1722 of the cylinder 1720 made of molten vermiculite and then anodizing the aluminum layer. Alternatively, the cylinder 1720 can be made entirely of aluminum, and then the inner or outer surface of such a cylinder can be anodized to form a porous surface. Anodizing the aluminum layer can be carried out by passing an electric current through the electrolyte (usually an acid) by acting as a positive electrode (anode) in the aluminum layer.

In an alternative embodiment, the nanostructured porous layer can be fabricated using a self-assembled monolayer or by direct writing techniques such as laser ablation or ion beam lithography.

As shown in FIG. 17A, the holes 1729 may not penetrate the entire depth of the structured porous layer 1730. If the hole 1729 does not extend downward through the structured porous layer 1730 to the inner surface 1722 of the cylinder, the material of the structured porous layer can be etched back by etching (etch Back). If the etch process is isotropic, the original dimensions of the holes 1729 must be formed to be small enough to account for the growth during the etch process. For example, if the desired final diameter of the hole is 300 nm and the original diameter of the hole 1729 is 50 nm, the isotropic etching must remove the porous material of 125 nm to expand the diameter of the hole 1729 to 300 nm. Additionally, if the etching process is isotropic, only 125 nm of material can be removed from the bottom of the hole to extend the hole to the inner surface 1722 of the cylinder. If more material has to be removed to reach the inner surface 1722, the diameter of the hole 1729 can be larger than desired. Figure 17B shows the enlarged aperture 1729 extending completely through the nanostructured porous layer 1730.

After the holes 1729 have been etched to the correct size and depth, the radiation sensitive material 1731 can be deposited over the exposed portions of the nanostructured porous layer 1730 and the inner surface 1722, as shown in Figure 17C. By way of example and not limitation, the radiation-sensitive material 1731 can be deposited by dipping, spraying, rolling, or any combination of the above. By way of example and not limitation, the radiation-sensitive material 1731 can be a photoresist or a UV-curable polymer. Examples of suitable photoresists include commercially available formulations such as TOK iP4300 or Shipley 1800 from Dow Chemical Co. Examples of suitable UV curable materials include UV polymerizable adhesives for polymers and glass. Additionally, the radiation-sensitive material 1731 contains niobium and other components that allow the material to be annealed after it has been cured to produce a glassy material. Can be used to help form glassy materials Other ingredients include oxygen and helium. The radiation-sensitive material 1731 may be a solid film, or it may be a liquid layer as long as it does not excessively flow during exposure.

Next, Figure 17D shows the cured material 1732 in the hole 1729. Radiation sensitive material 1731 is cured by exposure to radiation 1723 from a source of radiation (not shown). By way of example and not limitation, radiation 1723 may be generated by a source of radiation that produces ultraviolet light, or radiation 1723 may be produced by a source of radiation that produces light in the visible spectrum. The radiation source can be located outside of the cylinder and can emit radiation 1723 that passes through the wall of the cylinder 1720. Exposure of material 1731 deposited in AAO holes 1729 is limited by illumination of cylinder 1720. Additionally, the exposure cures the material 1731 to a depth that is approximately twice the exposure wavelength. For example, when the ultraviolet wavelength is used to cure, the cured material 1732 can have a thickness of approximately 600 nm. The curing sensitivity of the radiation sensitive material 1731 must be sufficiently high to allow the radiation sensitive material inside the void 1729 to be cured prior to curing of the material 1731 above the void 1729. Also, the depth of the hole 1729 can be greater than the protruding thickness of the cured material 1732 to prevent exposure of the radiation-sensitive material 1731 just above the hole 1729.

Figure 17E shows the master mold 1700 after the excess radiation sensitive material has been removed after the cured material 1732 has been formed. The remaining unexposed radiation-sensitive material 1721 can be removed with a developer or other solvent. Then, as shown in FIG. 17F, the cured material 1732 is annealed to form a glassy material 1733. Finally, once the annealing is completed, The AAO layer 1730 can be selectively etched away by a wet etch process. Figure 17G shows the final structure of the master mold 1700. The glass material 1733 protrudes from the inner surface 1722 of the cylinder 1720.

According to further aspects disclosed herein, the protrusions can be formed via an epitaxial growth process. FIG. 18A is a plan view of the main mold 1800. The master mold 1800 is a hollow cylinder 1820 having an outer surface 1821 and an inner surface 1822. Cylinder 1820 can be made of a material that is transparent to radiation at visible and/or ultraviolet wavelengths. By way of example and not limitation, the cylinder may be glass, such as molten vermiculite. An epitaxial seed layer 1824 can be formed on the inner surface 1822. By way of example and not limitation, the epitaxial seed layer 1824 can be a semiconductor material such as germanium or gallium arsenide (GaAs). The master mold 1800 has a protrusion 1833 that extends outwardly from the epitaxial seed layer 1824. The protrusions can be the same material as the epitaxial seed layer 1824. 18B through 18D are cross-sectional views of the master mold 1800 taken along line 4-4 of Fig. 18A.

FIG. 18B shows a structured porous layer 1830 deposited over the epitaxial seed layer 1824. As shown in FIG. 18B, the holes 1829 may not penetrate the entire depth of the structured porous layer 1830.

When the holes 1829 do not extend downward through the structured porous layer 1830 to the epitaxial seed layer 1824, the material of the structured porous layer can be etched back by etching. If the etch process is isotropic, the original dimensions of the holes 1829 must be formed to be small enough to account for the growth during the etch process. For example, if the desired final diameter of the hole is 300 nm and the original diameter of the hole 1829 is 50 nm, then isotropic The 125 nm porous material must be removed by etching to expand the diameter of the hole 1829 to 300 nm. Additionally, if the etchant is an isotropic etchant, only 125 nm of material can be removed from the bottom of the hole to extend the hole to the epitaxial seed layer 1824. If more material has to be removed to reach the epitaxial seed layer 1824, the diameter of the hole 1829 can be larger than desired. FIG. 18C shows the enlarged aperture 1829 that extends completely through the structured porous layer 1830.

Once the holes 1829 have been completed, the protrusions 1833 can be formed using an epitaxial growth process, such as, but not limited to, vapor-phase epitaxy (VPE). The growth of the protrusion 1833 is guided by the holes 1829 in the structured porous layer 1830. The protrusion 1833 can be grown to allow the protrusion 1833 to protrude beyond the height of the structured porous layer 1830. However, if the structured porous layer 1830 is subsequently etched back to expose the protrusion 1833, the protrusion 1833 can be shorter than the structured porous layer 1830.

In accordance with aspects disclosed herein, the protrusions 1833 formed via epitaxial growth of the semiconductor material can be further constructed into LEDs (light emitting diodes). Each of the protrusions 1833 can be individually addressed such that each can be controlled to emit light as desired. This is beneficial for use as a master mold because no external light source is required for the molding process. The protrusion 1833 can function as a physical mold and can be used to simultaneously cure the mask being molded. In addition, the ability to control individual protrusions allows a single master to be used to form multiple differences by selecting which protrusions will also cure the material of the mask. The pattern.

In accordance with additional aspects disclosed herein, a self-assembled monolayer can be used as a mask to pattern the protrusion 1933 of the master mold 1900. 19A through 19C are cross-sectional views of the master mold 1900 at different processing steps during fabrication of the mold. FIG. 19A shows a self-assembled monolayer (SAM) 1940 overlying a radiation sensitive material 1931 over the inner surface 1922 of the cylinder 1920. By way of example and not limitation, SAM 1940 may be formed from metal nanospheres or quantum dots. By way of example and not limitation, the radiation-sensitive material 1931 can be a photoresist or a UV-curable polymer. Additionally, the radiation sensitive material 1931 contains niobium and other components that allow the material to be annealed to produce a glassy material.

Next, in Figure 19B, the radiation sensitive material 1931 is exposed from radiation 1923 from a source of radiation (not shown). If SAM 1940 contains metallic nanospheres, for example, plasmonic lithography can be used. Metal nanospheres can be used as plasmonic mask antennae. The portion of the radiation-sensitive material 1931 that is exposed to radiation can be soluble in the developer solvent used to develop the radiation-sensitive material. The unexposed portion 1932 of the radiation sensitive material can remain insoluble to the developer solvent. It is noted that the alternative aspects disclosed herein include the use of a reverse tone process in which a portion of the radiation-sensitive material 1931 exposed to radiation becomes insoluble to the developer and the unexposed portion of the radiation-sensitive material The portion remains soluble to the developer. The SAM1940 disclosed herein contains Alternative aspects of quantum dots may not require additional light sources to expose the radiation sensitive material 1931. As shown in Figure 19B', the quantum dots in the SAM 1940 can be activated to expose the radiation sensitive material 1931. When exposure is performed by quantum dots, the radiation-sensitive material can be cured by exposure. Therefore, the unexposed portion of the radiation-sensitive material 1931 can be removed by the developer. Finally, in Figure 19C, the protrusion 1933 is annealed to convert the cured radiation-sensitive material 1932 into a glassy material.

An alternative aspect disclosed herein includes the embodiment in which the mask itself is made of a light emitting diode (LED). Such a mask can be implemented, for example, using a polymeric mask, wherein the polymeric mask has an array of apertures that are smaller than the features that are desired to be printed, with the corresponding LED layer positioned over it. A particular subset of LEDs can be turned on to define the pattern to be printed.

In accordance with additional aspects disclosed herein, SAM 2040 can be formed on outer surface 2021 of cylinder 2020 as shown in FIG. 20A. The SAM2040 can be substantially similar to the SAM1940. The formation of the SAM 2040 that allows light to be exposed on the outer surface can be derived from the exterior of the cylinder 2020 as shown in Figure 20B. In FIG. 20B, the radiation sensitive material 2031 can be exposed with radiation 2023 emitted by a radiation source (not shown) located outside of the cylinder 2020. Alternatively, if the SAM 2040 contains quantum dots, the source of radiation that produces the radiation 2023 can be omitted, and as shown in Figure 23B', the quantum dots can alternatively be used to expose the radiation-sensitive material 2031. Finally, Figure 20C shows that the unexposed radiation-sensitive material is removed, And the protrusion 2033 is annealed to form a glassy material.

V. Use a rolled stack to form a rotatable mask

Aspects disclosed in this section V include methods and apparatus for using a rolled laminate to form a rotatable mask. A variety of other methods and devices are also included in this section. Forming a rotatable mask in accordance with aspects of this section can be used to form a compliant layer for a rotatable mask that can provide a variety of benefits, including reducing any seam where the edges of the stack meet Minimize or eliminate. The implementation aspects of this section can have a variety of other advantages.

It should also be noted that this section V may be applied to the various aspects of the remaining sections I to IV and VI described herein and may be readily implemented in such aspects, including but not limited to any that may involve being wound on a rotatable The sections of the compliant layer on the outer surface of the substrate. By way of example and not limitation, the various aspects disclosed in this section V can be readily applied to the embodiments described herein that relate to the use of a coaxial assembly to form a compliant layer.

A process flow for a method 2100 for fabricating a free standing polymer mask in accordance with various aspects disclosed herein is shown in Figures 21A-21G. The various steps in the process flow of Figures 21A through 21G can be implemented in accordance with the various aspects described above for forming a self-contained polymer mask.

Method 2100 can include first forming a patterned master mode/mask 2112 (here alternately referred to as a first master mask or "deputy master" A "submaster" mask because it can be a mask that is used to pattern the main rotatable mask for subsequent processes, as shown in Figures 21A and 21B. The patterned secondary main mask can be created by patterning the substrate 2105 to produce a pattern 2110 on the secondary main mask 2112. The patterning of the sub-master mask can be achieved in a variety of different ways. In some implementations, patterning the substrate to create a sub-master mask involves successively overlapping the cured imprints on the substrate 2105 with a smaller mask in accordance with various aspects disclosed in Section III herein. To create a quasi-seamless pattern 2110 for the sub-master mask. In other embodiments, the sub-master mask can be patterned using any of a variety of different known techniques, such as nanotransfer lithography, nanocontact printing, photolithography, and the like.

Method 2100 can additionally comprise casting elastomeric material 2115 (here alternatively referred to as a polymer precursor liquid or liquid polymer precursor) such as polydimethyloxane (PDMS) in sub-main mask 2112 On the patterned area, as shown in Fig. 21C. The cast elastomeric material 2115 can comprise a polymeric precursor liquid deposited on the secondary main mask and a cured polymeric precursor liquid to produce a cured polymer. Thus, aspects of the pattern of the sub-master mask 2112 can be transferred to the elastomeric material 2115 to form a patterned polymer mask upon curing. The elastomeric material 2115 can be cast such that a strip of elastomeric material 2115 is not cast over a strip portion 2120 of the patterned secondary main mask 2112. In some embodiments, this can be accomplished by removing or cutting a strip of cast material 2115 after curing of the cast material 2115. In other implementations, this can be done simply by not This is accomplished by casting the elastomeric material or by depositing a polymer precursor liquid on a portion of the patterned secondary main mask. In other embodiments, this can be achieved by some combination of the above. The uncast strip portion 2120 of the patterned secondary main mask 2112 can be positioned at the end of the secondary main mask so that it can be laminated with the laminate when it is rolled inside the casting assembly The opposite ends overlap.

Next, as shown in Fig. 21D, the strip portion 2125 can be removed from the sub-master mask of the laminate produced by the previous steps, so that the missing portion of the cured polymer 2115 is missing. 2120 and the lost strip portion 2125 of the patterned secondary main mask 2112 are at a staggered position relative to each other. The strip portion 2125 removed from the patterned sub-master mask can be positioned at the opposite end of the stack relative to the lost strip portion 2120 of the cured polymer, thereby allowing the laminate to be in these The strips are rolled up when they overlap each other. In some embodiments, the strip portion 2125 of the patterned secondary main mask 2112 can be removed prior to removal of the strip portion 2120 of the cast elastomeric material.

Then, as shown in FIG. 21E, the stack of the sub-master mask 2112 and the cast polymer 2115 can be rolled up and placed in the casting cylinder 2130, wherein the substrate 2105 of the sub-master mask 2112 is unpatterned. The surface is in contact with the inner surface of the casting cylinder 2130. Thus, the outer surface of the laminate can be adjacent to the inner surface of the casting cylinder 2130 when the laminate is rolled up. In some embodiments, the casting cylinder 2130 into which the laminate is rolled up is a sacrificial casting assembly and utilizes various aspects disclosed in Section II described herein.

Instead of winding the laminate in the interior of the sacrificial casting cylinder 2130 such that the unpatterned surface of the substrate 2105 is in contact with the inner surface of the casting cylinder 2130, in some embodiments, the laminate is wound into a sacrificial casting circle. The barrel, in accordance with various aspects disclosed in Section II described herein, causes the unpatterned surface of the sub-monitor substrate to contact the outer surface of the sacrificial casting cylinder.

The gap 2120 can be formed in the polymer mask 2115 along the length of the cylinder, and the gap 2120 can correspond to the strip portion 2120 of the elastomeric material 2115 being removed/uncast. The patterned portion of the submaster mold 2112 below the polymeric mask 2115 can be exposed from the gap 2120 and extend across the gap 2120. The staggered position of the removed/lost strip portions of the laminate may cause the laminate to be rolled such that the gap 2120 is exposed to the patterned portion of the sub-master mask 2112, but will not be due to overlapping portions Another seam is formed at the boundary between the opposite ends of the rolled stack.

Then, as shown in FIG. 21F, the gap 2120 can be filled with more liquid elastomeric material (ie, more polymer precursor liquid) to fill the gap 2120 in the cured polymer 2115. As such, the pattern on the sub-master mold 2112 can be transferred to the added elastomeric material upon curing to thereby fill the seam and form a substantially seamless polymer mask pattern. In some implementations, the filling gap can use various aspects disclosed in Section I. For example, in some embodiments, the coaxial cylinder can be assembled using an assembly device that allows the liquid polymer precursor to be poured into the gap.

After curing, the casting cylinder 2130 can be removed from the stack of sub-master molds 2112 and polymer masks 2115 that have been filled from the gap 2120. The polymeric mask 2115 can also be separated from the secondary master 2112 to create a self-contained polymeric mask having a substantially seamless pattern 2140 on the outer surface, as shown in Figure 21F.

In some embodiments, the cast elastomeric material is a PDMS having a thickness ranging from about 1 mm to about 3 mm to thereby produce a cylindrical mask having a compliant layer of 1 mm to 3 mm thick.

In some embodiments, the sub-master mold may have a PET (polyethylene terephthalate) film substrate, and the pattern may be formed on the PET film substrate using a UV-cured polymer.

Some embodiments disclosed herein can include self-existing polymeric masks and methods of making the same.

In some implementations, the method includes first forming a patterned main mode (the patterned main mode may alternatively be referred to herein as a main mask). Secondly, an elastomeric material such as polydimethylsiloxane (PDMS) is cast onto the patterned area of the master mold to form a patterned polymer mask upon curing (elastomer material can be used here) It is alternatively referred to as a polymer, a pre-polymer, a polymer precursor, or a polymer precursor liquid. The polymeric mask is constructed to have a lost portion at the end of the main mask mold, wherein a portion of the end of the polymeric mask can be truncated, or the elastomeric material can be uncast in the main mold On a strip at the end. The laminate of the mask mold and the polymer mask is then rolled up and placed in the casting cylinder such that the substrate of the master mold is in contact with the casting cylinder. Clearance along the circle The length of the barrel is formed in a polymeric mask wherein the gap corresponds to the lost portion of the cured polymeric mask and the master mold under the polymeric mask is exposed from the gap and extends across the gap. The gap is then filled with additional liquid elastomeric material. As such, the pattern on the master mold is transferred to the added elastomeric material upon curing and is thus filled into the seams in the polymer mask pattern. After curing, the stack of the master and polymer masks can be removed from the casting cylinder and the polymer mask can be separated from the master, thereby creating a self-contained polymer mask.

22A is a top plan view of a cylindrical master mold assembly 2230 that can be used to form a polymer mask in accordance with various aspects disclosed herein. The cylindrical master mold assembly 2230 includes a cast cylinder 2223, a master mold 2234, and a patterned polymer mask 2236 having a gap 2237 along the length of the cylinder. Figure 22B is a perspective view of the cylindrical main mold assembly shown in Figure 22A.

The patterned polymeric mask 2236 can be patterned into a masked pattern in a variety of different ways. In one example, the inner surface of the master mold can contain a mask pattern such that the pattern is transferred to the outer surface of the polymeric mask. As another example, the polymeric mask can be patterned after subsequent manufacturing steps and removal of the casting cylinder by using various lithography methods to pattern the outer surface of the polymer. As another example, the pattern can also be patterned by a combination of the above.

Once the substrate of the master mold 2234 is patterned, the elastomeric material can be cast onto the patterned regions of the master mold 2234. In some aspects of the embodiments, the elastomeric material may be a poly silicon bis methyl siloxane (PDMS), Dow Corning ^TM is e.g. Sylgard 184, h-PDMS (hard PDMS), PDMS soft gel. The elastomeric material can be deposited according to any of several known methods. By way of example and not limitation, the elastomeric material may be deposited by dipping, ultrasonic spraying, microjet or inkjet dispensing, and possibly in combination with spin impregnation. After the curing process, a polymer such as PDMS is cured to form a patterned polymeric mask 2236 on the master mold 2234. The cured polymer can depend on the type of polymer being cured and other factors. For example, curing can be carried out using thermal energy, UV radiation, or other means.

The stack of master mold 2234 and polymer mask 2236 is rolled up and coaxially embedded into casting cylinder 2232 such that the substrate of master mold 2234 is in contact with casting cylinder 2232 (i.e., adjacent the outer surface of the laminate) On the inner surface of the casting cylinder). Because a portion of one end of the polymeric mask 2236 has been lost, the gap 2237 is formed in the polymeric mask along the length of the cylinder 2232, and the underlying master mold is exposed from the gap and extends across the gap. The strip portion 2239 of the master mold 2234 (i.e., the patterned substrate) can also be removed from the stack at a position staggered relative to the gap 2237 so that the laminate can be rolled without seams. Inside the cylinder 2232. The lost strip portions 2237, 2239 of the laminate can be positioned at opposite ends of the laminate to allow the laminate to be rolled up with the ends of the laminate overlapping each other, as shown in Figures 22A and 22B. .

The casting cylinder 2232 should be removed after the cylindrical master mold assembly disclosed herein is formed. In accordance with aspects disclosed herein, the casting cylinder 2232 can be a thin-walled cylinder formed of a material that is susceptible to cracking. By way of example and not by way of limitation, the material may be a glass, a sugar, or an aromatic hydrocarbon resin, e.g. Piccotex ^TM, styrene or aromatic hydrocarbon resins such as Piccolastic ^TM. Piccotex ^TM and Piccolastic ^TM is a trademark of Kingsport, Tennessee, Eastman Chemical Company of. By way of example and not limitation, the casting cylinder 2232 can be approximately 1 mm to 10 mm thick, or within any thickness range encompassed by this range, such as 2 mm to 4 mm thick. As shown in Figure 22A, the polymeric mask 2236 is not in contact with the casting cylinder 2232, so the nanopattern on the polymeric mask is protected from damage during removal. In accordance with additional aspects disclosed herein, the casting cylinder 2232 can be made of a material that can be dissolved by a solvent that does not damage the polymeric mask 2236. For example, a suitable soluble material can be a sugar based material and the solvent can be water. Dissolving the casting cylinder 2232 instead of breaking it provides additional protection to the nanopattern.

In accordance with additional aspects disclosed herein, the casting cylinder 2232 can be a thin walled sealing cylinder made of a malleable material such as plastic or aluminum. Instead of rupturing the sacrificial casting cylinder 2232, the sealed assembly can be removed by evacuating air from the interior of the cylinder to collapse the assembly. According to another aspect disclosed herein, the casting cylinder 2232 can be a pneumatic cylinder made of an elastic material. Suitable elastomeric materials for the pneumatic cylinder examples include, but are not limited plastic, polyethylene (Polyethylene), PTFE (polytetrafluoroethylene (PTFE)), in which the PTFE-based name Teflon ^® sold, and Teflon ^® for the German Registered trademark of EI du Pont de Nemours and Company, Wilmington, Latvia. During the molding process, the casting cylinder 2232 can be inflated to expand to form a cylinder, and once the polymeric mask 2236 has cured, the casting cylinder 2232 can be deflated to be undamaged without damaging the polymeric mask. Remove. In some embodiments, such a pneumatic cylinder can be reused or discarded depending on, for example, whether its manufacture is relatively inexpensive and easy to clean.

Next, a gap 2237 in the polymer mask 2236 along the length of the cylinder is filled with a polymer, such as liquid PDMS. During the curing process, the pattern on the master mold 2234 is transferred to the added polymer. As such, the cylindrical master mold assembly 2230 of Figures 22A and 22B can be formed.

Curing the liquid polymer can involve applying UV radiation, heat, or other means. As an example of the application of radiation, the radiation source can be coaxially located within the main mold assembly 2230. Alternatively, when the casting cylinder 2232 and the main mold 2234 are transparent to the wavelength of radiation required to cure the liquid polymer, the radiation source can be positioned outside of the main mold assembly 2230, and exposure can be through the casting cylinder 2232 and the main The modulo 2234 is implemented.

The stack of master mold 2234 and patterned polymer mask 2236 can then be removed from casting cylinder 2232. Removal of the casting cylinder can be carried out in a variety of different ways. By way of example and not limitation, the casting cylinder 2232 can be removed by cracking, dissolving, deflation, or collapse. By way of example and not limitation, the casting cylinder can be cut by using a saw, laser, wet or dry etch, or other means. When cutting the casting cylinder, care must be taken not to damage the layer/mask underneath. If a laser is used to cut the casting cylinder, a special layer of material can be deposited on the inner surface of the casting cylinder to act as an etch stop layer, and this material The layer should be reflective to the light used to cut the cast cylindrical material. Cutting can be performed by using one or more cut lines to facilitate subsequent stripping of the casting cylinder from the laminate. Once the casting cylinder is cut, the casting cylinder can be mechanically stripped from the laminate. By way of example and not limitation, the casting cylinder can be chemically etched by using an etch chemistry that does not etch away the main mold and polymer mask therein. The casting cylinder can also be removed by other means, and such other removal means are also within the scope of the invention. In some embodiments, the casting cylinder 2232 is a sacrificial casting assembly in accordance with various aspects of Section II described herein.

Second, the polymer mask 2236 can be separated from the master mold 2234, for example by peeling it off, resulting in a self-contained PDMS mask having a thickness of 1 mm to 3 mm.

Aspects disclosed herein include a process 2300 that can use a cylindrical master mold assembly 2230 to form a self-contained polymer mask. A flow chart showing a process 2300 incorporating the various aspects disclosed above is shown in FIG. Various aspects of process 2300 are also described with reference to main mode assembly 2230 of Figures 22A and 22B. First, at step 2310, the master mode 2234 is patterned. The master can be patterned by successively transferring the master with a smaller main mask. At step 2320, a patterned polymeric mask is formed by casting an elastomeric material or polymer onto the master mold 2234 and curing the material/polymer. At step 2330, the stack of master mold 2334 and patterned polymer mask 2236 is rolled up and coaxially embedded into casting cylinder 2232. At step 2340, the patterned polymer mask The gap is filled with a liquid polymer. At step 2342, the liquid polymer is cured during the curing process and thus transfers the pattern along the gap along the master to the cured polymer. At step 2350, the casting cylinder 2232 and the master mold 2234 are removed to form a self-contained polymer mask.

VI. Using a casting assembly to form a multi-layered mask

Aspects disclosed in this Section VI include methods and apparatus for forming a multi-layered mask in a plurality of stages using a coaxial cast assembly. A variety of other methods and devices are also included in this section. A multi-layered mask according to aspects of this section can be used to form a compliant layer for a rotatable mask that can provide a variety of benefits, including allowing the rotatable mask to include additional cushioning and compliance Sex. The implementation aspects of this section can have a variety of other advantages.

It should also be noted that this section VI can be applied to various aspects of the remaining sections I to V described herein and can be readily implemented in such aspects, including but not limited to any that may involve forming a rotatable mask. Patterning the sections of the compliant layer. By way of example and not limitation, the various aspects disclosed in this section VI can be readily applied to the embodiment of the section IV of the drawings relating to the surface of the casting assembly described herein.

Aspects disclosed herein include a multilayered polymeric mask and methods of making the same. The method of making a multilayered polymeric mask can involve two stages.

Figure 24A shows some implementations in accordance with the disclosure herein. A top view of the cylindrical master mold assembly in the first stage to form a multi-layered polymeric mask. The cylindrical main mold 2410 is formed with features/patterns on the inner surface of the cylinder. Second, the first casting cylinder 2420 is coaxially embedded into the master mold 2410 to create a cylindrical region between the casting cylinder 2420 and the master mold 2410. Next, the cylindrical region between the casting cylinder 2420 and the master mold 2410 is filled with a liquid polymer to form a patterned polymer mask 2430 upon curing. Then, the first casting cylinder 2420 is removed, and the polymer mask 2430 is peeled off from the inside of the cylindrical main mold 2410. In this way, a self-contained polymer mask can be formed. In some embodiments, the self-contained polymer mask 2430 can alternatively be formed using aspects of Section V described herein, wherein the laminate is drawn into the cylinder and filled in the gap of the laminate. To create a substantially seamless pattern on the cylindrical mask. In some embodiments, the self-existing polymer mask 2430 is formed using various aspects of Section II described herein, including where the first casting cylinder 2420 is a sacrificial component and the removal of the first casting cylinder is Implementations implemented in accordance with aspects of this section. In some embodiments, the cylindrical main mask is formed by patterning the inner surface of the cylinder in accordance with various aspects of Section IV described herein.

24B shows a top view of a cylindrical master mold assembly in a second stage to form a multi-layered polymeric mask in accordance with some embodiments disclosed herein. The polymer mask 2430 is covered by the protective film 2432 and embedded in the second casting cylinder 2440, wherein the protective film abuts against the inner surface of the second casting cylinder 2440. The mask cylinder 2450 of molten vermiculite is in turn coaxially embedded in the second casting cylinder 2440 and the polymer covered by the film A cylindrical region is created within the mask 2430 and thus between the masking cylinder of the molten vermiculite and the inner diameter of the polymeric mask 2430. This gap (cylindrical region) is then filled with a liquid polymer to form a buffer layer 2460 upon curing. Then, the second casting cylinder 2440 and the protective film 2432 are removed. As a result, a multilayered polymer mask is formed. In some embodiments, the second casting cylinder 2440 is also a sacrificial casting assembly in accordance with various aspects of Section II described herein, thereby permitting additional formation by repeating a process similar to the second stage. Floor.

2 shows an assembly 200 that can be used to form a patterned polymer mask in accordance with various aspects disclosed herein. In some embodiments, the aspects disclosed herein can be used in the first stage of the polymeric mask described above for forming a multilayer. Assembly 200 includes a master mold 204 and a first casting cylinder 202 that is surrounded by a master mold 204. The first casting cylinder 202 can correspond to the first casting cylinder 2420 of Figure 24A. The first casting cylinder 202 may also correspond to a sacrificial casting cylinder, such as the sacrificial casting assembly 830 of Figure 8A. The master mold 204 and the casting cylinder 202 are coaxially assembled in alignment with their axes 206, thereby creating a cylindrical region 208 having a uniform thickness around the master mold 204, and the cylindrical region 208 can be defined The shape of the polymer layer of the cylindrical mask. The outer diameter of the casting cylinder 202 is greater than the outer diameter of the masking cylinder 2450 of the final molten vermiculite of the multilayered mask. The polymer precursor can be injected into the space 208 between the master mold 204 and the casting cylinder 202. The master mold 204 and the casting cylinder 202 can be held in position by use of an assembly device (not shown) that aligns the axes of the master mold 204 and the casting cylinder 202 and allows The liquid polymer is injected into the cylindrical region 208 of the assembly, such as by pouring a liquid polymer through an opening or aperture of the assembly device. Injection of the polymer precursor can be carried out, for example, by casting a liquid or semi-liquid polymer precursor material through the top of the assembly device into the space between the master mold 204 and the cylinder 202. The polymer precursor can be in the form of a monomer, a polymer, a partially crosslinked polymer, or any mixture of the above, in liquid or semi-liquid form. The polymer precursor can be cured to form the inner polymeric layer of the cylindrical mask. Curing the polymer precursor can involve applying UV radiation or heat. The pattern on the inner surface of the master mold 204 can be transferred to the outer surface of the polymer during the curing process.

In the first stage described above, patterning the inner surface of the master mold 2410 can be implemented using a variety of different techniques. For example, the inner surface of the master mold can be patterned by successively transferring the inner surface of the master mold with a smaller primary mask as described in Section III, described herein above. As another example, a cylindrical surface can be patterned by using any of a variety of different known techniques, including nano transfer lithography, nanocontact printing, photolithography, and the like.

In the first stage described above, the casting cylinder 2420 can be removed. The patterned polymeric mask can in turn be stripped from the master mold 2410 to form a self-contained polymeric mask having a thickness of between about 1 mm and 3 mm. It is noted that the removal of the casting cylinder 2420 and the polymeric mask 2430 can be implemented in a variety of different manners, including the various manners described above in this disclosure.

In the first stage described above, the polymer mask 2430 can be The protective film or protective layer 2432 is covered. In one example, the protective layer can be a polyethylene terephthalate (PET) film. A protective layer 2432 can be deposited on the polymer mask 2430, and then the film covered polymer mask 2430 is coaxially embedded into the second casting cylinder 2440, wherein the protective film 2432 abuts the second casting cylinder 2440 The inner surface. The inner diameter of the second casting cylinder 2440 is equal to the inner diameter of the main mold 2410 used in the first stage described above. The second casting cylinder 2440 can be a thin-walled cylinder formed of a material that is susceptible to cracking thereof, such as those discussed in connection with the casting cylinder 2232 of Figures 22A and 22B, or with reference to the sacrificial casting assembly of Section II. Narrator. In some embodiments, the protective film can cause the second casting cylinder 2440 to be made from a plurality of separate components.

In the second stage described above, a mask cylinder 2450 for a substrate of a rotatable mask, such as molten vermiculite, is coaxially embedded within the second casting cylinder 2440 and the polymeric cover 2430 covered by the film. The mask cylinder 2450 of molten vermiculite may be a hollow cylinder having an outer diameter that is smaller than the inner diameter of the polymer mask 2430, thus creating between the outer surface of the mask cylinder and the inner surface of the polymer mask 2430. A cylindrical region having a uniform thickness surrounding the mask cylinder 2450.

In the second stage described above, the cylindrical region created between the polymeric mask 2430 and the masked cylinder 2450 of molten vermiculite is filled with a liquid polymer and thus within the polymeric mask upon curing. A buffer layer 2460 is formed at the surface. The liquid polymer can be cast into the cylindrical region in a variety of different ways, including in a variety of different manners as described above in this disclosure.

In the second stage described above, the second casting cylinder 2440 can be removed. Also, the protective film 2432 can be separated from the polymer mask 2430 having the cured buffer layer 2460. As a result, a multilayered polymer mask comprising a polymer mask 2430 and a buffer layer 2460 can be formed. Removal of the casting cylinder and protective film can be carried out in a variety of different manners, such as the various manners described above in this disclosure.

Aspects disclosed herein include a process 2500 in which a cylindrical master mold assembly 2400 and 2401 can be used to form a multilayer polymer mask. A flow chart showing a process 2500 that can include various aspects disclosed above is shown in FIG. Various aspects of process 2500 are also described with reference to Figures 24A and 24B. At step 2510, the process or method 2500 can include patterning the master mold/mask 2410 such that the inner surface of the master mold includes a pattern. At step 2520, the patterned master mold 2410 is assembled coaxially with the first casting cylinder 2420 such that the axes of both the master mold and the cylinder are the same. The first casting cylinder 2420 may be a hollow cylinder having an outer diameter smaller than the inner diameter of the main mold 2410 such that the space is left between the main mold and the cylinder. At step 2530, the space between the master mold 2410 and the casting cylinder 2420 is filled with a liquid polymer precursor, resulting in a polymeric mask that becomes patterned upon curing. At step 2540, the first casting cylinder 2420 is removed and the patterned polymer mask 2430 is stripped from the master mold 2410, thereby forming a self-contained polymer mask. In some embodiments, the casting cylinder 2420 can be a sacrificial casting assembly in accordance with various aspects of Section II described herein such that the main mold 2410 can be saved for future use, thereby allowing the casting cylinder 2420 to be Broken, dissolved, collapsed and removed, Alternatively, the casting cylinder 2420 can be removed to allow the cured polymer to be subsequently removed from the master mold 2410 at step 2540 after removal of the casting cylinder 2420. At step 2550, the polymer mask 2430 is covered by a protective layer or film 2432. At step 2560, the film covered polymer mask 2430 is coaxially embedded within the second casting cylinder 2440. At step 2570, the mask cylinder 2450 of molten vermiculite is coaxially embedded into the second casting cylinder 2440 and the mask 2430 covered by the film. The mask cylinder 2450 of molten vermiculite may be a hollow cylinder having an outer diameter that is smaller than the inner diameter of the polymer mask 2430, thus leaving a space left between the cylinder and the mask. At step 2580, the space between the mask cylinder 2450 of molten vermiculite and the polymer mask 2430 is filled with an additional liquid polymer precursor, thereby forming a buffer layer 2460 upon curing. At step 2590, the casting cylinder 2440 and the protective film can be removed to form a multi-layer polymeric mask. In some embodiments, the casting cylinder 2440 can also be a sacrificial casting assembly.

The formation of a multi-layered mask in accordance with various aspects disclosed herein can provide several advantages. For example, a casting cylinder, such as the first casting cylinder 2420 described above that is used to form the outer layer, can be made from a separable component having seams, thereby potentially simplifying the process and reducing cost. A polymer used to form a layer in contact with a surface that is not patterned, such as the polymer (buffer layer) 260 described above, which is used to form an inner layer adjacent to the inner surface of the outer layer 2430, may also be filled in Within the seam created by the use of such a separable component. Similarly, in some embodiments disclosed herein, a protective film disposed over the surface of the pattern can be cast The tubular member, such as the second casting cylinder 2440 described above, can be made of a detachable component such that the protective film prevents the seam of the detachable component from being transferred to the patterned features covered by the film. Additionally, in some embodiments, the mold or mask used for the casting process, such as the cylindrical master mold 2410, does not have to be broken to remove the molded material, so it can be preserved for future use and prevented from molding. The material was damaged due to breaking the treatment.

Those skilled in the art can readily appreciate that various aspects disclosed herein can be combined with various other aspects without departing from the scope of the present disclosure. The various aspects disclosed in the above Sections I through VI can be readily incorporated into the teachings disclosed herein by way of example and not by way of limitation. Manufacturing methods and innumerable variations in the rotatable mask.

It is noted that the various aspects disclosed herein have been described with reference to a multi-layered mask that generally has two compliant layers. It should be noted that the aspects disclosed herein can be readily implemented to form a multi-layered mask having more than two compliant layers.

It is further noted that the various aspects disclosed herein have been described with reference to a rotatable mask having a cylindrical shape. It should be noted that the aspects disclosed herein can be readily implemented in rotatable masks having other shapes, such as shapes containing truncated cone elements or other axially symmetric shapes.

It is also noted that the various aspects disclosed herein can be reversed, exchanged, reordered, etc., on different desired surfaces. A seamless or quasi-seamless feature pattern is produced, such as on the inner or outer surface of the casting cylinder, the final mask cylinder, the layer, or other components used in the process.

More generally, it is important to note that while the above is a complete description of the preferred embodiments of the invention, various alternatives, modifications, and equivalents are possible. Therefore, the scope of the invention should be determined not by reference to the above description, but rather by the scope of the accompanying claims and their full equivalents. Any feature described herein, whether preferred or not, can be combined with any of the other features described herein, whether preferred or not.

In the accompanying claims claim, the indefinite article "a" or "an" refers to an indefinite article when used in a request containing an open transitional term such as "comprising". Subsequent items have one or more quantities, unless otherwise stated otherwise. In addition, the use of the word "said or the" to refer back to the same claim term above does not change its meaning, but merely re-inspires that it is not a singular meaning. The accompanying claims are not to be construed as limiting the meaning of the means of the means or the limitation of the function of the step, unless the use of the words "means for" or "step for" It is clearly recorded in a given request.

408‧‧‧ hole

402a‧‧‧First board

412‧‧‧mask cylinder

414‧‧‧casting cylinder

406‧‧ sales

402b‧‧‧second board

Claims (195)

A method of manufacturing a cylindrical mask, comprising: assembling a hollow casting cylinder coaxially with a mask cylinder, wherein one of the casting cylinder and the mask cylinder has a casting cylinder and the mask An outer diameter of the outer diameter of the other of the cylinders; a liquid polymer precursor is injected into the space between the casting cylinder and the mask cylinder; solidified in the casting cylinder and the mask cylinder The liquid polymer in the space between the precursors, thereby forming a layer of cured polymer; removing the casting cylinder leaving the layer of cured polymer on the surface of the mask cylinder; The surface of the cured polymer is patterned. The method of manufacturing a cylindrical mask according to claim 1, wherein the coaxial assembly comprises using an assembly device having a first plate member, a second plate member, and a pin, wherein the pin is constructed The first plate member and the second plate member are fastened together at opposite ends of the casting cylinder and the mask cylinder, wherein the injecting of the liquid polymer precursor comprises pouring the liquid polymer precursor Passing through the hole of the first plate. The method of manufacturing a cylindrical mask according to claim 2, wherein the first plate has a first groove aligned with the mask cylinder, and a first alignment with the casting cylinder Two grooves, and the second plate has a first groove aligned with the mask cylinder and a second groove aligned with the casting cylinder. The method of manufacturing a cylindrical mask as described in claim 1 of the patent application scope The method wherein the casting cylinder has an inner diameter that is greater than an outer diameter of the shroud cylinder, wherein the casting cylinder has a patterned inner surface, wherein the patterning of the polymer comprises using the patterning The inner surface transfers the pattern on the patterned inner surface to the surface of the polymer. The method of manufacturing a cylindrical mask according to claim 4, further comprising patterning the inner surface of the casting cylinder prior to the coaxial assembly. A method of manufacturing a cylindrical mask according to claim 5, wherein the patterning of the inner surface of the casting cylinder comprises performing an anodizing treatment to produce a nanoporous surface. The method of producing a cylindrical mask according to claim 6, wherein the casting cylinder is made of aluminum. The method of producing a cylindrical mask according to claim 6, wherein the casting cylinder has aluminum deposited on an inner surface thereof. The method of manufacturing a cylindrical mask according to claim 5, wherein the patterning the inner surface of the casting cylinder comprises: depositing self-assembled nanoparticles in the casting cylinder On the inner surface; etching the inner surface of the casting cylinder using the nanoparticle as an etching mask; and removing the nanoparticle. The method of producing a cylindrical mask according to claim 9, wherein the nanoparticle is a nanosphere. Manufacturing a cylindrical mask as described in claim 5 The method wherein patterning the inner surface of the casting cylinder comprises successively transferring the inner surface of the casting cylinder with a primary mask having a smaller area of the pattern. A method of manufacturing a cylindrical mask according to claim 5, wherein the patterning of the inner surface of the casting cylinder comprises performing nano transfer lithography. A method of making a cylindrical mask according to claim 5, wherein the patterning of the inner surface of the casting cylinder comprises performing nanocontact lithography. A method of manufacturing a cylindrical mask according to claim 5, wherein the patterning of the inner surface of the casting cylinder comprises performing photolithography. A method of producing a cylindrical mask according to claim 1, wherein the patterning of the polymer comprises patterning the outer surface of the polymer after the removal. The method of manufacturing a cylindrical mask according to claim 1, wherein the patterning of the polymer comprises using a mask cylinder having a patterned outer surface such that the pattern is externalized. The pattern of the surface is transferred to the inner surface of the polymer during the method of making the cylindrical mask. The method of manufacturing a cylindrical mask according to claim 1, further comprising: depositing a liquid polymer on an inner surface of the casting cylinder before the coaxial assembly; and assembling the coaxially Previously cured on the inner surface of the casting cylinder The polymer is such that the injection of the liquid polymer precursor comprises injecting the liquid polymer precursor into the space between the outer surface of the mask cylinder and the inner surface of the cured polymer. A cylindrical mask manufactured by the method of manufacturing a cylindrical mask according to claim 1, wherein the cylindrical mask comprises: a mask cylinder; and a mask cylinder A seamless polymer layer on the outer surface, wherein the seamless polymer layer has a pattern on the surface of the seamless polymer layer. A cylindrical mask as described in claim 18, wherein the pattern is seamless. A cylindrical mask manufactured by the method of manufacturing a cylindrical mask according to claim 17, wherein the cylindrical mask comprises: a mask cylinder; outside the mask cylinder a seamless first polymer layer on the surface; and a seamless second polymer layer on the outer surface of the first polymer layer, wherein the second polymer layer is more than the first polymer layer Hard, and the second polymer layer has a pattern on its outer surface. A cylindrical mask as claimed in claim 20, wherein the pattern is seamless. a cylindrical mask comprising: a mask cylinder; A seamless compliant layer on the surface of the mask cylinder, the compliant layer having a pattern on the surface. The cylindrical mask of claim 22, wherein the pattern is on an outer surface of the compliant layer. A cylindrical mask as described in claim 22, wherein the pattern is seamless. The cylindrical mask of claim 22, wherein the compliant layer comprises an inner polymer layer and an outer polymer layer, wherein the inner polymer layer is on an outer surface of the mask cylinder, and The outer polymer layer is on the outer surface of the inner polymer layer. The cylindrical mask of claim 25, wherein the outer polymer layer is a material that is harder than the inner polymer layer, and the outer polymer layer is thinner than the inner polymer layer. The cylindrical mask of claim 22, wherein the pattern comprises a nanoscale feature. The cylindrical mask of claim 22, wherein the compliant layer has a uniform thickness. A lithography method comprising repeatedly patterning a substrate by rolling a cylindrical mask as described in claim 22 on a substrate. A substrate is patterned by a lithography method as described in claim 29 of the patent application. A rotatable mask comprising: an axially symmetrical substrate; a compliant layer on the outer surface of the substrate; and a seamless pattern on the outer surface of the compliant layer, wherein the rotatable mask is made by a method comprising the steps of: (a) A casting assembly is coaxially assembled within the interior of the first main shroud, wherein the first main shroud includes an inner diameter that is greater than an outer diameter of the first casting assembly, wherein the inner surface of the first main shroud includes a pattern (b) depositing a first polymer precursor liquid in a space between an outer surface of the first casting component and the inner surface of the first main mask; (c) curing the first polymer first a liquid to produce a first cured polymer, such that an outer surface of the first cured polymer includes a pattern corresponding to the pattern of the first primary mask; (d) the first casting assembly is from the first Removing a cured polymer; (e) removing the first cured polymer from the first main mask; (f) assembling the first cured polymer inside the second casting assembly; (g) The second casting assembly is coaxially assembled inside the first cured polymer, wherein the second casting component has a smaller An outer diameter of an inner diameter of the first cured polymer; (h) depositing a second polymer precursor liquid in a space between an outer surface of the second casting component and an inner surface of the first cured polymer; (i) curing the second polymeric precursor liquid to produce a second cured polymer such that the second cured polymer and the first cured polymer together form the compliant layer of the rotatable mask. A method of making a rotatable mask comprising: (a) depositing a first polymer precursor liquid on the first surface of the first main mask, wherein the first surface of the first main mask comprises a pattern; (b) curing the first polymer first a liquid to produce a first cured polymer, wherein the first cured polymer and the first main mask together form a laminate; (c) the first end of the laminate is constructed to form the first cured polymer Losing a strip portion, and constructing the second end portion of the laminate to cause the first main mask to lose a strip portion; (d) rolling the stack up inside the first casting assembly; (e) depositing a second polymer precursor liquid in a gap of the rolled stack corresponding to the strip portion of the first cured polymer; (f) curing the second polymer precursor liquid Forming a second cured polymer such that the first cured polymer and the second cured polymer together form a compliant layer for the rotatable mask, thereby causing the outer surface of the compliant layer to comprise a corresponding The pattern of the pattern of a main mask. The method of making a rotatable mask of claim 32, further comprising: (g) removing the first casting component from the laminate after the (f). A method of making a rotatable mask as described in claim 32, further comprising: (h) removing the first main mask from the compliant layer after the (f). Manufacturing a rotatable mask as described in claim 32 The method, wherein the first casting component has a cylindrical shape. A method of making a rotatable mask as described in claim 32, wherein the pattern of the first main mask comprises a nanoscale feature. A method of manufacturing a rotatable mask according to claim 32, wherein the (c) comprises removing a strip portion of the first cured polymer after the (b). The method of manufacturing a rotatable mask according to claim 32, wherein the (c) includes a strip portion of the first surface of the first main mask when the (a) is implemented exposure. A method of making a rotatable mask as described in claim 32, wherein the (d) comprises overlapping the first and second ends of the laminate. The method of making a rotatable mask of claim 32, wherein the first end of the laminate is opposite the second end of the laminate. A method of manufacturing a rotatable mask according to claim 32, wherein the first main mask comprises a PET substrate. The method of manufacturing a rotatable mask of claim 32, further comprising: (i) forming the pattern on the first surface of the first main mask prior to (a). A method of manufacturing a rotatable mask according to claim 42 wherein the pattern is formed in the first table of the first main mask. The surface includes: a second main mask transfer substrate having a pattern, the pattern of the second main cover having a smaller area than the substrate; the transfer is repeated one by one until the desired of the substrate The regions are patterned, wherein each of the successively overlapping portions of the previously transferred portion of the substrate; wherein transferring the substrate with the second main mask comprises: depositing a third polymer a precursor liquid; applying pressure to the third polymer precursor liquid between the second main mask and the substrate; and curing the third polymer precursor liquid. The method of making a rotatable mask of claim 32, wherein the first and second polymeric precursor liquids comprise PDMS. A method of making a rotatable mask as described in claim 32, wherein the method is practiced such that the thickness of the compliant layer is between 1 mm and 3 mm. A method of making a rotatable mask as described in claim 32, wherein the first casting component is a sacrificial casting component. A method of making a rotatable mask as described in claim 33, wherein the first casting component is a sacrificial casting component, wherein the (g) comprises breaking, dissolving, or venting the first casting component. The method of manufacturing a rotatable mask according to claim 32, wherein the (d) is when the second surface of the first main mask is adjacent to an inner surface of the first casting component. Implemented. A method of making a rotatable mask comprising: (a) coaxially assembling a first casting assembly within a first main shroud, wherein the first main shroud comprises a larger outer diameter than the first casting assembly An inner diameter, wherein an inner surface of the first main mask comprises a pattern; (b) depositing a first polymer precursor liquid on the outer surface of the first casting assembly and the first main mask (c) curing the first polymer precursor liquid to produce a first cured polymer, thereby causing the outer surface of the first cured polymer to include the map corresponding to the first main mask a pattern of the type; (d) removing the first casting assembly from the first cured polymer; (e) removing the first cured polymer from the first primary mask; (f) the first a cured polymer assembled within the interior of the second casting assembly; (g) coaxially assembling the second casting assembly within the first cured polymer, wherein the second casting assembly has less than the first cured polymer An outer diameter of the inner diameter; (h) depositing a second polymer precursor liquid in the second casting a space between the outer surface of the piece and the inner surface of the first cured polymer; (i) curing the second polymer precursor liquid to produce a second cured polymer, thereby causing the second cured polymer to The first cured polymer together form a compliant layer for the rotatable mask. The method of manufacturing a rotatable mask according to claim 49, further comprising: (j) covering the first cured polymer with a protective layer before the (f) The outer surface. A method of making a rotatable mask as described in claim 49, wherein the second casting component is a substrate for the rotatable mask. A method of making a rotatable mask as described in claim 49, wherein the second casting component comprises molten vermiculite. A method of manufacturing a rotatable mask according to claim 49, wherein the first and second casting assemblies have a cylindrical shape. The method of manufacturing a rotatable mask according to claim 49, further comprising: (k) patterning the inner surface of the first main mask before the (a), wherein the (k) </ RTI> comprising: forming a structured porous layer overlying the inner surface of the first main mask, wherein the first main mask is transparent to optical radiation; filling the plurality of structured porous layers with a filling material a portion of the filling material that is not within one of the plurality of holes; and a plurality of protrusions formed from the filling material within the plurality of holes, wherein the protrusion extends beyond the structured porous layer . The method of making a rotatable mask of claim 49, wherein the first and second polymeric precursor liquids comprise PDMS. A method of making a rotatable mask as described in claim 49, wherein the (d) comprises breaking, dissolving, or deflation of the first casting component. The method of manufacturing a rotatable mask according to claim 49, wherein a difference between the inner diameter of the first main mask and the outer diameter of the first casting component is between 2 mm and 6 mm. between. A method of making a rotatable mask as described in claim 49, wherein the pattern of the first main mask comprises a nanoscale feature. A rotatable mask comprising: an axially symmetrical substrate; a compliant layer on an outer surface of the substrate; and a seamless pattern on an outer surface of the compliant layer, wherein the rotatable mask It is produced by a method of manufacturing a rotatable mask as described in claim 32 of the patent application. A method of patterning a substrate, comprising: (a) transferring a substrate with a pattern of a main mask, the pattern having a smaller area than the substrate; and (b) repeating the (a) successively until the The desired area of the substrate is patterned, wherein each of the successively overlapping portions of the previously transferred portion of the substrate, wherein the primary mask transfer substrate comprises: (i) Depositing a polymer precursor liquid; (ii) applying pressure to the polymer precursor liquid between the main mask and the substrate; and (iii) curing the polymer precursor liquid. The method of patterning the substrate as described in claim 60 of the patent application scope The method additionally includes forming the pattern on the main mask prior to the transferring. A method of patterning a substrate as described in claim 61, wherein forming the pattern comprises patterning the main mask by electron beam lithography. A method of patterning a substrate as described in claim 61, wherein forming the pattern comprises patterning the main mask by photolithography. A method of patterning a substrate as described in claim 61, wherein forming the pattern comprises patterning the main mask by interference lithography. A method of patterning a substrate as described in claim 61, wherein forming the pattern comprises patterning the main mask by self-combination. A method of patterning a substrate as described in claim 61, wherein the patterning comprises patterning the main mask by oxidation of the anode aluminum. A method of patterning a substrate as described in claim 61, wherein forming the pattern comprises patterning the main mask by nanosphere lithography. A method of patterning a substrate as described in claim 61, wherein forming the pattern comprises patterning the main mask by nanotransfer lithography. A method of patterning a substrate as described in claim 60, wherein depositing the polymer precursor liquid comprises depositing the polymer precursor liquid Deposited on the main mask. A method of patterning a substrate as described in claim 60, wherein depositing the polymer precursor liquid comprises depositing the polymer precursor liquid on the substrate. A method of patterning a substrate as described in claim 60, wherein depositing the polymer precursor liquid comprises depositing droplets of one or more discrete polymer precursor liquids in an area to be transferred Inside. A method of patterning a substrate as described in claim 60, wherein depositing the polymer precursor liquid comprises by immersion, spin, spray coating, knife-edge coating, and gravure coating A polymer precursor liquid is continuously deposited (gravure coating) or the like. The method of patterning a substrate as described in claim 60, wherein applying pressure to the polymer precursor liquid between the main mask and the substrate comprises controlling the polymer precursor liquid in the main mask The transfer between the cover and the substrate. The method of patterning a substrate as described in claim 73, wherein the controlling the distribution comprises maintaining a mechanical pressure along a contact line between the main mask and the substrate, and directing the contact line toward the main cover One end of the cover moves continuously. A method of patterning a substrate as described in claim 60, wherein applying pressure to the polymer precursor liquid between the main mask and the substrate comprises pressing the main mask against the substrate. The method of patterning a substrate according to claim 60, wherein the polymer precursor liquid between the main mask and the substrate is applied Pressing includes pressing the substrate against the main mask. A method of patterning a substrate as described in claim 60, wherein the substrate has a flat surface. A method of patterning a substrate as described in claim 60, wherein the substrate has a curved surface. A method of patterning a substrate as described in claim 60, wherein the substrate is rigid. A method of patterning a substrate as described in claim 60, wherein the substrate is flexible. A method of patterning a substrate as described in claim 60, wherein the pattern comprises a nanoscale feature. A method of patterning a substrate as described in claim 60, wherein the pattern of the main mask comprises an array of pillars. A method of patterning a substrate as described in claim 82, wherein the pillar is of a nanometer scale. A method of patterning a substrate as described in claim 83, wherein the pillar has a characteristic size (CD) between 1 nm (nano) and 1000 nm, and a depth between 10 nm and 10000 nm. A method of patterning a substrate as described in claim 83, wherein the pillar has a CD between 50 nm and 400 nm, and a depth between 100 nm and 1000 nm. A method of patterning a substrate as described in claim 84, wherein the array has twice the pitch of the CD. The method of patterning the substrate as described in claim 60 of the patent application scope The method wherein the pattern of the primary mask comprises an array of apertures. A method of patterning a substrate as described in claim 60, wherein the pattern of the main mask is a one-dimensional continuous surface relief profile. A method of patterning a substrate as described in claim 88, wherein the continuous surface relief profile is a sinusoidal surface relief profile. A method of patterning a substrate as described in claim 60, wherein the pattern of the main mask is a two-dimensional continuous surface relief contour. A method of patterning a substrate as described in claim 90, wherein the continuous surface relief profile is a sinusoidal surface relief profile. A method of patterning a substrate as described in claim 60, wherein the substrate is a plastic film. A method of patterning a substrate as described in claim 60, wherein the substrate is a metal film. A method of patterning a substrate as described in claim 60, wherein the substrate is a thin glass sheet. A method of patterning a substrate as described in claim 60, wherein the substrate is a glass panel. A method of patterning a substrate as described in claim 60, wherein the substrate is a semiconductor wafer. A method of patterning a substrate as described in claim 60, wherein the (b) comprises repeating the transfer of the substrate in a random manner in a random configuration for producing a transfer portion. A substrate patterned by a method of patterning a substrate as described in claim 60, comprising: a first surface; and a patterned layer disposed on the first surface, wherein The patterned layer includes a plurality of imprints, and each of the boundaries between the plurality of imprints includes an imprint that overlaps a portion of the other imprint. A patterned substrate comprising: a first surface; and a patterned layer disposed on the first surface, wherein the patterned layer comprises a plurality of imprints, and each boundary between the plurality of imprints Contains an imprint that overlaps with a portion of another imprint. The patterned substrate of claim 99, wherein the first surface comprises a curved surface. The patterned substrate of claim 99, wherein the first surface is a flat surface. The patterned substrate as described in claim 99, wherein the substrate is a plastic film. The patterned substrate of claim 99, wherein the substrate is a glass panel. The patterned substrate of claim 103, wherein the patterned substrate is a lithography mask. The patterned substrate of claim 99, wherein the substrate is a nano transfer lithography mold. The patterned substrate as described in claim 99, Wherein the patterned layer comprises a pattern having features of a nanometer scale. The patterned substrate of claim 99, wherein the patterned layer comprises a pattern having an array of pillars. A patterned substrate as described in claim 107, wherein the pillar is of a nanometer scale. The patterned substrate of claim 108, wherein the pillar has a CD between 1 nm and 10000 nm, and a depth between 10 nm and 1000 nm. The patterned substrate of claim 109, wherein the array has twice the pitch of the CD. The patterned substrate of claim 99, wherein the patterned layer comprises a pattern having an array of apertures. The patterned substrate of claim 99, wherein the patterned layer has an area greater than ^20,000 mm ² (square millimeters). The patterned substrate of claim 99, wherein the patterned layer has an area greater than 400,000 mm ² . The patterned substrate as described in claim 99, wherein the area of each of the imprints is less than 2500 mm ² . Pattern of the substrate as defined in claim 99 of the first range, wherein each mark area is between 100mm ² and 2500mm ^2. The patterned substrate of claim 99, wherein the plurality of imprints are arranged in a regular array. The patterned substrate of claim 116, wherein the plurality of imprints are arranged in a rectangular array. The patterned substrate of claim 116, wherein the plurality of imprints are arranged in a hexagonal array. The patterned substrate of claim 99, wherein the plurality of imprints are configured in a random configuration. A method of forming a master mold for a cylindrical lithography mask, the method of forming a master mold comprising: forming a structured porous layer overlying an inner surface of a cylinder, wherein the cylinder pair The optical radiation is transparent; filling the one or more holes in the structured porous layer with a filling material; removing a portion of the filling material that is not within one of the one or more holes; and from the one or The fill material within the plurality of holes forms one or more protrusions, wherein the protrusions extend beyond the structured porous layer. A method of forming a master mold as described in claim 120, wherein the filling material is a radiation sensitive material. The method of forming a master mold according to claim 121, wherein removing the portion of the filling material that is not within one of the one or more holes comprises: exposing the outer surface of the cylinder with radiation a sufficient duration to cure the filling material in the pores of the structured porous layer; and the filler material to be constructed to remove the portion of the filling material that is not cured development. A method of forming a master mold as described in claim 122, wherein the radiation-sensitive material further comprises ruthenium. The method of forming a master mold as described in claim 123, further comprising: annealing the cured radiation-sensitive material. The method of forming a master mold of claim 121, wherein forming the one or more protrusions comprises etching away at least a portion of the structured porous layer. The method of forming a master mold according to claim 120, wherein the inner surface of the cylinder is an epitaxial seed layer. The method of forming a master mold according to claim 126, wherein the filling material is epitaxial growth of the epitaxial seed layer. The method of forming a master mold according to claim 127, wherein the epitaxial seed layer is a semiconductor material. A method of forming a master mold as described in claim 128, wherein each of the one or more protrusions is configured to function as a light emitting diode (LED), thereby having one or more LEDs. A method of forming a master mold as described in claim 129, wherein each of the one or more LEDs can be individually addressed. The method of forming a master mold according to claim 127, wherein the filling material in the one or more holes is allowed to form one or more protrusions extending beyond the structured porous layer to include the epitaxial layer The growth grows beyond the thickness of the structured porous layer. A method of forming a master mold as described in claim 120, wherein the one or more protrusions have a feature size between 1 nm and 100 microns. A method of forming a master mold as described in claim 120, wherein the one or more protrusions have a feature size between 10 nanometers and 1 micrometer. The method of forming a master mold according to claim 120, wherein the one or more protrusions have a feature size between 50 nm and 500 nm. A master mold for a cylindrical reticle comprising: a cylinder transparent to optical radiation, the cylinder having an inner surface and an outer surface; and one or more protrusions from the cylinder The inner surface extends inwardly toward the center of the cylinder. The master mold for a cylindrical reticle of claim 135, wherein the one or more protrusions have a feature size between 1 nm and 100 microns. A master mold for a cylindrical reticle according to claim 135, wherein the one or more protrusions have a feature size of between 10 nm and 1 μm. The master mold for a cylindrical reticle of claim 135, wherein the one or more protrusions have a feature size between 50 nm and 500 nm. A master mold for a cylindrical reticle according to claim 135, wherein the one or more protrusions are made of an annealed photosensitive material having a crucible. For use in a cylindrical reticle as described in claim 135 The master mold, wherein the inner surface of the cylinder is an epitaxial seed layer. The master mold for a cylindrical reticle according to claim 140, wherein the one or more protrusions are the same material as the epitaxial seed layer. The master mold for a cylindrical reticle according to claim 141, wherein the epitaxial seed layer is a semiconductor material. A master mold for a cylindrical reticle as described in claim 142, wherein each of the one or more protrusions is an LED. A master mold for a cylindrical reticle as described in claim 143, wherein each of the one or more protrusions can be individually addressed. A method of forming a master mold for a cylindrical reticle, the method of forming a master mold comprising: forming a radiation sensitive layer overlying an inner surface of the cylinder, wherein the cylinder is optical radiation Transparent; forming a self-assembled monolayer (SAM), wherein the SAM covers the first portion of the radiation-sensitive layer, and the second portion of the radiation-sensitive layer is uncovered; the radiation is sensitive to optical radiation Exposing one of the first and second portions of the layer, wherein the optical radiation is configured to cure the portion of the radiation-sensitive layer that is exposed; and developing the radiation-sensitive layer with a developing solution such that The second portion of the radiation sensitive layer is selectively removed. The party forming the master model as described in claim 145 The method wherein the SAM is formed on an exposed surface of the radiation sensitive layer. A method of forming a master mold as described in claim 146, wherein the SAM comprises metal nanospheres. The method of forming a master mold according to claim 147, wherein the optical radiation is emitted from a radiation source located within the cylinder, and wherein the optical radiation is the second portion of the radiation sensitive layer exposure. The method of forming a master mold according to claim 148, wherein the developing solution selectively removes the cured portion of the radiation-sensitive layer. A method of forming a master mold as described in claim 146, wherein the SAM comprises quantum dots. A method of forming a master mold as described in claim 150, wherein the optical radiation is emitted from the quantum dot, and wherein the optical radiation exposes the first portion of the radiation sensitive layer. The method of forming a master mold according to claim 151, wherein the developing solution selectively removes an uncured portion of the radiation-sensitive layer. A method of forming a master mold as described in claim 145, wherein the SAM system is formed on the outer surface of the cylinder. A method of forming a master mold as described in claim 153, wherein the SAM comprises metal nanospheres. The method of forming a master mold according to claim 154, wherein the optical radiation is emitted from a radiation source located in the cylinder, and Wherein the optical radiation exposes the second portion of the radiation sensitive layer. The method of forming a master mold according to claim 155, wherein the developing solution selectively removes the cured portion of the radiation-sensitive layer. A method of forming a master mold as described in claim 153, wherein the SAM comprises quantum dots. A method of forming a master mold as described in claim 157, wherein the optical radiation is emitted from the quantum dot, and wherein the optical radiation exposes the first portion of the radiation sensitive layer. The method of forming a master mold according to claim 158, wherein the developing solution selectively removes an uncured portion of the radiation-sensitive layer. A method of forming a master mold as described in claim 153, wherein the radiation-sensitive layer further comprises ruthenium. The method of forming a master mold as described in claim 160, further comprising: annealing the cured radiation-sensitive layer. A cylindrical main mold assembly comprising: a patterned assembly having a first radius; and a sacrificial casting assembly having a second radius, wherein the second radius is different from the first radius, wherein the patterning The assembly and the sacrificial casting assembly are constructed such that a component having a smaller radius of both the patterned assembly and the sacrificial casting assembly can be coaxially embedded into the interior of the component having a larger radius, and wherein the sacrifice is faced The surface of the patterned component of the casting assembly One or more graphical features. The cylindrical master mold assembly of claim 162, wherein the first radius is greater than the second radius. The cylindrical master mold assembly of claim 163, wherein the sacrificial casting assembly is made of a material that is susceptible to cracking. The cylindrical main mold assembly of claim 164, wherein the material which is liable to be broken is molten vermiculite or glass. The cylindrical master mold assembly of claim 163, wherein the sacrificial casting assembly is made of a material that will dissolve. The cylindrical master mold assembly of claim 166, wherein the material to be dissolved is sugar. The cylindrical master mold assembly of claim 163, wherein the sacrificial casting assembly is made of a malleable material. The cylindrical master mold assembly of claim 168, wherein the malleable material is aluminum. The cylindrical main mold assembly of claim 168, wherein the extensible material is plastic. The cylindrical master mold assembly of claim 163, wherein the sacrificial casting assembly is a sealed cylinder. The cylindrical master mold assembly of claim 171, wherein the seal cylinder is inflatable and deflated. The cylindrical master mold assembly of claim 162, wherein the second radius is greater than the first radius. The total cylindrical master mold as described in claim 173 The sacrificial casting assembly is made of a material that is susceptible to cracking. The cylindrical main mold assembly of claim 174, wherein the material which is liable to be broken is molten vermiculite or glass. The cylindrical master mold assembly of claim 173, wherein the second radius is no more than 2 mm greater than the first radius. The cylindrical master mold assembly of claim 162, wherein the one or more patterned features have a feature size between 1 nanometer and 100 micrometers. The cylindrical master mold assembly of claim 162, wherein the one or more patterned features have a feature size between 10 nanometers and 1 micrometer. The cylindrical master mold assembly of claim 162, wherein the one or more patterned features have a feature size between 50 nanometers and 500 nanometers. A method of forming a cylindrical mask from a cylindrical master mold assembly, the cylindrical mask being constructed to have one or more features formed on a surface, wherein the cylindrical master mold assembly comprises a cylindrical patterned assembly having a first radius, and a sacrificial casting assembly having a second radius, wherein the second radius is different from the first radius, wherein the cylindrical patterning of the sacrificial casting assembly The surface of the component has one or more patterned features, and the method of forming the cylindrical mask comprises: (a) coaxially patterning the cylindrical patterned component and the component having a smaller radius in the sacrificial casting component Embedding into a component having a larger radius; (b) filling the cylindrical patterned component with the liquid precursor a space between the cast components; (c) curing the liquid precursor to form an elastomeric material; and (d) removing the sacrificial casting assembly. The method of forming a cylindrical mask of claim 180, wherein removing the sacrificial casting assembly comprises rupturing the sacrificial casting assembly. A method of forming a cylindrical mask as described in claim 180, wherein removing the sacrificial casting assembly comprises dissolving the sacrificial casting assembly in a solvent. A method of forming a cylindrical mask as described in claim 182, wherein the sacrificial casting assembly is made of a sugar-based material, and wherein the solvent is water. A method of forming a cylindrical mask as described in claim 180, wherein the second radius is smaller than the first radius. A method of forming a cylindrical mask as described in claim 184, wherein removing the sacrificial casting assembly comprises plastically deforming the sacrificial casting assembly. A method of forming a cylindrical shroud as described in claim 184, wherein the sacrificial casting assembly is a sealed cylinder, and wherein removing the sacrificial casting assembly comprises venting the sacrificial casting assembly. A method of forming a cylindrical mask as described in claim 180, wherein the first radius is smaller than the second radius. The method of forming a cylindrical mask as described in claim 187, further comprising: After (d), the elastomeric material is pulled back over itself in a direction parallel to the axis of the cylindrical patterning assembly such that the elastomeric material is patterned from the cylinder The assembly is removed and flipped inside and out. A method of forming a cylindrical mask as described in claim 188, wherein the difference between the second radius and the first radius is no more than 2 mm. A cylindrical mask comprising: a cylindrical elastomer assembly having an inner radius, the cylindrical elastomer assembly having a major surface, and a nanopattern formed on the major surface; a rigid transparent cylindrical component, An outer radius, wherein the outer radius is sized to fit within the cylindrical elastomer assembly; and a gas retaining member configured to retain a volume of gas in the cylindrical elastomer assembly The inner surface is between the outer surface of the rigid transparent cylindrical component. The cylindrical mask of claim 190, wherein the gas holder comprises two seals, wherein each seal seals a respective end of the volume of gas. The cylindrical mask of claim 191, wherein the seal is an O-ring or a leak-proof gasket. The cylindrical mask of claim 190, wherein the gas retaining member is an air bag. The cylindrical mask of claim 190, wherein the major surface of the cylindrical elastomer assembly is a cylindrical outer surface. A method of making a rotatable mask as described in claim 49, wherein the second casting component is a sacrificial casting component, wherein the method additionally comprises removing the second casting component.