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WO2002017347A1 - Traitement de composition sol-gel et formation de motifs dans cette composition sol-gel par faisceau electronique - Google Patents

Traitement de composition sol-gel et formation de motifs dans cette composition sol-gel par faisceau electronique Download PDF

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Publication number
WO2002017347A1
WO2002017347A1 PCT/US2001/020264 US0120264W WO0217347A1 WO 2002017347 A1 WO2002017347 A1 WO 2002017347A1 US 0120264 W US0120264 W US 0120264W WO 0217347 A1 WO0217347 A1 WO 0217347A1
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WO
WIPO (PCT)
Prior art keywords
sol
gel
fluorine
group
hydrolyzable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2001/020264
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English (en)
Inventor
Ljerka Ukrainczyk
Nick J Visovsky
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Corning Inc
Original Assignee
Corning Inc
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Application filed by Corning Inc filed Critical Corning Inc
Priority to AU2001275842A priority Critical patent/AU2001275842A1/en
Publication of WO2002017347A1 publication Critical patent/WO2002017347A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/13—Integrated optical circuits characterised by the manufacturing method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/122—Basic optical elements, e.g. light-guiding paths
    • G02B6/1225—Basic optical elements, e.g. light-guiding paths comprising photonic band-gap structures or photonic lattices
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/13—Integrated optical circuits characterised by the manufacturing method
    • G02B6/132—Integrated optical circuits characterised by the manufacturing method by deposition of thin films
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B29C2035/0877—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • B29C2059/023—Microembossing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms
    • B29L2011/0075—Light guides, optical cables
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B2006/12083—Constructional arrangements
    • G02B2006/12119—Bend
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B2006/12133—Functions
    • G02B2006/12145—Switch
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/24—Coupling light guides
    • G02B6/36—Mechanical coupling means
    • G02B6/3628—Mechanical coupling means for mounting fibres to supporting carriers
    • G02B6/3684—Mechanical coupling means for mounting fibres to supporting carriers characterised by the manufacturing process of surface profiling of the supporting carrier
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/30—Electron or ion beam tubes for processing objects
    • H01J2237/317—Processing objects on a microscale
    • H01J2237/31735—Direct-write microstructures

Definitions

  • the present invention relates to the field of patterning a material deposited on a substrate, and more particularly to a method for creating patterns with ultra-fine features in a thin film carried on a surface of a substrate for uses such as fabricating as micro-molding or nano-molding tools or molds or photonic crystal structures.
  • devices having microscopic and or nanoscopic features include planar optical devices or waveguides used in optical communications systems, semiconductor integrated electrical circuits, hybrid opto-electrical devices, as well as certain micro- mechanical or microelectro-mechanical systems (MEMS) devices, medical diagnostic devices, and so forth.
  • MEMS micro- mechanical or microelectro-mechanical systems
  • a photo-mask is prepared having areas that are transparent to at least a particular radiation (e.g., ultraviolet radiation) which are surrounded by adjacent areas that are opaque to the particular radiation.
  • the mask defines a pattern that is a replica of the desired pattern that is to be formed in a material at the surface of a substrate.
  • a desired relief pattern can be created in a substrate or in a film deposited on the surface of a substrate using conventional photolithography.
  • a film i.e., a thin layer of material
  • a substrate is deposited on a substrate using any of a variety of deposition or coating techniques, (e.g., sputtering, flame hydrolysis deposition, chemical vapor deposition, etc.).
  • a photoresist layer (typically a polymer material) is deposited (such as by spin- coating) over the substrate or film layer that is to be patterned.
  • the photo-mask is positioned over the photoresist layer and radiation is directed at the mask and through the transparent areas of the mask to the photoresist layer.
  • the areas of the photoresist layer that have been exposed to the radiation are chemically modified so that either the irradiated areas are soluble in a developer solvent (positive resist) or the non-irradiated areas are soluble in a developer solvent (negative resist), while the adjacent areas are insoluble in the developer solvent.
  • a patterned resist layer that corresponds to a desired pattern for the substrate or film layer remains.
  • etching or reactive ion etching may then be used to replicate the pattern into the substrate or film.
  • Typical film materials include dielectric materials such as silica, semiconductive materials such as germanium-doped silica, and conductive materials such as copper, silver, gold, etc.
  • These photolithographic techniques may be employed to form additional layers of patterned material to fabricate relatively complex devices having ultra-fine features. Although these techniques involving deposition, lithography, and etching are commonly employed for mass production of various devices, they have the disadvantages of being relatively expensive and are not ideally suited for rapid prototyping of devices.
  • An alternative process for patterning a substrate or a film on a substrate involves the use of micro-molding techniques.
  • a layer of a moldable material is deposited on a surface of a substrate, or a film deposited on a substrate.
  • the moldable material is a thermoplastic polymer that is heated to a temperature to allow sufficient softening to facilitate shaping of the moldable material during a compressive molding step.
  • a molding tool having protruding features and adjacent recessed features is pressed into the moldable material so that the thickness of the moldable material under the protruding features is thinner than the thickness of the moldable material under the recessed features.
  • a relief pattern corresponding to the features that are desired is thus created in the moldable material. The relief pattern generally conforms to the shape of the features of the molding tool.
  • the molding tool is then removed from the moldable material, and the molded material is processed such as by wet etching of reactive ion etching so that the thinner areas of the molded material in the relief are removed to expose the underlying substrate or film.
  • the pattern in the molding tool is replicated in the moldable material.
  • the pattern in the moldable material can be replicated in a material that is added onto the substrate. This can be achieved by depositing a material over the patterned moldable material and over the areas of the substrate film that have been exposed. Materials which may be deposited on the exposed areas of the substrate film include electrical conductors, semiconductors, ceramics, glasses, or dielectrics of the type commonly used to fabricate integrated electrical circuits, optical circuits, etc.
  • a lift off technique is performed in which a selective chemical etch is applied to remove the remaining moldable material and any material deposited on the moldable material, leaving a replica of the pattern in the material deposited on the substrate film.
  • the pattern in the moldable material can be replicated directly into the substrate or a film deposited on the substrate using an etching process such as ion etching or chemical etching, such that recesses are formed in the areas of the substrate or film deposited on the substrate that are exposed through the molded and patterned thermoplastic layer.
  • micro-molding techniques may be advantageously employed to mass- produce devices having ultra-fine features at a low cost.
  • a first disadvantage relates to the process by which the micro-molding tools are prepared.
  • a micro-molding tool is prepared using the conventional lithographic techniques that are to a certain extent avoided when the micro-molding tools are employed to fabricate devices.
  • a relatively large number of micro-molding tools may need to be fabricated.
  • each of these micro-molding tools is separately prepared from a hard substrate such as a metal, glass or ceramic material by depositing a photoresist layer on the substrate, exposing the photoresist material to radiation through a mask, developing the desired pattern in the photoresist material, and etching the substrate.
  • a hard substrate such as a metal, glass or ceramic material
  • a release agent may be used to facilitate smoother release of the patterned material from the micro-molding tools whereby pattern defects can be eliminated or reduced, however; mold release agents wear off the mold surfaces and must be regularly reapplied. Regular application of a mold release agent on surfaces of a micro-molding tool requires additional labor and equipment.
  • Another problem with release agents is that they may adversely affect properties (i.e., functionality) of the devices being fabricated or subsequent steps during fabrication. For example, release agents can interfere with subsequent fabrication steps involving the use of adhesives (i.e., release agents can prevent adhesives from effectively adhering to surfaces). While such problems can be overcome, they add to the cost and complexity of the process.
  • This invention concerns a process for creating a pattern with ultra-fine features on a surface of a substrate or in a film deposited on a surface of a substrate.
  • the method of the present invention may be advantageously used for directly patterning a material on the surface of a substrate for the fabrication of various miniature devices such as planar optical devices or waveguides, semiconductor integrated electrical devices, opto-electrical devices, and so forth, without employing conventional lithographic and etching techniques.
  • the method of this invention may also be advantageously used for fabricating micro-molding tools that can be employed in the mass production of miniature devices having a patterned material with microscopic and/or nanoscopic features. More particularly, the invention facilitates rapid fabrication of inexpensive prototypes and/or micro-molding tools.
  • the method of this invention may also be used to fabricate integrated optical or "planar" type photonic crystal waveguide structures.
  • a process for solidifying (or "curing") and patterning a sol-gel composition on a substrate involves depositing a layer of a sol-gel composition on a surface of a substrate to form a sol-gel film, curing or solidifying selected areas of the film that correspond to a predetermined desired pattern by directing an electron-beam at those selected areas of the sol-gel film, and contacting the partially cured sol-gel with a solvent to dissolve and remove areas of the sol-gel film that have not been cured to leave the predetermined pattern of cured sol-gel material.
  • the process also allows direct patterning and curing of a sol-gel film to create ultra-fine features.
  • the desired pattern is created in a solid glass-like material without conventional lithography techniques, (e.g., radiation exposure through a mask and development), and without convention etching techniques. Additional features and advantages of the invention will be set forth in the detailed description which follows and will be apparent to those skilled in the art from the description or recognized by practicing the invention as described in the description which follows together with the claims and appended drawings.
  • Figs. 1-7 are scanning electron micrographs (SEMs) of a patterned sol-gel film prepared using a process of the invention
  • Figures 8-11 are SEMs of photonic crystal waveguide structures fabricated using sol-gel photomasks fabricated using the method of the present invention as described herein
  • Figures 12-17 are SEMS of sol-gel photomasks fabricated using the process of the present invention as described.
  • ultra-fine features for example, such as those normally associated with conventional photonic crystal waveguide structures, or micro-molding and nano-molding tools or molds
  • ultra-fine features are features having dimensions in the microscopic range and/or the nanoscopic range (e.g., dimensions from about 100 nanometers or less up to about 1,000 micrometers or more), with a resolution (i.e., variation from a desired dimension) that is less than or about 5 nanometers.
  • sol-gel compositions are well known. Such compositions are comprised of at least one compound that can be hydrolyzed and condensed to form a metal oxide or metalloid oxide structure in which a metal atom or a metalloid atom is connected with a plurality of other metal or metalloid atoms though bridging oxygen atoms.
  • hydrolyzable/condensable compound or compounds present in a sol-gel are compounds that are capable of being thermally cured through a series of hydrolysis reactions, alcohol condensation reactions, and water condensation reactions in accordance with the following general reaction sequence. (Hydrolysis)
  • the hydrolyzable/condensable compounds in the sol-gel composition can be represented by the general formula M(OR) n X m , where Mis a metal or metalloid (e.g., an electrically semiconductive material) having a valence of n + m, each R is independently a hydrogen or a hydrocarbyl group (e.g., an alkyl group) each X is an organic group that does not participate in the hydrolysis or condensation reactions, n is a positive integer, m is zero or a positive integer, and n + m is equal to the valence of the metal or metalloid atom, M.
  • Mis a metal or metalloid e.g., an electrically semiconductive material having a valence of n + m
  • each R is independently a hydrogen or a hydrocarbyl group (e.g., an alkyl group)
  • each X is an organic group that does not participate in the hydrolysis or condensation reactions
  • n is a positive integer
  • m is
  • metal or metalloid atoms, M examples include Si, Ti, Al, Ge, Ta, B, Ga, Zr and Sb.
  • M metal or metalloid atoms
  • M(OR) n examples include tetraethylorthosilicate (TEOS) and tetraisopropoxy germane (TIPG).
  • the sol-gel compositions may contain relatively minor amounts of partially hydrolyzable/condensable compounds having the general formula M(OR) n X m , where M, R, X, and n are as defined above, and m is a positive integer.
  • M, R, X, and n are as defined above, and m is a positive integer.
  • An example of a compound of this type is methacryloxypropyltrimethoxysilane (MPTS).
  • MPTS methacryloxypropyltrimethoxysilane
  • Partially hydrolyzable compounds having an organic group may be employed in the sol-gel composition to impart greater flexibility to the cured or condensed solid metal oxide or metalloid oxide network derived from the sol-gel composition.
  • Cured materials prepared from sol-gel compositions containing partially hydrolyzable compounds having an organic group that does not participate in the hydrolysis or condensation reactions may also exhibit enhanced toughness, reduced brittleness, and relatively thicker films (up to 10 nanometers or more) may be cured without cracking using the electron-beam patterning and curing technique of this invention.
  • the sol-gel cladding compositions of this invention may also contain a partially hydrolyzable fluorine-containing compound in an amount that is effective to provide a highly non-wetting surface that eliminates, or substantially reduces, the need for release agents on surfaces of the patterned material, when the patterned material is used on a micro-molding tool.
  • the partially hydrolyzable fluorine-containing compounds include a metal atom or metalloid atom, such as Si, Ti, Al, Ge, Ta, B, Ga, Zr or Sb, at least one hydrolyzable group (e.g., an alkoxy group) and at least one non-hydrolyzable group that contains at least one fluorine atom.
  • a metal atom or metalloid atom such as Si, Ti, Al, Ge, Ta, B, Ga, Zr or Sb
  • at least one hydrolyzable group e.g., an alkoxy group
  • at least one non-hydrolyzable group that contains at least one fluorine atom.
  • Examples of partially hydrolyzable fluorine- containing compounds suitable for use in the sol-gel compositions utilized in the processes of this invention may be represented by the general formula M(OR) Z q , where M is a metal or metalloid atom having a valence ofp + q, each R is independently a hydrogen atom or a hydrocarbyl group (e.g., an alkyl group), each Z is a fluorine-containing group, and/? and q are each at least 1.
  • the fluorine-containing group may be an alkyl group having fluorine substituents
  • partially hydrolyzable fluorine-containing compounds include fluoroalkyltrialkoxysilianes, such as (3,3,3- trifluoropropyl) trimethoxysilane.
  • the amount of partially hydrolyzable fluorine- containing compound that may be required to achieve a desired non-wetting surface can be determined by routine experimentation.
  • An example of a sol-gel composition containing a partially hydrolyzable fluorine-containing compound in an amount sufficient to impart a non- wetting surface (hydrophobic surface) to a cured material derived from the composition is set forth below.
  • Partially hydrolyzable fluorine- containing compounds may also be added to sol-gel compositions in order to lower the refractive index of a cured material derived from the composition.
  • partially hydrolyzable fluorine-containing compounds may be utilized in those situations in which a micro-molding tool is prepared with a release surface, and in those situations in which optical devices having components with a low refractive index are fabricated.
  • the sol-gel composition of this invention can contain other ingredients.
  • partially hydrolyzable compounds having a non-hydrolyzable moiety that is organically polymerizable may be added, either with or without other non- hydrolyzable, organically polymerizable compounds (e.g., polymerizable ethylenically unsaturated monomers such as methacrylic acid or a methacrylic acid ester).
  • organically polymerizable compounds e.g., polymerizable ethylenically unsaturated monomers such as methacrylic acid or a methacrylic acid ester.
  • sol-gel compositions containing a high proportion of fully hydrolyzable compounds, and a relatively low proportion of partially hydrolyzable compounds and non- hydrolyzable compounds are suitable.
  • compositions when thermally cured, will have properties similar to glass, whereas compositions containing a relatively high proportion of partially hydrolyzable, organically functionalized compounds and non- hydrolyzable, organic monomers, will tend to exhibit hybrid properties intermediate between that of an organic polymer and a glass material.
  • Sol-gel compositions for use in the processes of this invention may have a mole ratio of fully hydrolyzable compounds (compound in which each of the moieties bonded to a metal or metalloid atom are capable of being hydrolyzed so that an alkoxy group bonded to the metal or metalloid atom is replaced with a hydroxyl group) to partially hydrolyzable compounds (compounds that include at least one moiety that is not capable of being hydrolyzed) is at least 50:50 and more suitably at least 70:30.
  • the compositions should contain little, if any, organic monomers.
  • sol-gel compositions of this invention may be deposited on the surface of a substrate using any suitable coating technique, such as spin-coating or dip-coating. Suitable coating thicknesses depend on the particular application for the device or micro-molding tool being fabricated using the processes of the invention. However, typical sol-gel film thicknesses are from about 1 or 2 micrometers to about 10 or 15 micrometers.
  • the film may be prebaked to partially cure the sol-gel composition to stabilize the film on the substrate, and/or to eliminate tackiness at the surface of the substrate.
  • a preheating step is not required, and may not be desirable in many applications.
  • a desired pattern can be formed in the sol-gel film by selectively curing predetermined areas of the sol-gel film that correspond to a desired pattern by directing an electron beam at the selected areas of the film.
  • a desired pattern is written directly into the sol-gel film using an electron beam.
  • An apparatus for patterning and curing a sol-gel film by writing the desired pattern directly into the sol- gel film using an electron beam can be provide by converting a scanning electron microscope (e.g., JEOL 840) for use as an electron beam patterning tool using a commercially available SEM conversion package.
  • the commercially available package includes pattern generation software and hardware that directs the electron beam to write patterns that are created by the user in a computer aided design (CAD) software package.
  • CAD computer aided design
  • a system of this type is capable of writing generally any type of pattern that can be drawn using the CAD software.
  • the mechanism by which curing of the sol-gel film is achieved using an electron beam is perhaps not fully understood, it is believed that the electron beam induces localized heating of the sol-gel film, and that this localized heating causes localized curing or condensation of the sol-film in those areas of the film bombarded with or exposed to the electron beam by way of the hydrolysis and condensation reactions schematically illustrated above.
  • the cured areas of the sol-gel film form a condensed three-dimensional network comprised of metal or metalloid atoms linked together through an oxygen atom.
  • the resulting cured product has chemical and physical properties that are very similar, and in some cases almost identical, to conventional glasses.
  • the film is contacted with a solvent to dissolve areas of the film that have not been cured. This allows the uncured areas of the film to be easily removed, leaving behind the desired pattern of cured sol-gel material.
  • a suitable solvent that may be used to remove the areas of the sol-gel film that have not been cured is toluene.
  • the solvent may include a small amount of a surfactant.
  • the processes of this invention may be used to fabricate optical waveguides for planar optical devices, microfluidic channels for biological sensing devices and/or biological diagnostic devices, etc.
  • the processes of this invention may be used to design patterns for micro-molding tools that may be used during the fabrication of various miniature devices including planar optical devices, semiconductor electrical circuit devices, etc.
  • Electron-beam patterning of sol-gel films was accomplished by using a custom built electron-beam lithography system.
  • the system was based on a JEOL 840 scanning electron microscope that was converted to write patterns using a commercially available SEM conversion package.
  • the package included pattern generation software and hardware that is used to direct the electron beam to write patterns that are created by the user in a computer aided design (CAD) software package.
  • CAD computer aided design
  • Figs. 1-7 show scanning electron microscope images of test pattern wheels written using electron-beam lithography into an inorganic-organic hybrid sol-gel material in accordance with the principles of this invention.
  • Fig. 1 is an overall view of a 3 X 3 pattern of wheels and Figs. 2-7 are magnified images of individual wheels.
  • the wheel patterns shown in Figs. 3-5 were written at electron-beam dosages of 90, 150, and 270 nC/cm respectively.
  • the sol-gel composition used in these experiments was comprised of 53.6 mole percent of tetraethylorthosilicate (TEOS), 13.4 mole percent tetraisopropoxygermane (TIPG), and
  • the composition is UN sensitive on account of the methacryloxy group on the MPTS, and can be patterned with light at 248 nm which cross links double bonds on the MPTS.
  • the sol-gel composition was deposited onto a substrate using a spin-coating technique to provide a sol-gel film having a uniform thickness of from about 0.5 to 6 microns. When the sol- gel films were, exposed to an electron beam and developed (contacted with a solvent such as toluene to dissolve and remove the area of the film that have not been exposed to, or written with, the electron beam), the film behaved as a negative resist.
  • Infrared spectra of the electron-beam cured film did not show any decrease in the band corresponding to the double bond of MPTS.
  • infrared spectra indicated that the double bond disappeared. This demonstrates the curing mechanism for electron-beam curing is not by cross-linking of the double bond.
  • the infrared spectra showed that essentially none of the double bonds in the MPTS were reacted after exposure to an electron beam.
  • An expanded FTIR spectra showed that OH stretch as a function of electron-beam dosage decreased with increasing electron-beam energy. This is consistent with a conventional sol-gel condensation reaction in which a silica framework is formed.
  • Figs. 1-7 films having a thickness of from 0.5 to 6 microns were used to write lines having a width of about 100 nanometers.
  • Fig. 1 shows a mesa-like structure having the 3 X 3 wheel pattern written on the top surface of the mesa-like structure. It is believed that electron scattering coupled with thermal conduction cured the surrounding areas of the wheels.
  • the magnified images shown in Figs. 2-7 show very well defined wheel patterns (a circular rim with spokes extending radially from the center of the wheel to the rim). This is due to the focus or concentration of the electron beam on the surface of the sol-gel film.
  • the linewidths of the wheels are about 100 nanometers, and provide positive relief on top of the mesa-like structure.
  • This structure can be used as a nanoimprint mold (i.e., a nano-molding tool) to emboss only the wheel lines into a thin polymer film.
  • the second result is that the areas of the mesa-like structure that were not directly written upon with the electron beam (i.e., the areas between the spokes and rim, and the areas outside of the rim that are immediately adjacent the rim) formed a relatively large structure.
  • the processes of the invention have utility in rapidly writing large structures (e.g., long waveguides), and may allow direct fabrication of micromolds with tailored surface properties.
  • a pure TEOS sol-gel film may be patterned with an electron beam to rapidly form a waveguide having properties that are substantially the same as a glass waveguide formed using more conventional methods such as flame hydrolysis deposition or chemical vapor deposition.
  • FIGs. 8-17 photonic crystal waveguide structures fabricated using the electron-beam cured sol-gel photomask technique according to the present invention are shown in Figs. 8-11, and the sol-gel photomasks utilized to prepare photonic crystal structures are shown in Figs. 12-17. It may be seen that each fabrication process can produce photomasks and waveguide paths having a lattice or array of holes (or "wells") and wall structures disposed on opposing sides of the waveguide, with the side walls of the holes and walls evidencing good depth, side wall smoothness, and verticality.
  • photomasks having a more rectangular configuration of substantially similar pitch (hole-to-hole center spacing) and thin wall thickness.
  • suitable photonic crystal waveguide structures of the desired shape, pitch, wall thickness, and array or lattice structure may be fabricated using the process of the present invention, and used to achieve any number of photonic crystal device or waveguide patterns, such as the right-angle bends shown in Figs. 8-15, X- and Y-splits for couplers or switches as shown in Figures 16 and 17, or any other pattern or array that might be suitable and appropriate to accomplish desired light-guiding properties.
  • the method of the present invention may be utilized to fabricate other types of photonic crystal structures, such as a waveguide having an array of rods (rather than holes or wells) disposed on opposing sides of the waveguide, and other patterns conventionally utilized in fashioning photonic crystal structures. It is also understood that the method of the present invention may lead to the fabrication of new and unique photonic crystal waveguide structures and patterns (particularly considering multi-layer or three-dimensional photonic crystal structures or waveguide patterns otherwise requiring repeated or overlapping lithographic and etching steps) that would be impracticable or impossible to achieve using conventional patterning and etching processes with silica-on-insulator materials.
  • sol-gel compositions Further background information relevant to sol-gel compositions, the formation of sol-gel films, methods for patterning, curing, and etching of such sol-gels, and the fabrication of waveguides and other structures using sol-gels are contained in United

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Abstract

L'invention concerne un procédé de formation et d'élaboration d'un motif présentant des caractéristiques microscopiques et/ou nanoscopiques. Ce procédé consiste à déposer une couche d'une composition sol-gel sur la surface d'un substrat pour former un film sol-gel, à diriger un faisceau électronique sur des zones sélectionnées du film afin de traiter ces zones du film, et à mettre le film sol-gel en contact avec un solvant afin de dissoudre et éliminer lesdites zones du film qui n'ont pas été traitées pour obtenir le motif désiré de matière sol-gel traitée. Ce procédé est utile pour la fabrication rapide de dispositifs miniature, tels que des dispositifs optiques plans, des structures de guidage d'onde en cristal photonique, des capteurs médicaux et des dispositifs diagnostiques, et pour la formation d'outils de micromoulage ou nanomoulage utiles dans l'élaboration de dispositifs miniatures optiques, électroniques, mécaniques, médicaux, et autres.
PCT/US2001/020264 2000-08-21 2001-06-26 Traitement de composition sol-gel et formation de motifs dans cette composition sol-gel par faisceau electronique Ceased WO2002017347A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10243827A1 (de) * 2002-09-14 2004-03-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Direktschreibendes Lithographieverfahren zur Herstellung einer zweidimensionalen Struktur im Submikrometerbereich
WO2004099835A1 (fr) * 2003-05-09 2004-11-18 Hernan Miguez Procede d'ecriture laser de motifs d'indices de refraction dans des cristaux photoniques de silicium
DE102004059034B4 (de) * 2003-12-11 2007-11-29 Infineon Technologies Ag Verfahren zum Herstellen einer Hartmaske in einem Kondensatorbauelement und eine Hartmaske zur Verwendung in einem Kondensatorbauelement
WO2008078161A3 (fr) * 2006-12-21 2008-08-21 Inglass Spa Installation informatisée pour produire des structures en résine, en composites ou autre
DE102011107123A1 (de) * 2011-07-12 2013-01-17 Robert Bosch Gmbh Verfahren zur Herstellung einer Oberflächenbeschichtung mit einem Mikrostruktur-Gitter und Solarkollektor mit einer solchen Oberflächenbeschichtung
WO2015066573A3 (fr) * 2013-11-01 2015-06-25 South Dakota State University Nouvelle solution pour le dépôt électrophorétique de nanoparticules sur des films minces
WO2019089409A1 (fr) * 2017-10-30 2019-05-09 Corning Incorporated Systèmes et procédés de formation de structures dimensionnellement sensibles

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04149090A (ja) * 1990-10-09 1992-05-22 Onoda Cement Co Ltd 結晶質誘電体薄膜の作成方法
JPH05294863A (ja) * 1992-04-20 1993-11-09 Dainippon Printing Co Ltd 電離放射線硬化型金属アルコキシド及びそれを用いた硬化塗膜の形成方法
US5271797A (en) * 1991-10-28 1993-12-21 Rohm Co., Ltd. Method for patterning metal oxide thin film
US5605723A (en) * 1994-05-16 1997-02-25 Mitsubishi Materials Corporation Method for forming a pattern of non-volatile ferroelectric thin film memory
US5772905A (en) * 1995-11-15 1998-06-30 Regents Of The University Of Minnesota Nanoimprint lithography
JPH10230560A (ja) * 1997-02-18 1998-09-02 Dainippon Printing Co Ltd 光学機能性膜及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04149090A (ja) * 1990-10-09 1992-05-22 Onoda Cement Co Ltd 結晶質誘電体薄膜の作成方法
US5271797A (en) * 1991-10-28 1993-12-21 Rohm Co., Ltd. Method for patterning metal oxide thin film
JPH05294863A (ja) * 1992-04-20 1993-11-09 Dainippon Printing Co Ltd 電離放射線硬化型金属アルコキシド及びそれを用いた硬化塗膜の形成方法
US5605723A (en) * 1994-05-16 1997-02-25 Mitsubishi Materials Corporation Method for forming a pattern of non-volatile ferroelectric thin film memory
US5772905A (en) * 1995-11-15 1998-06-30 Regents Of The University Of Minnesota Nanoimprint lithography
JPH10230560A (ja) * 1997-02-18 1998-09-02 Dainippon Printing Co Ltd 光学機能性膜及びその製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
RANTALA J.T. ET AL.: "Electron radiation sensitive hybrid sol-gel materials for electron-beam lithography and diffractive optics", SPIE, vol. 3469, July 1998 (1998-07-01), pages 30 - 37, XP002949078 *
RANTALA J.T. ET AL.: "Negative tone hybrid sol-gel material for electron-beam lithography", THIN SOLID FILMS, vol. 345, 1999, pages 185 - 187, XP002949079 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10243827A1 (de) * 2002-09-14 2004-03-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Direktschreibendes Lithographieverfahren zur Herstellung einer zweidimensionalen Struktur im Submikrometerbereich
DE10243827B4 (de) * 2002-09-14 2004-09-09 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Direktschreibendes Elektronenstrahl - Lithographieverfahren zur Herstellung einer zweidimensionalen Struktur im Submikrometerbereich
WO2004099835A1 (fr) * 2003-05-09 2004-11-18 Hernan Miguez Procede d'ecriture laser de motifs d'indices de refraction dans des cristaux photoniques de silicium
DE102004059034B4 (de) * 2003-12-11 2007-11-29 Infineon Technologies Ag Verfahren zum Herstellen einer Hartmaske in einem Kondensatorbauelement und eine Hartmaske zur Verwendung in einem Kondensatorbauelement
WO2008078161A3 (fr) * 2006-12-21 2008-08-21 Inglass Spa Installation informatisée pour produire des structures en résine, en composites ou autre
DE102011107123A1 (de) * 2011-07-12 2013-01-17 Robert Bosch Gmbh Verfahren zur Herstellung einer Oberflächenbeschichtung mit einem Mikrostruktur-Gitter und Solarkollektor mit einer solchen Oberflächenbeschichtung
WO2015066573A3 (fr) * 2013-11-01 2015-06-25 South Dakota State University Nouvelle solution pour le dépôt électrophorétique de nanoparticules sur des films minces
WO2019089409A1 (fr) * 2017-10-30 2019-05-09 Corning Incorporated Systèmes et procédés de formation de structures dimensionnellement sensibles

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