WO2013142344A1 - Procédés et appareil pour le dépôt de couche atomique à la pression atmosphérique - Google Patents

Procédés et appareil pour le dépôt de couche atomique à la pression atmosphérique Download PDF

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Publication number
WO2013142344A1
WO2013142344A1 PCT/US2013/032203 US2013032203W WO2013142344A1 WO 2013142344 A1 WO2013142344 A1 WO 2013142344A1 US 2013032203 W US2013032203 W US 2013032203W WO 2013142344 A1 WO2013142344 A1 WO 2013142344A1
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WO
WIPO (PCT)
Prior art keywords
substrate
vapor
gas delivery
gas
flow
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PCT/US2013/032203
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English (en)
Inventor
Gregory N. Parsons
Christopher John OLDHAM
Jesse S. JUR
Moataz Bellah MOUSA
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North Carolina State University
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Publication of WO2013142344A1 publication Critical patent/WO2013142344A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45519—Inert gas curtains
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
    • C23C16/45548—Atomic layer deposition [ALD] characterized by the apparatus having arrangements for gas injection at different locations of the reactor for each ALD half-reaction
    • C23C16/45551—Atomic layer deposition [ALD] characterized by the apparatus having arrangements for gas injection at different locations of the reactor for each ALD half-reaction for relative movement of the substrate and the gas injectors or half-reaction reactor compartments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C23C16/45574—Nozzles for more than one gas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates

Definitions

  • the presently disclosed subject matter relates to the modification of substrates, such as porous substrates, by the Atomic Layer Epitaxy (ALE) process, which is also commonly referred to as Atomic Layer Deposition (ALD), and related gas-phase deposition processes.
  • ALE Atomic Layer Epitaxy
  • ALD Atomic Layer Deposition
  • the presently disclosed subject matter relates in particular to processes and apparatuses for the modification of substrates by low-temperature, atmospheric pressure ALD that can be performed in the presence or absence of a closed reaction chamber and without the need for substrate movement.
  • Atomic Layer Deposition which can sometimes be referred to as Atomic Layer Epitaxy (ALE), Atomic Layer Chemical Vapor Deposition (ALCVD), or Molecular Layer Deposition (MLD), is a process, described, for example, in U.S. Patent No. 4,058,430, for the fabrication of thin films.
  • ALD Atomic Layer Deposition
  • ALE Atomic Layer Epitaxy
  • ACVD Atomic Layer Chemical Vapor Deposition
  • MLD Molecular Layer Deposition
  • ALD Atomic Layer Deposition
  • Al 2 0 3 Aluminum oxide has many desirable traits such as strong adhesion to various materials, good dielectric properties, and chemical and thermal stability.
  • Conventional ALD processes are often designed to rapidly pulse different gaseous substances onto a substrate in a closed reaction chamber in a sequence. However, it can be difficult to introduce the gases into the chamber at useful speeds and without unwanted mixing. In order to maximize the flux of gases in to the chamber, they are often pulsed at high pressure and then removed by vacuum. Thus, current nanoscale coating technology often requires expensive vacuum equipment
  • the presently disclosed subject matter provides a method for modifying a substrate, the method comprising: providing a substrate; contacting the substrate with a vapor-phase precursor comprising an organic or an inorganic component for a first period of time to create a partial atomic layer of the organic or inorganic component on the substrate, wherein the contacting comprises placing the substrate in proximity to an outlet directing a flow of the vapor-phase precursor to the substrate; and contacting the substrate with a vapor-phase reactant for a second period of time to complete the formation of an atomic layer on the substrate, wherein the contacting comprises placing the substrate in proximity to an outlet directing a flow of the vapor-phase reactant to the substrate; wherein said method further comprises providing a flow of a non-reactive gas to the substrate during and/or after one or both of the contacting steps; and wherein said method is performed at atmospheric pressure, wherein the contacting is performed in the presence or absence of a closed reaction chamber, and wherein the method can be performed in the absence of substrate or
  • the contacting steps are repeated one or more times to provide a thin film of a desired thickness on the substrate. In some embodiments, the contacting steps are repeated to provide a thin film having a thickness of between about 1 nanometer and about 10 microns.
  • the substrate is a porous substrate. In some embodiments, the substrate is a fiber-based substrate, a metal organic framework, a zeolite, or anodic aluminum oxide.
  • the substrate is a fiber-based substrate comprising natural fibers, synthetic fibers, or both natural and synthetic fibers.
  • the fiber-based substrate is selected from the group comprising cotton fiber, cotton fabric, woven cotton fabric, non-woven cotton fabric, protein-based fiber, polyvinyl alcohol fiber, polyvinyl alcohol fabric, woven polyvinyl alcohol fabric, non-woven polyvinyl alcohol fabric, polyolefin polymer fiber, polyolefin fabric, woven polyolefin fabric, non-woven polyolefin fabric, polyethylene terephthalate fiber, polyethylene terephthalate fabric, woven polyethylene terephthalate fabric, non-woven polyethylene terephthalate fabric, polyamide fiber, polyamide fabric, woven polyamide fabric, non-woven polyamide fabric, acrylic fiber, acrylic fabric, woven acrylic fabric, non-woven acrylic fabric, polycarbonate fiber, polycarbonate fabric, woven polycarbonate fabric, non-woven polycarbonate fabric, fluorocarbon fiber, fluorocarbon fabric, fluorocarbon fabric, flu
  • the substrate comprises a natural or synthetic polymer-based surface.
  • said polymer-based surface comprises a material selected from polyimide, polyethersulfone, cellophane, polydimethylsiloxane, polytetrafluoroethylene, wood, cellulose, cotton, polyvinyl alcohol, polyvinyl chloride, polystyrene, polyacrylonitrile, polyethylene, polybutylene, and polyethylene terephthalate.
  • the substrate is substantially stationary. In some embodiments, the substrate is non-planar.
  • the flow of vapor-phase precursor, vapor-phase reactant, and non-reactive gas are provided by an apparatus comprising one or more gas delivery units, each gas delivery unit comprising: a first input for the non-reactive gas; one or more gas delivery channels, wherein a first end of each gas delivery channel is in flow communication with at least an input for receiving the vapor-phase precursor or the vapor-phase reactant, and wherein a second end of each gas delivery channel comprises an outlet for directing a flow of gas to the substrate; and an output face in flow communication with the outlet of each of the one or more gas delivery channels, with the first input for the non-reactive gas, and with a deposition zone exterior to the gas delivery unit.
  • the outlet or outlets of the one or more gas delivery channels are coplanar with the output face. In some embodiments, the outlet or outlets of the one or more gas delivery channels are in an interior space of the gas delivery unit.
  • At least one gas delivery unit comprises a gas delivery channel wherein the first end of the gas delivery channel is in flow communication with one or more input for sequentially receiving the vapor- phase precursor, the non-reactive gas, and the vapor-phase reactant, such that the outlet of the gas delivery channel can sequentially direct a flow of vapor- phase precursor, the non-reactive gas, and the vapor-phase reactant to the substrate.
  • At least one gas delivery unit comprises at least two gas delivery channels, wherein said at least two gas delivery channels comprise: a first gas delivery channel, wherein said first gas delivery channel has a first end in flow communication with one or more inputs for the vapor- phase precursor or for the vapor-phase precursor and the non-reactive gas, and a second end comprising an outlet for delivering the vapor-phase precursor or for sequentially delivering the vapor-phase precursor and the non-reactive gas; and a second gas delivery channel, wherein said second gas delivery channel has a first end in flow communication with one or more inputs for the vapor-phase reactant or for the vapor-phase reactant and the non-reactive gas, and a second end comprising an outlet for delivering the vapor-phase reactant or for sequentially delivering the vapor-phase reactant and the non-reactive gas.
  • the first and second gas delivery channels are substantially parallel to one another.
  • the gas delivery unit comprises a partition between the first and second gas delivery channels extending in a direction parallel to said first and second gas delivery channels and at or beyond the outlets of the first and second gas delivery channels toward the output face, and further wherein the gas delivery unit comprises a second input for the non-reactive gas such that the first input for the non- reactive gas is located on one side of the partition and the second input for the non-reactive gas is located on the other side of the partition.
  • the first and second gas delivery channels join one another near their second ends to form a single outlet.
  • providing the substrate comprises positioning an outer or external surface of the substrate between about 0.01 millimeters and about 20 millimeters from an output face of a gas delivery unit. In some embodiments, providing the substrate comprises positioning an outer or external surface of the substrate between about 0.02 millimeters and about 1.0 millimeters from an output face of a gas delivery unit. In some embodiments, providing the substrate comprises positioning an outer or external surface of the substrate between about 0.02 millimeters and about 0.5 millimeters from an output face of a gas delivery unit.
  • an outlet for delivering the vapor-phase precursor is located substantially in the center of the output face.
  • providing the substrate comprises positioning the substrate such that a plurality of portions of an outer or external surface of the substrate are in proximity to the output faces of a plurality of gas delivery units.
  • the vapor-phase precursor comprises a metal- containing compound.
  • the vapor-phase precursor comprises trimethylaluminum (TMA), diethyl zinc (DEZ), titanium tetrachloride (TiCI 4 ), tungsten hexafluoride, titanium isopropoxide, or zirconium tertbutoxide (ZTB).
  • the flow of the vapor-phase precursor is provided at a flow rate between about 0.001 and about 5.0 standard liters per minute (slm). In some embodiments, the flow of the vapor-phase precursor is provided at a flow rate between about 0.05 slm and about 0.2 slm. In some embodiments, the first period of time is between about 0.01 seconds and about 60.0 seconds. In some embodiments, the first period of time is between about 0.1 seconds and about 2 seconds.
  • the vapor-phase reactant is selected from the group comprising H 2 0, NH 3 , ozone, 0 2 , C0 2 , CO, NO, N 2 0, N0 2 , SiH 4 , and Si 2 H 6 .
  • the vapor-phase reactant is provided at a flow rate between about 0.001 and about 5.0 slm.
  • the vapor- phase reactant is provided at a flow rate between about 0.05 slm and about 0.2 slm.
  • the second period of time is between about 0.01 seconds and about 60.0 seconds. In some embodiments, the second period of time is between about 0.1 seconds and about 2 seconds.
  • the vapor-phase precursor is TMA and the method comprises modifying the substrate with aluminum oxide.
  • the non-reactive gas is selected from nitrogen and argon. In some embodiments, non-reactive gas is provided at a flow rate between about 1 and about 100 slm. In some embodiments, the non-reactive gas is provided at a flow rate between about 5 and about 20 slm.
  • the method comprises providing a flow of a non- reactive gas for between about 1 second and about 300 seconds after the first period of time and before the second period of time and/or after the second period of time. In some embodiments, the method comprises providing a flow of a non-reactive gas for about 40 seconds after the first period of time and before the second period of time and/or after the second period of time. In some embodiments, the method comprises providing a flow of a non-reactive gas for about 10 seconds after the first period of time and before the second period of time and/or after the second period of time.
  • the method comprises providing a flow of a non-reactive gas for more than about 300 seconds after the first period of time and before the second period of time and/or after the second period of time. In some embodiments, the method comprises providing a flow of a non-reactive gas during the first and/or second periods of time.
  • one or both contacting steps are conducted at a temperature between about 20°C and about 200°C. In some embodiments, one or both contacting steps are conducted at a temperature of about 120°C. In some embodiments, one or both contacting steps are conducted at a temperature of about 50°C.
  • the presently disclosed subject matter provides an apparatus for modifying a substrate, wherein the apparatus comprises one or more gas delivery units, each gas delivery unit comprising: a first input for the non-reactive gas; one or more gas delivery channels, wherein a first end of each gas delivery channel is in flow communication with at least an input for receiving the vapor-phase precursor or the vapor-phase reactant, and wherein a second end of each gas delivery channel comprises an outlet for directing a flow of gas to a substrate; and an output face in flow communication with the outlet of each of the one or more gas delivery channels and with the first input for the non-reactive gas, and is adapted for gaseous and/or flow communication with an exterior of the gas delivery unit.
  • the outlet or outlets of the one or more gas delivery channels are coplanar with the output face. In some embodiments, the outlet or outlets of the one or more gas delivery channels are in an interior space of the gas delivery unit. In some embodiments, an outlet for delivering a flow of the vapor-phase precursor is at or near the center of the output face. In some embodiments, the outlet or outlets of the one or more gas delivery channels each have a diameter that is between about 0.1 mm and about 0.5 mm.
  • the output face is square or rectangular. In some embodiments, the output face is substantially circular. In some embodiments, the output face has a diameter that is about 0.5 cm or smaller. In some embodiments, the output face has a diameter that is between about 0.5 cm and about 4.0 cm. In some embodiments, the output face has one or more openings, wherein the one or more openings each have a diameter that is between about 0.1 mm and about 0.5 mm.
  • the gas delivery unit comprises a tubular body comprising an input face at a first end of the tubular body adapted to receive one or more input ports and/or one or more gas delivery channels, and wherein the output face is at a second end of the tubular body.
  • the tubular body is tapered such that the output face has a smaller diameter than the input face.
  • the input face has a diameter that is between about 0.5 and about 4.0 centimeters. In some embodiments, the input face has a diameter that is between about 0.5 and about 1.0 centimeters.
  • At least one gas delivery unit comprises a gas delivery channel wherein the first end of the gas delivery channel is in flow communication with one or more input for sequentially receiving the vapor- phase precursor, the non-reactive gas, and the vapor-phase reactant.
  • At least one gas delivery unit comprises at least two gas delivery channels, wherein said at least two gas delivery channels comprise: a first gas delivery channel, wherein said first gas delivery channel has a first end in flow communication with one or more inputs for the vapor- phase precursor or for the vapor-phase precursor and the non-reactive gas, and a second end comprising an outlet for delivering the vapor-phase precursor or for sequentially delivering the vapor-phase precursor and the non-reactive gas; and a second gas delivery channel, wherein said second gas delivery channel has a first end in flow communication with one or more inputs for the vapor-phase reactant or for the vapor-phase reactant and the non-reactive gas, and a second end comprising an outlet for delivering the vapor-phase reactant or for sequentially delivering the vapor-phase reactant and the non-reactive gas.
  • the first and second gas delivery channels are substantially parallel to one another.
  • the gas delivery unit comprises a partition between the first and second gas delivery channels extending in a direction parallel to said first and second gas delivery channels and extending beyond the outlets of first and second gas delivery channels toward the output face, and further wherein the gas delivery unit comprises a second input for the non-reactive gas such that the first input for the non- reactive gas is located on one side of the partition and the second input for the non-reactive gas is located on the other side of the partition.
  • the first and second gas delivery channels join one another near their second ends to form a single outlet.
  • the apparatus further comprises a support for supporting a substrate when the substrate is positioned about 20 mm or less from, but not in direct contact with, the output face.
  • the support is adapted to hold the substrate stationary.
  • the support is adapted to translate the substrate with respect to an output face.
  • one or more gas delivery units can be translated with respect to a length, width, and/or height of a substrate.
  • the apparatus further comprises a roller system for positioning a substrate sheet relative to the apparatus.
  • the apparatus comprises a plurality of gas delivery units.
  • the plurality of gas delivery units are arranged in a single row to form a linear array of gas delivery units.
  • the plurality of gas delivery units are arranged in a plurality of rows to form a square or rectangular array of gas delivery units.
  • the apparatus further comprises an exhaust system. In some embodiments, the apparatus further comprises one or more spacers extending from the exterior of the output face to assist in positioning the substrate. In some embodiments, the apparatus further comprises one or more satellite gas delivery units, wherein each satellite gas delivery unit comprises a gas delivery channel for delivery of a flow of non-reactive gas to the substrate.
  • the presently disclosed subject matter provides a modified substrate created by a method comprising: providing a substrate; contacting the substrate with a vapor-phase precursor comprising an organic or an inorganic component for a first period of time to create a partial atomic layer of the organic or inorganic component on the substrate, wherein the contacting comprises placing the substrate in proximity to an outlet directing a flow of the vapor-phase precursor to the substrate; and contacting the substrate with a vapor-phase reactant for a second period of time to complete the formation of an atomic layer on the substrate, wherein the contacting comprises placing the substrate in proximity to an outlet directing a flow of the vapor-phase reactant to the substrate; wherein said method further comprises providing a flow of a non- reactive gas to the substrate during and/or after one or both of the contacting steps; and wherein said method is performed at atmospheric pressure, wherein the contacting is performed in the presence or absence of a closed reaction chamber, and wherein the method can be performed in the absence of substrate or outlet movement.
  • the presently disclosed subject matter provides a modified substrate produced using an apparatus that comprises one or more gas delivery units, each gas delivery unit comprising: a first input for the non- reactive gas; one or more gas delivery channels, wherein a first end of each gas delivery channel is in flow communication with at least an input for receiving the vapor-phase precursor or the vapor-phase reactant, and wherein a second end of each gas delivery channel comprises an outlet for directing a flow of gas to a substrate; and an output face in flow communication with the outlet of each of the one or more gas delivery channels and with the first input for the non-reactive gas, and is adapted for gaseous and/or flow communication with an exterior of the gas delivery unit.
  • the modified substrate is patterned with a thin film.
  • the presently disclosed subject matter provides an apparatus for modifying a substrate, wherein the apparatus comprises a roller system and an array of vapor-phase precursor delivery units and vapor- phase reactant delivery units, wherein each vapor-phase precursor delivery unit comprises a vapor-phase precursor delivery channel, wherein a first end of the channel is in flow communication with one or more inputs for receiving the vapor-phase precursor or receiving the vapor-phase precursor and a non- reactive gas, and wherein a second end of the channel comprises an outlet for directing a flow of vapor-phase precursor and/or non-reactive gas to a substrate; wherein each vapor-phase reactant delivery unit comprises a vapor- phase reactant delivery channel, wherein a first end of the channel is in flow communication with one or more inputs for receiving the vapor-phase reactant or receiving the vapor-phase reactant and a non-reactive gas, and wherein a second end of the channel comprises an outlet for directing a flow of vapor- phase reactant and/or non-reactive
  • the apparatus further comprises an exhaust system for creating a pressure differential between the outlets of the delivery channels and the substrate and/or to remove excess vapor-phase precursor, excess vapor-phase reactant, non-reactive gas, and/or any gaseous side products formed during use of the apparatus.
  • the presently disclosed subject matter provides a modified substrate produced using said apparatus.
  • an inner surface or both an outer surface and an inner surface of the substrate are modified.
  • directing a flow of gas to the substrate comprises directing the flow of gas to an outer and/or an inner surface of the substrate.
  • Figure 1 is a schematic drawing illustrating a single channel apparatus
  • Apparatus 100 has a valve design and gas lines 110 suitable for vapor delivery from a liquid source for vapor-phase precursor A (shown by cross-hatching) and a high pressure gas source for vapor-phase reactant B (shown by zigzag lines).
  • the flow of inert gas (shown by stippling) from inert gas source IG to a liquid source for vapor- phase precursor A can be controlled via valve V-1.
  • Valve V-2 can control the flow from the liquid source to the single gas delivery channel in the delivery head.
  • Valve V-3 can control the flow of inert gas into gas delivery channel 140, e.g., allowing gas delivery channel 140 to be purged of A or B as necessary.
  • Valve V-4 controls flow between inert gas source IG, the liquid source for vapor-phase reactant B, and gas delivery channel 140 in delivery head 120.
  • Delivery head 120 also contains separate input 150 for the inert gas.
  • Delivery head 120 can direct the flow of A, B and the inert gas to a surface of substrate 160 from outlet 70.
  • Optional exhaust system 180 can draw excess gases from the opposite side of the porous substrate to a vacuum.
  • FIG. 2 is a schematic drawing illustrating single channel apparatus 200 of the presently disclosed subject matter.
  • Apparatus 200 includes single gas delivery channel 210 with inlet 212 that can sequentially direct a flow of vapor A (i.e., a vapor-phase precursor; shown by cross-hatching), inert "purge” gas (IG, shown by stippling), vapor B (i.e., a vapor-phase reactant; shown by zigzag lines) and inert "purge” gas to a surface of substrate 260 (e.g., a porous substrate) via outlet 270.
  • vapor A i.e., a vapor-phase precursor; shown by cross-hatching
  • inert "purge” gas IG, shown by stippling
  • vapor B i.e., a vapor-phase reactant; shown by zigzag lines
  • inert "purge” gas i.e., a vapor-phase reactant
  • Gas delivery unit 220 includes separate input 215 for inert "purge” gas that allows further inert gas to be directed to the surface of substrate 260 from output face 240 of delivery unit 220.
  • an optional exhaust system 280 can carry excess gas away from substrate 260.
  • Substrate 260 can optionally be translated relative to output face 240 as indicated by the heavy solid arrows.
  • FIG. 3 is a schematic drawing illustrating dual channel apparatus 300 of the presently disclosed subject matter.
  • Apparatus 300 includes gas delivery unit 380 that includes two gas delivery channels, 320 and 340.
  • Gas delivery channel 320 with inlet 318 can sequentially deliver vapor A (i.e., a vapor-phase precursor, shown by cross-hatching) and inert "purge” gas (IG, shown by stippling).
  • Gas delivery channel 340 with inlet 338 can sequentially deliver vapor B (i.e., a vapor-phase reactant, shown by zigzag lines) and inert "purge" gas.
  • Gas delivery channels 320 and 340 are oriented such that they form single output 385 at the vertex of a right or acute angle formed between terminal portions 322 and 342 of the two channels.
  • Delivery unit 380 also includes separate input 360 for an inert "purge" gas. Gases from output face 390 of delivery unit 380 are directed to a surface of substrate 395 (e.g., a porous substrate), which can optionally be translated relative to output face 390 as indicated by the heavy arrows. On a side of the substrate opposite to output face 390, optional exhaust system 397 can be used to carry excess gases away from substrate 395.
  • substrate 395 e.g., a porous substrate
  • exhaust system 397 can be used to carry excess gases away from substrate 395.
  • FIG 4 is a schematic drawing illustrating dual channel apparatus 400 of the presently disclosed subject matter.
  • Apparatus 400 includes gas delivery unit 405 that includes two substantially parallel gas delivery channels 410 and 415.
  • Parallel gas delivery channel 410 with inlet 408 can direct a flow of vapor A (i.e., a vapor-phase precursor, shown by cross-hatching) to a surface of substrate 460 (e.g., a porous substrate) via outlet 412, while gas delivery channel 415 with inlet 413 can direct a flow of vapor B (i.e., a vapor-phase reactant, shown by zigzag lines) to the surface of the substrate through outlet 417.
  • Outlets 412 and 417 are coplanar with output face 440 of gas delivery unit 405.
  • Partition 420 is located between and parallel to gas delivery channels 410 and 415, and extends beyond output face 440 toward substrate 460.
  • Gas delivery unit 405 includes additional inputs 430 and 435 for inert "purge" gas IG (shown by stippling), one on each side of partition 420, such that the flow from each of gas delivery channels 410 and 415 is surrounded by a flow of inert gas.
  • Substrate 460 can optionally be translated relative to output face 440 as indicated by the heavy arrows.
  • optional exhaust system 480 can be used to carry excess gases away from substrate 460.
  • Figure 5 is a schematic drawing illustrating a bottom view of a gas delivery unit having a circular output face.
  • the outlet of a single gas delivery channel (cross-hatching) is located substantially in the center of the output face, having a diameter d.
  • An input for non-reactive gas e.g., an inert gas IG, shown by stippling
  • Figure 6 is a schematic drawing illustrating a bottom view of a gas delivery unit having a rectangular output face.
  • a rectangular output of a gas delivery channel (cross-hatching) is located substantially in the center of the output face and has dimensions I and w.
  • An input for non-reactive gas e.g., an inert gas IG, shown by stippling
  • Figure 7 is a schematic drawing illustrating the modification of the surface of substrate 720 wherein single channel gas delivery unit 710 is rastered over the surface of the substrate to provide patterned film 725.
  • Single gas delivery channel 712 of unit 710 can sequentially deliver vapor-phase precursor A, inert gas (inert), vapor-phase reactant B, and inert gas.
  • Unit 710 also includes separate input 714 for inert gas.
  • Optional exhaust system 730 is located under the substrate to direct excess gases away from the substrate.
  • FIG. 8 is a schematic drawing illustrating an apparatus of the presently disclosed subject matter containing an array of single point reactors (gas delivery units).
  • Apparatus 800 includes array 810 of reactors 812 wherein each reactor can deliver either only the vapor-phase precursor (A) and inert gas (I) or only the vapor-phase reactant (B) and the inert gas (I).
  • Apparatus 800 also includes roller system 820 for moving substrate 840 (e.g., a porous substrate) past array 810.
  • Optional exhaust system 860 can be used to direct excess gases away from the substrate.
  • FIG. 9 is a schematic drawing illustrating an apparatus of the presently disclosed subject matter.
  • Apparatus 900 shows linear array 902 of single point reactors 904 (i.e., gas delivery units), wherein each single point reactor includes separate delivery channels 906 for a vapor-phase reactant R (e.g., water) and a vapor-phase precursor P (e.g., trimethylaluminum, TMA) and inlet 908 for a non-reactive (e.g., nitrogen, N 2 ) gas.
  • R e.g., water
  • P e.g., trimethylaluminum, TMA
  • Outlets 910 and 912 of the delivery channels can be located at (i.e., be co-planar with) or near (e.g., recessed about 1 to 20 millimeters from) output face 914 of the single point reactor.
  • a substrate S which can be movable or fixed, is positioned such that an outer surface of the substrate is in proximity to the output faces (e.g., within about 20 mm or less) of the reactors. Gases can be removed from the underside of the substrate by an optional exhaust system. The flow of gases from each reactor provides a deposition zone DZ over a portion of the substrate where an atomic layer is deposited to provide a coated substrate CS. In the linear array shown, a series of adjoining portions of the substrate can be modified/coated. At its widest point, single point gas delivery reactor 904 can have an outer diameter of between about 0.5 cm and about 1.0 cm, and tapers toward the output face.
  • Figure 10 is a schematic drawing illustrating an apparatus of an embodiment of the presently disclosed subject matter.
  • Apparatus 1000 comprises single point reactor 1010 with two delivery channels, 1020 and 1030 (i.e., one for delivery of a vapor phase precursor (A) and one for delivery of a vapor phase reactant (B)) and side input 1040 for a non-reactive gas (NRG).
  • Outlets 1050 of delivery channels 1020 and 1030 are in the interior of single point reactor 1010, recessed from output face 1060. Gas flow is directed from opening 1070 in output face 1060 to substrate 1080. Spacers 1075 are extended from output face 1060 toward substrate 1080.
  • Satellite non-reactive gas delivery units 1090 are positioned on either side of the single point reactor 1010. Exhaust gases 1095 can exit from openings between spacers 1075 of single point reactor 1010 and satellite non-reactive gas delivery units 1090.
  • FIG 11 is a graph showing the average growth (in nanometers, nm) of an aluminum oxide film on a silicon substrate as a function of the number of atomic layer deposition (ALD) cycles to which the substrate is exposed.
  • ALD atomic layer deposition
  • Each ALD cycle includes a 1.0 second dose of trimethylaluminum (TMA, 0.05 standard liters per minute (slm)) and a 1.0 second dose of water (0.05 slm).
  • TMA trimethylaluminum
  • slm 0.05 standard liters per minute
  • Water 0.05 slm
  • Nitrogen gas was used as a purge at a flow rate of 10 slm.
  • the bulk nitrogen flow was heated to 120°C.
  • the data (diamonds) is given for 0, 50, 150, 225, and 300 ALD cycles as indicated at the x axis.
  • the error bars represent the extra film growth observed at the center of the substrate (i.e., at the center of the ALD deposition zone) or the reduced growth at the substrate border.
  • the single data point shown by a circle represents aluminum oxide film growth after 300 cycles of TMA only dosing (i.e., no water dose).
  • Figure 12 is a micrograph image of a silicon substrate after 300 cycles of atomic layer deposition (ALD) process as described in Figure 1.
  • the labeled regions i.e., SP, i.e., Stagnant point; Z1 , i.e., Zone 1 ; Z2, i.e., Zone 2; and Z3, i.e., Zone 3) represent different deposition regions within the total deposition zone.
  • the relative sizes and/or presence of the different regions can be controlled by ALD reactor dimensions and ALD deposition conditions (e.g., inert gas flow rate, dose times, purge times, etc.).
  • SP is at the center of a flat, rigid, fixed substrate region in proximity to a single point reactor, where gas from the reactor impinges the substrate in an approximately vertical flow.
  • SP has a diameter approximately equivalent to a reactor outlet/output face opening.
  • SP gives rise to deposition of a relatively thicker film at the center of the substrate surface.
  • the gas starts accelerating radially, leading to a laminar flow region (Z1), followed by a transition zone (Z2), which is turbulent and full of eddies.
  • Z1 laminar flow region
  • Z2 transition zone
  • ALD deposition can be relatively thicker in Z2 than in Z1 due to these eddies.
  • Past transition zone Z2 the gas starts decelerating as it goes further away from the reactor outlet, which gives rise to a third deposition zone, Z3, with less uniform coating.
  • Figure 13 is a drawing showing a schematic illustration of the image shown in Figure 12. SP is shown in light grey, Z1 in medium grey, Z2 in black, and Z3 in dark grey.
  • Figure 14 shows, in the top view, a side-on schematic illustration of gas (flow indicated by arrows) impinging a flat, non porous substrate 1420 from an opening 1410 in the output face 1415 of a single point reactor 1400 of the presently disclosed subject matter.
  • the middle view of Figure 14 shows a schematic illustration of the laminar and turbulent boundary gas layers that form as gas flows in a radial direction away from a point under opening 1410.
  • the bottom view of Figure 14 is a schematic illustration of radial gas flow velocity (in arbitrary units) from the impinging gas along the substrate surface.
  • Figure 15 is a micrograph image of a silicon substrate treated to 300 cycles of atomic layer deposition (ALD) as described above for Figure 11 , only wherein the nitrogen gas is provided at a flow rate of 7 standard liters per minute (slm) instead of 10 slm.
  • ALD atomic layer deposition
  • the presently disclosed subject matter relates generally to methods and apparatuses for the modification of substrates, such as fibers and textile media or other porous substrates. More particularly, the presently disclosed subject matter relates to methods and apparatuses for ALD and related processes that can be performed at atmospheric pressure, low temperature, and wherein the substrate can be present in the ambient environment (i.e., not inside a closed reaction chamber, such as a chamber or vessel than can be placed under vacuum).
  • the substrate can have a variety of different shapes and can be stationary or moving. In some embodiments, movement of neither the substrate nor the apparatus delivering the reactants is necessary.
  • the term "about”, when referring to a value or to an amount of time, flow rate, temperature, distance, diameter, or thickness is meant to encompass variations of in one example ⁇ 20% or ⁇ 10%, in another example ⁇ 5%, in another example ⁇ 1%, and in still another example ⁇ 0.1 % from the specified amount, as such variations are appropriate to perform the disclosed methods.
  • the substrate can be porous or non-porous.
  • the substrate can be flexible or non-flexible.
  • the substrate can have any suitable shape, such as but not limited to, planar, conical, rod-shaped, spherical, irregular or combinations thereof.
  • the term "porous substrate” refers to a substrate that contains pores or voids. Porous substrates can comprise inorganic, organic, or hybrid inorganic- organic materials.
  • Porous substrates can have outer surfaces and inner surfaces, wherein the term “inner surface” refers to the surface of the substrate located within a pore or void and wherein the term “outer surface” refers to a substrate surface located on an exterior surface of the porous substrate (e.g., as a whole).
  • the term "a surface” can refer to an interior surface, an exterior surface or both an interior and an exterior surface.
  • metal-organic framework refers to porous substrates comprising crystalline compounds of metal ions or metal clusters coordinated to organic molecules (e.g. rigid organic molecules).
  • organic molecules e.g. rigid organic molecules.
  • the organic molecules can be mono- or multi-dentate.
  • Suitable organic molecules for metal-organic frameworks include bi- and tri-dentate carboxylates or amides, as well as triazole and other nitrogen-containing aromatics.
  • fiber and fiber-based substrate are meant in their broadest sense to encompass all materials having a fibrous structure.
  • any polymer, fiber or textile material of a continuous shape is encompassed within the meaning of the terms fiber and fiber-based substrate as they are used herein.
  • the fiber and fiber-based substrates of the presently disclosed subject matter include both synthetic and natural fibers as well as fiber-based materials produced by natural or synthetic approaches, such as but not limited to, cotton fibers and fabrics, protein-based fibers such as silk, elastomeric polymers and fabrics (e.g., polyolefins such as polypropylene) and polyvinyl alcohol polymers and fabrics.
  • the fabrics of the presently disclosed subject matter include both woven and non-woven fabrics, and include, for example, a woven cotton fabric comprising yarns made up of many cotton fibers of different sizes and shapes.
  • micro- and “nano-” have the meaning that would be ascribed to them by one of ordinary skill in the art.
  • “micro” can refer to a structural feature having a dimension (e.g., a thickness) ranging from about 100 microns to about 1 nanometer in size. In some embodiments, the structural feature has a dimension ranging from about 10 microns to about 1 micron in size. In some embodiments, “nano” refers to a structural feature having a dimension ranging from about 1 micron to about 1 nm in size. In some embodiments, the structural feature has a dimension ranging from about 1 micron to about 10 nm in size. In some embodiments, the structural feature has a dimension ranging from about 100 nm to about 1 nm in size.
  • the term "thin film” refers to a film deposited on a surface of a substrate wherein the film has a thickness ranging between about .1 nm to about 100 microns. In some embodiments, the thin film has a thickness that is between about 1 nm and about 10 microns.
  • non-reactive or “inert” refer to a gas that does not react with any component present in the process (e.g., with a vapor-phase reactant or vapor-phase precursor or with the substrate surface).
  • the non-reactive gas is a noble gas (e.g., argon (Ar), helium (He), or neon (Ne)) or nitrogen (N 2 ) gas.
  • closed reaction chamber refers to a chamber that can be maintained under vacuum.
  • a closed reaction chamber refers to a chamber or a vessel than can be maintained under a vacuum of about 10 ⁇ 1 Torr to about 10 ⁇ 4 Torr.
  • a closed reaction chamber refers to a chamber or a vessel that can be maintained at a pressure of about 0.0001 Torr to about 500 Torr.
  • Low temperature ALD can be considered deposition at temperatures less than about 200°C.
  • the temperature can approach room temperature (i.e., about 20 or 25°C), depending on the reactant chemicals and reaction conditions employed.
  • the presently disclosed subject matter relates generally to methods and apparatuses for modifying a substrate (e.g., depositing a thin film) by an ALD or similar process (e.g., molecular layer deposition (MLD), sequential vapor infiltration (SVI), and multi-pulse infiltration (MPI)).
  • an ALD process can be defined by sequential exposures of a substrate to vapors that react with a surface of the substrate, separated by an inert gas purge.
  • An SVI process can be defined by increased exposure of a gas to a surface and material growth that is characterized as being sub-surface.
  • ALD can comprise a repeated binary sequence of self- limiting precursor adsorption and reaction steps.
  • the self- limiting nature of the precursor adsorption results in material being built up as a series of atomic layers.
  • Vapor-phase precursor molecules can be pulsed over a substrate and react with available substrate surface groups, creating a saturated substrate surface.
  • Excess precursor can be removed from the vapor phase by a purge gas (e.g., Ar).
  • the reactant gas can be pulsed onto the substrate, where it reacts with the adsorbed precursor layer to form a layer of the target film-forming material. Since no gas phase reaction occurs, the target film can be grown layer-by-layer on the substrate. Therefore, the film thickness is directly controlled by the number of reactant exposure cycles used.
  • a single ALD cycle can typically deposit about 0.1 to about 0.5 nm of a film.
  • Thin film thicknesses of from about 3 nm to about 30 nm can be formed by repeated ALD cycles for semiconductor applications. Even thicker films (e.g., up to 100 nm, up to 1 micron, or up to 10 microns or more) can be provided by repeated ALD cycles for other applications.
  • the growth rate can be adjusted by changing one or more of a number of parameters of the ALD process (e.g., the precursor and reactant, pulse time, gas flow, gas velocity, temperature, pressure, and such).
  • the self-limitation of the ALD process can allow increased conformality of ALD films on various substrates. Due to the fact that surface saturation can occur on all surfaces, conformality can be achieved for very high aspect ratio substrates.
  • the partial reaction of the precursor in each deposition cycle differentiates ALD from more common chemical vapor deposition (CVD) processes and provides ALD an ability for high precision film formation.
  • the modification process can be performed at atmospheric pressure and in the absence of a closed reaction chamber.
  • the presently disclosed processes and/or apparatuses do not rely on the movement of the substrate (e.g., to complete the formation of a complete atomic layer by moving the substrate between a zone for depositing one reactant (e.g., a precursor) and a zone for depositing a second reactant).
  • the presently disclosed subject matter does not relate to a "spatial" ALD process.
  • the substrate of the presently disclosed subject matter can be porous and the reactant and/or non-reactive gases can be directed in a flow or flows to an outer surface of the substrate and/or within the substrate (e.g., to an interior surface of the substrate). In some embodiments, the flow or flows can be directed through a substrate.
  • the presently disclosed apparatus or methods can provide infiltration or bulk modification of a porous substrate. In some embodiments, all of the surfaces (both inner and outer) of a substrate are coated to provide a conformally coated porous substrate.
  • the presently disclosed subject matter more particularly relates to the production of conformal, uniformly thin films on a surface of a substrate with precise thickness and composition control over large scales.
  • the presently disclosed subject matter provides a relatively low cost method to deposit thin conformal coatings of metal oxides and other materials onto surfaces with arbitrary size and shape, wherein the surface can be maintained in the ambient environment during the deposition.
  • a wide variety of materials can be deposited by the present methods, including metals, metal oxides, metal nitrides, polymers, organic-inorganic hybrid layers, and other materials.
  • the deposition of certain materials can be conducted by ALD at relatively low temperatures (e.g., less than about 200°C, less than about 150°C, less than about 100°C), thereby limiting thermal damage to temperature-sensitive materials, such as textiles and polymer fiber media.
  • ALD can also be used to create microstructures and nanostructures, such as but not limited to nanolaminates of different materials.
  • the presently disclosed subject matter pertains in some embodiments to the use of ALD as a method of coating fiber-based substrates (e.g., textiles or polymer fiber-based materials) or fibers (e.g., nanofibers) with thin films of materials, such as but not limited to metals and metal oxides.
  • fiber-based substrates e.g., textiles or polymer fiber-based materials
  • fibers e.g., nanofibers
  • thin films of materials such as but not limited to metals and metal oxides.
  • the coating of textile media can provide UV protection (e.g. , in clothing applications), pigment protection, chemical protection and/or mechanical or chemical stabilization.
  • the textile materials that can be coated can comprise fibers, yarns, and fabrics either natural, man-made, or combinations of the two, and the textile materials can be in woven, knit, or nonwoven form.
  • inorganic coatings including coatings of silver, copper, and various metal oxides, can increase the conductivity of textile material (e.g., carpet) to reduce static electricity build-up.
  • Coatings of inorganic materials also allow the creation of multifunctional textiles. Multifunctional textiles are materials that possess a combination of many different properties such as flame retardancy, water repellency, and antibacterial activity.
  • multifunctional textiles can be used for a number of different tasks, for example in such industries as medical, geotextiles and construction, upholstery, and filtration, to name a few.
  • modified textile materials can protect against mechanical, thermal, chemical, and biological attacks, and at the same time offer improved durability and performance.
  • the ALD-grown conformal thin films provided by the presently disclosed methods and apparatuses can be utilized, for example, as coatings for the creation of fabrics, such as cotton fabrics, with improved moisture barrier properties, as well as for the functionalization of polypropylene and other polymer-based materials.
  • Inorganic materials are of particular interest as thin film coatings for fiber and textile materials. Coatings that are of particular interest are those which (1 ) improve stability of a material for mechanical, chemical, photo-chemical, or thermal destruction, (2) improve water, oil, and soil repellency properties of a material, (3) exhibit unique light absorption and emission properties in the UV and IR regions, (4) change the electrical conductivity of a material, (5) control release or immobilization of various active species.
  • fibers and textile materials that are modified by such films can exhibit increased yield strength, reduced strain at yield stress, increased elastic modulus, increased fiber toughness, as well as increased wettability. It will be recognized by one of ordinary skill in the art upon a review of the instant disclosure that many materials are useful for more than one of these applications and that inorganic thin films will be useful for other applications not described here.
  • inorganic materials that can change the physical properties of fiber and textiles materials include, for example, various oxides, nitrides, and non-oxide materials.
  • Titanium dioxide is a particular example of an oxide that can influence many different properties. Titanium dioxide is a wide band-gap semiconductor and is known to be a good oxidizing agent for photo-excited molecules and functional groups, making it useful as a photocatalyst or sensor material. Fibers coated with a thin film of titanium dioxide could provide high surface area catalytic mantles.
  • Aluminum oxide is another good example of a coating material that can be deposited using ALD. Aluminum oxide has many favorable traits including strong adhesion to different substrate surfaces, good dielectric properties, and good chemical and thermal stability.
  • Inorganic materials useful in the controlled release or immobilization of active species include, for example, titanium nitride, silver, and copper. IN. Methods of Modifying a Substrate
  • the presently disclosed subject matter provides, in some embodiments, methods of performing modification of substrate surfaces via atmospheric atomic layer deposition or related processes.
  • the methods can be performed without having to place the substrate in a closed reaction chamber.
  • the method does not comprise "spatial" ALD.
  • the methods do not rely on movement of the substrate or the apparatus providing chemical reactants to complete a deposition cycle.
  • the presently disclosed subject matter provides a method for modifying a substrate, the method comprising: providing a substrate; contacting the substrate with a vapor-phase precursor comprising an organic or an inorganic component for a first period of time to create a partial layer (e.g., a partial atomic or molecular layer) of the organic or inorganic component on the substrate, wherein the contacting comprises placing the substrate in proximity to an outlet directing a flow of the vapor-phase precursor to the substrate (e.g., to an outer and/or inner surface of the substrate or through the substrate); and contacting the substrate with a vapor-phase reactant for a second period of time to complete the formation of a layer (e.g., an atomic or molecular layer) on the substrate, wherein the contacting comprises placing the substrate in proximity to an outlet directing a flow of the vapor-phase reactant to the substrate (e.g., to an outer and/or inner surface of the substrate); wherein said method further comprises providing a flow of
  • Providing a flow of non-reactive gas to the substrate during and/or after one or both of the contacting steps can purge excess vapor-phase precursor and/or excess vapor-phase reactant. Provision of the flow of non- reactive gas can also prevent undesired non-surface reaction of the precursor and the reactant.
  • the contacting (or "dosing") steps can be repeated one or more times, e.g., until the film attains the desired thickness.
  • the contacting steps are repeated to provide a thin film having a thickness of between about 1 nanometer (nm) and about 10 microns (i.e., about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 125, 150, 75, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, or 950 nm or about 1 , 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10 microns).
  • the contacting steps are repeated at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 75, 100, 200,
  • the film can have a thickness of less than about 1 nanometer. In some embodiments, the film can have a thickness that is about 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or about 0.9 nm.
  • the substrate can have any shape (e.g., planar, curved, pointed, spherical, cylindrical, cubic, irregular, etc.) and can comprise any suitable material or combination of materials.
  • the substrate is non-planar (e.g., curved, pointed, spherical, irregular, etc).
  • the substrate is flexible.
  • the substrate is non-flexible.
  • the substrate is non-porous.
  • the substrate is a porous substrate.
  • the substrate e.g., the porous substrate
  • the substrate can be selected from the group including, but not limited to, a fiber-based substrate, a metal organic framework, a zeolite, or anodic aluminum oxide.
  • the substrate used can comprise any fiber or textile material, such as, but not limited to, a fiber or textile material of a continuous shape.
  • the shape of the fiber or textile material need not be limited to common cylindrical fibers or planar substrates.
  • the presently disclosed methods can be used to create a conformal coating of individual fibers having complex shapes and surface topologies (e.g., corrugated substrate, non-woven web).
  • a woven cotton fabric comprising yarns made up of many cotton fibers of different sizes and shapes can be used as a substrate.
  • the textile material can be formed from melt blown polyolefin (e.g.
  • the textile material can be spun bond polyolefin nonwoven fiber mats, e.g., where molten polymer is extruded through a spin pack, quenched by cold air, lengthened and tangled by warm air, and calendared and compacted by rollers.
  • the fiber mats produced in this manner can have a more uniform size distribution, with fibers having diameters of approximately 12 to 50 microns.
  • the substrate is a fiber-based substrate
  • the fiber-based substrate can comprise natural fibers, synthetic fibers or both natural and synthetic fibers.
  • the fiber-based substrate is selected from, but not limited to, cotton fiber, cotton fabric, woven cotton fabric, non-woven cotton fabric, protein- based fiber, polyvinyl alcohol fiber, polyvinyl alcohol fabric, woven polyvinyl alcohol fabric, non-woven polyvinyl alcohol fabric, polyolefin polymer fiber, polyolefin fabric, woven polyolefin fabric, non-woven polyolefin fabric, polyethylene terephthalate fiber, polyethylene terephthalate fabric, woven polyethylene terephthalate fabric, non-woven polyethylene terephthalate fabric, polyamide fiber, polyamide fabric, woven polyamide fabric, non-woven polyamide fabric, acrylic fiber, acrylic fabric, woven acrylic fabric, non-woven acrylic fabric, polycarbonate fiber
  • the substrate can comprise a natural or synthetic polymer-based surface.
  • the polymer-based surface can comprise a material selected from, but not limited to, polyimide, polyethersulfone, cellophane, polydimethylsiloxane, polytetrafluoroethylene, wood, cellulose, cotton, polyvinyl alcohol, polyvinyl chloride, polystyrene, polyacrylonitrile, polyethylene, polybutylene, and polyethylene terephthalate.
  • the substrate is substantially stationary during the contacting steps.
  • the method can be performed without moving the substrate between contacting it with the vapor-phase precursor and contacting it with the vapor-phase reactant.
  • it can be advantageous to move the substrate after the contacting steps so that the contacting steps can be repeated when another portion of the substrate is in proximity to an outlet.
  • the substrate is moved between contacting steps.
  • the flow of vapor-phase precursor, vapor-phase reactant, and non-reactive gas can be provided by an apparatus comprising one or more gas delivery units, each gas delivery unit comprising: a first input for the non-reactive gas; one or more gas delivery channels, wherein a first end of each gas delivery channel is in flow communication (e.g., gaseous flow communication) with at least an input for receiving the vapor-phase precursor or the vapor-phase reactant, and wherein a second end of each gas delivery channel comprises an outlet for directing a flow of gas to the substrate; and an output face in flow communication with the outlet of each of the one or more gas delivery channels, with the first input for the non-reactive gas, and with the exterior of the gas delivery unit.
  • each gas delivery unit comprising: a first input for the non-reactive gas; one or more gas delivery channels, wherein a first end of each gas delivery channel is in flow communication (e.g., gaseous flow communication) with at least an input for receiving the vapor-phase precursor or the vapor
  • the outlet or outlets of the gas delivery channel or channels can each be between about 0.1 mm and about 0.5 mm (e.g., about 0.1 , about 0.2, about 0.3, about 0.4, or about 0.5 mm) in diameter.
  • the gas delivery units can also be referred to herein as "gas delivery heads” "reactors” (e.g., “single point reactors”), or “manifolds.”
  • the gas delivery unit can have a single channel or a dual channel configuration, i.e., depending upon how many channels the unit has for vapor delivery of reactive vapors (i.e., for vapor-phase precursor and vapor phase reactant).
  • the delivery units can comprise inner outlets for vapor delivery of the reactive vapors, surrounded by an inert gas flow sheath.
  • one face or outer surface of a substrate e.g., one face of a porous substrate (i.e., the "delivery surface")
  • a substrate e.g., one face of a porous substrate (i.e., the "delivery surface"
  • the apparatus of the presently disclosed subject matter can also include an exhaust system, which can be positioned in proximity to the opposite face of a porous substrate being modified than the face in proximity to the gas delivery unit.
  • the use of the exhaust system can provide one or more of: (1) assist in controlling the flow direction of the vapors from the delivery head through a porous substrate without potential mixing on the delivery surface or perpendicular to the flow direction, (2) promote a more linear pathway or vapor penetration into the porous substrate, (3) increase purge gas velocity and/or materials growth rate, and (4) allow for containment of excess reactive vapors to prevent materials deposition on unwanted regions of the substrate and/or of non- substrate surfaces.
  • the exhaust system can be used to provide pressure differential.
  • the outlet or outlets of the one or more gas delivery channels are coplanar with the output face. In some embodiments, the outlet or outlets are in an interior space of the gas delivery unit. Thus, in some embodiments, the outlet or outlets are recessed (e.g., by between about 1 mm and about 20 mm) within the gas delivery unit, but the output face of the gas delivery unit has at least one opening (e.g., that is between about 0.1 mm and about 0.5 mm in diameter or larger (e.g., is about the diameter of the output face as a whole)) such that the outlet or outlets of the delivery channel or channels are still in flow communication with the exterior of the gas delivery unit.
  • the reactant gases can be directed to a deposition zone on a surface of the substrate from the output face.
  • At least one gas delivery unit comprises a gas delivery channel wherein the first end of the gas delivery channel is in flow communication with one or more input for sequentially receiving the vapor- phase precursor, the non-reactive gas, and the vapor-phase reactant, such that the outlet of the gas delivery channel can sequentially direct a flow of vapor- phase precursor, the non-reactive gas, and the vapor-phase reactant to the substrate.
  • At least one gas delivery unit comprises at least two gas delivery channels, wherein said at least two gas delivery channels comprise: a first gas delivery channel, wherein said first gas delivery channel has a first end in flow communication with one or more inputs for the vapor- phase precursor or for the vapor-phase precursor and the non-reactive gas, and a second end comprising an outlet for delivering the vapor-phase precursor or for sequentially delivering the vapor-phase precursor and the non-reactive gas; and a second gas delivery channel, wherein said second gas delivery channel has a first end in flow communication with one or more inputs for the vapor-phase reactant or for the vapor-phase reactant and the non-reactive gas, and a second end comprising an outlet for delivering the vapor-phase reactant or for sequentially delivering the vapor-phase reactant and the non-reactive gas.
  • each of the one or more gas delivery units of the apparatus for the presently disclosed methods can comprise one or two gas delivery channels.
  • the first and second gas delivery channels can be substantially parallel to one another.
  • the first and second gas delivery channels are not substantially parallel to one another.
  • they can be oriented relative to one another such that they join at or near their outlet ends to form a single combined outlet.
  • the single outlet can be at the vertex of an angle (e.g., a right or an acute angle) formed by a portion of the first and second gas delivery channels.
  • the gas delivery unit comprises a first and a second gas delivery channel (e.g., in substantially parallel orientation) and a partition between said first and second gas delivery channels.
  • the partition can extend from the outlets of the first and second gas delivery channels to the output face of the gas delivery unit (i.e., in a direction parallel to the first and second gas delivery channels).
  • the partition can extend beyond the output face.
  • the gas delivery unit can comprise a second input for non-reactive gas such that the first input for the non-reactive gas is located on one side of the partition and the second input for the non-reactive gas is located on the other side of the partition.
  • providing the substrate comprises positioning an outer or external surface of the substrate between about 0.01 millimeters and about 20 millimeters from an output face of a gas delivery unit. In some embodiments, an outer or external surface of the substrate can be positioned between about 0.02 millimeters and about 1.0 millimeters from an output face of a gas delivery unit.
  • an outer or external surface of the substrate can be positioned between about 0.02 millimeters and about 0.5 millimeters (e.g., about 0.02, 0.04, 0.06, 0.08, 0.1 , 0.12, 0.14, 0.16, 0.18, 0.2, 0.22, 0.24, 0.26, 0.28, 0.3, 0.32, 0.34, 0.36, 0.38, 0.4, 0.42, 0.44, 0.46, 0.48, or 0.5 mm) from an output face of a gas delivery unit.
  • 0.5 millimeters e.g., about 0.02, 0.04, 0.06, 0.08, 0.1 , 0.12, 0.14, 0.16, 0.18, 0.2, 0.22, 0.24, 0.26, 0.28, 0.3, 0.32, 0.34, 0.36, 0.38, 0.4, 0.42, 0.44, 0.46, 0.48, or 0.5 mm
  • the output face can have any desired shape, such as, but not limited to, circular, oval, square, rectangular, etc.
  • an outlet for delivering the vapor-phase precursor and/or reactant is located substantially in the center of the output face or in flow communication with the center of the output face.
  • at least an outlet for the vapor-phase precursor is located such that it is substantially at, or can direct a flow of vapor- phase precursor through, the center of the output face, (e.g., through an opening located at or about at the center of the output face).
  • a spacer can be extended from the output face (e.g., from an outer edge of the output face).
  • the spacer can be useful in positioning the substrate relative to the gas delivery unit, in directing the flow of gases, and/or to prevent unwanted surface modification on portions of the substrate where no surface modification is desired.
  • the apparatus comprises a plurality of gas delivery units (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 100, 500, or more gas delivery units).
  • the plurality of gas delivery units can be in a linear or two-dimensional array.
  • providing the substrate comprises positioning the substrate such that a plurality of portions of an outer or external surface of the substrate are in proximity to the output faces of a plurality of gas delivery units.
  • the use of a plurality of gas delivery units can provide for simultaneous surface modification of a large continuous portion of a substrate or can provide for surface modification of a plurality of separate portions of a substrate.
  • the use of an array of gas delivery units can provide a patterned modified substrate.
  • the gas delivery unit or gas delivery units can be translated relative to the substrate between ALD cycles. This translation can be done manually or mechanically (e.g., via a robotic arm). Particularly as there is no need for an enclosed reaction chamber, the gas delivery unit or units (e.g., an array of gas delivery units) can be provided as a portable or hand held ALD "gun", "pen”, or “jet.”
  • the ALD gun can be used to modify the surfaces of large and/or complex geometry substrates (e.g., steel I-beams or ship hulls) by coating a plurality of portions of the outer surface of the substrate sequentially, moving the ALD gun from proximity to one portion of the surface into proximity with another portion of the surface between ALD cycles.
  • the vapor-phase precursor comprises a metal- containing compound, comprising a metal such as, but not limited to, aluminum, zinc, titanium, tungsten, or zirconium.
  • the vapor-phase precursor comprises, for example, trimethylaluminum (TMA), diethyl zinc (DEZ), titanium tetrachloride (TiCI 4 ), tungsten hexafluoride, titanium isopropoxide, or zirconium tertbutoxide (ZTB).
  • TMA trimethylaluminum
  • DEZ diethyl zinc
  • TiCI 4 titanium tetrachloride
  • ZTB zirconium tertbutoxide
  • the flow of the vapor- phase precursor is provided at a flow rate between about 0.001 and about 5.0 standard liters per minute (slm).
  • the flow rate can be about 0.001 , 0.005, 0.01 , 0.05, 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2.0, 3.0, 4.0, or about 5.0 slm.
  • the flow of the vapor-phase precursor is provided at a flow rate between about 0.05 slm and about 0.2 slm (e.g., about 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11 , 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, or about 0.2 slm).
  • the flow of the vapor-phase precursor is provided at a flow rate between about 0.15 slm and about 0.3 slm.
  • the first period of time i.e., the first "dose" time
  • the first period of time is between about 0.01 seconds and about 60 seconds.
  • the first period of time is between about 0.1 seconds and about 2.0 seconds (e.g., about 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0. 1.1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or about 2.0 seconds).
  • the vapor-phase reactant can comprise oxygen, nitrogen, carbon or silicon atoms, or combinations thereof.
  • the vapor-phase reactant is selected from the group including, but not limited to, H 2 0 (i.e., water vapor), NH 3 , ozone, 0 2 , C0 2 , CO, NO, N 2 0, N0 2 , SiH 4 , and Si 2 H 6 .
  • the vapor-phase reactant is provided at a flow rate between about 0.001 and about 5.0 slm.
  • the flow rate for the vapor-phase reactant can be about 0.001 , 0.005, 0.01 , 0.05, 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2.0, 3.0, 4.0, or about 5.0 slm.
  • the vapor-phase reactant is provided at a flow rate between about 0.05 slm and about 0.2 slm (e.g., about 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11 , 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, or about 0.20 slm).
  • the vapor-phase reactant is provided at a low rate between about 0.15 slm and about 0.3 slm.
  • the second period of time i.e., the second "dose" time
  • the second period of time is between about 0.01 seconds and about 60 seconds.
  • the second period of time is between about 0.1 seconds and about 2.0 seconds (e.g., about 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or about 2.0 seconds).
  • the vapor- phase reactant is H 2 0, the vapor-phase precursor is TMA and the method comprises modifying the substrate with aluminum oxide.
  • any suitable non-reactive (e.g., chemically inert) gas can be used.
  • the non-reactive gas is nitrogen or argon.
  • the non-reactive gas is provided at a flow rate between about 1 and about 100 slm (e.g., about 1 , 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90 or 100 slm).
  • the non-reactive gas is provided at a flow rate between about 5 and about 20 slm (e.g., about 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 slm).
  • a flow of a non-reactive gas is provided for between about 1 second and about 300 seconds after the first period of time and before the second period of time and/or after the second period of time. In some embodiments, the flow of a non-reactive gas is provided for about 40 seconds after the first period of time and before the second period of time and/or after the second period of time. In some embodiments, the flow of a non-reactive gas is provided for about 10 seconds after the first period of time and before the second period of time and/or after the second period of time. In some embodiments, the flow of a non-reactive gas is provided for more than about 300 seconds after the first period of time and before the second period of time and/or after the second period of time. In some embodiments, a flow of non-reactive gas is provided during the first and/or second periods of time.
  • the methods can comprise one or more purge steps and/or can involve the use of a continuous flow of purge gas.
  • the methods described herein can provide modified dose and purge times based on the nature of the substrates used. Depending on the characteristics of the substrate, longer dose and purge times can be necessary to completely saturate the surface. For example, a dense, layered, nonwoven fiber web would require longer dose and purge times when compared to a loosely knit fibrous structure. In addition, reactants generally require longer times to diffuse into the porous and/or fiber samples (such as cotton fiber samples), possibly leading to a change in the growth rate.
  • surface modification in accordance with the presently disclosed subject matter can include adjusting the dose times to allow for penetration into the bulk of a fibrous substrate and/or adjusting purge times to provide complete removal of reactive gases.
  • the presently disclosed methods can be performed at low temperatures ranging from 20 or 25 to 200°C, depending on the nature of the fiber or textile material being used.
  • Synthetic fibers may have a range of melting temperatures depending on the polymer they are constructed from.
  • polypropylene fibers have a melting point of 150°C.
  • Natural fibers, such as cotton fiber have a burning point rather than a melting point and start to degrade at temperatures over 100°C.
  • Precursors and reactants of sufficient reactivity, such as trimethylamines, can be used in order to improve deposition at low temperatures.
  • the ALD process can be carried out at low temperatures in order to prevent degradation of the fiber and textile substrates. Fiber and textile materials are often very sensitive to temperature changes, resulting in changes to their performance capabilities. Therefore, it can be advantageous to keep reaction temperatures as low as possible.
  • the reaction temperature can be increased or decreased depending on the nature of the particular fiber or textile substrate being used.
  • one or both contacting steps are conducted at a temperature between about 20°C and about 200°C (e.g., at about 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, or about 200°C). In some embodiments, one or both contacting steps are conducted at a temperature that is less than about 50°C or less than about 100°C. In some embodiments, the temperature is selected to limit thermal damage to the substrate (e.g., to a temperature-sensitive substrate such as a textile or polymer fiber-based substrate). In some embodiments, one or both contacting steps are conducted at 120°C. In some embodiments, one or both contacting steps are conducted at a temperature of about 50°C. In some embodiments, reaction temperature can be controlled by heating or cooling the gas delivery units of the presently disclosed subject matter or heating or cooling gas delivery lines running into the gas delivery units.
  • a method for depositing polymer films comprising providing a substrate (e.g., a fiber-based substrate); contacting the substrate with a vapor- phase precursor comprising an organic monomer to create an atomic layer of the organic monomer on the substrate; and contacting the substrate with a vapor-phase reactant comprising a complementary organic monomer; wherein said method further comprises providing a flow of a non-reactive gas to the substrate surface during and/or after one or both contacting steps.
  • the contacting steps can be repeated until the desired thickness of polymer films is deposited.
  • the polymer films are deposited on fiber- based substrates using a precursor and reactant that have complementary end- groups to enable binary self-limiting reaction steps.
  • the complementary end-groups include but are not limited to end-groups such as aldehyde, anhydride, amine, ethylene and sulfide.
  • the precursor comprising the organic monomer can be pyromellitic dianhydride and the reactant comprising the organic monomer can be phenylene diamine.
  • the precursor comprising the organic monomer can be phenylene diamine and the reactant comprising the organic monomer can be phenylene dialdehyde.
  • the final structure of the thin film can comprise a combination of layers, such as but not limited to metal containing layers stacked on one another.
  • a film comprising alternating layers of Al 2 0 3 and Ti0 2 can be fabricated.
  • the contacting steps are repeated one or more times and then the substrate is subjected to one or more cycles of a method involving a different vapor-phase precursor and/or vapor-phase reactant.
  • methods are provided for atomic layer deposition of a hybrid organic-inorganic film on a substrate.
  • the method can include providing a fiber-based substrate, contacting the substrate with a vapor-phase reactant comprising a first component comprising an organic or an inorganic component, and contacting the substrate with a vapor-phase reactant comprising an organic or an inorganic component (i.e., depending on the first component), wherein said method further comprises providing a flow of a non-reactive gas to the substrate during and/or after one or both contacting steps, and repeating the pulsing and purging steps as necessary until the desired thickness of hybrid films is deposited.
  • the co-reactant can be an inorganic component (or vice versa).
  • the presently disclosed method can be used for the step-wise deposition of ethylene glycol and diethyl zinc to provide a hybrid film.
  • the surface energy of fiber-based substrates can be modified.
  • the surface energy of the fiber-based structure can be modified to form a uniformly hydrophilic surface.
  • a uniformly hydrophilic surface will demonstrate the same contact angle ( ⁇ 90°) over the surface of the sample.
  • Replicate fiber structures can be created by performing ALD on various fiber formats (including cotton fiber formats), including single fibers, yarn bundles and woven fabrics, and subsequently removing the cotton fibers.
  • ALD atomic layer deposition
  • removal of the core fibers results in freestanding micro- and/or nanostructures (e.g., Al 2 0 3 tubules) as fibers, "yams" and woven structures.
  • the resulting yarns and woven structures are surprisingly flexible and robust, even after the fiber core is removed. Only a very small number of cycles are needed to obtain measurable free-standing micro- and/or nanostructures.
  • Such templated structures developed from readily available woven or non-woven fiber and fabric materials can act as an inorganic base material for a range of advanced devices. Moreover, the ability to fabricate and manipulate free-standing materials that are less than 10 A thick is a unique attribute of ALD that can be exploited for any of a variety of micro- and nanoscale applications.
  • ALD processes can be used to form porous micro- and/or nanostructures. The porous nanostructure can have a controlled porosity based on desired properties for the structure.
  • Microfluidics is an enabling technology that makes possible the study of a range of biological and chemical systems. Typical applications include microliter to femtoliter chemical analysis and reaction, medical diagnostics, chemical and bio-chemical separation, and environmental monitoring. Moreover, microfluidics offers engineered structures with dimensions comparable to that of individual cells, organelles, and single biomolecules. Laboratory microfluidic systems are typically fabricated by casting polydimethylsiloxane (PDMS) against a mold and affixing it to a suitable flat surface. PDMS has several advantages over other materials, particularly its low cost and ease of fabrication. However, PDMS has significant limitations, especially in contact with organic media.
  • PDMS polydimethylsiloxane
  • a key problem with PDMS is that it is hydrophobic, so the channels are difficult to wet and they tend to bind hydrophobic bio-materials.
  • the surface can be relatively inert, so that there is no available simple route for surface modification, although many methods to modify PDMS have been evaluated.
  • microfluidics structures involve material nucleation on a hydrophobic surface.
  • the ALD process can enable a structural characteristic (e.g., a dimension of a microfluidic channel) to be controlled at the atomic monolayer level.
  • an ALD process is performed in micro- or nanostructures (e.g., microfluidic channels) inside a mold, such as a PDMS template. Starting with a mold, channels can be coated using ALD. Then the mold can be removed, resulting in a micro- or nanostructure.
  • the micro- or nanostructure can be an AI 2 O3 based microfluidic structure.
  • micro- and nanoscale systems and uses are disclosed in the following published documents, which are incorporated herein by reference in their entirety: WO2005/101466, WO2005/084191 , WO2007/021755, WO2007/021809, WO2007/021810, WO2007/02181 1 , WO2007/021812, WO2007/021813, WO2007/021815, WO2007/021816, WO2007/021817, and WO2007/024485.
  • the presently disclosed subject matter provides an apparatus that allows chemical deposition (e.g., film deposition) on a substrate without a closed reaction chamber and without moving the substrate or apparatus (e.g., during a single ALD cycle or series of cycles).
  • the apparatus can be used to provide localized deposition on a particular portion or portions of a substrate (e.g., a portion with a dimension of about several centimeters or less).
  • the apparatus can provide localized pulsed and/or sequential gas flow of reactant gases.
  • Non-reactive gases can also be delivered by the apparatus to provide a barrier to enhance uniform deposition of the reactant gases.
  • the apparatus can provide an array of gas delivery units to provide deposition on a larger area of the substrate or to provide patterned deposition on a substrate.
  • the apparatus whether an array or non-array, can be rastered over or around the substrate to provide a patterned modified substrate.
  • Figures 1-10 show various exemplary apparatus and/or gas delivery unit configurations that are suitable for the presently disclosed methods.
  • Figures 1 , 2, 5, 6, and 7 provide examples of single channel gas delivery units.
  • Figures 3, 4, 9 and 10 provide examples of dual channel gas delivery units.
  • apparatus 100 having a delivery valve design (i.e., including valves V-1 , V-2, V-3, and V-4) suitable for vapor delivery from liquid vapor-phase precursor source A and high pressure vapor- phase reactant source B.
  • An inert gas, IG e.g., argon, nitrogen, or helium
  • gas lines 110 can be arranged such that inert gas IG is routed through liquid vapor-phase precursor source A and into delivery channel 140 of the delivery head 120.
  • valves V-1 and V-2 are opened and valve V-3 is closed.
  • Similar designs can be made with two-way and three-way valves and/or when the vapor-phase reactant is from a liquid source and/or when the vapor-phase precursor is from a high pressure source.
  • a three-way valve can inject gas into a stream leading to delivery channel 140 or stop the inert gas flow by opening valve V-4.
  • Valve sequencing and timing can be varied to supply the gases in a particular sequence and/or to provide a desired materials growth rate.
  • apparatus 100 further includes a separate input 150 for providing additional inert gas to delivery head 120.
  • Substrate 160 can be positioned relative to delivery head 120 such that a gas flow from a recessed outlet 170 of gas delivery channel 140 is directed to a surface of the substrate.
  • Optional exhaust system 180 can be positioned on the opposite face of substrate 160 to direct or pull the flow of excess vapors away from the substrate, such as in the direction of the arrows.
  • an apparatus 200 which includes gas delivery unit 220 having single gas delivery channel 210 for the sequential pulsing of vapor-phase precursor A, non-reactive gas ("inert 'purge' gas", IG), vapor-phase reactant B, and non-reactive gas.
  • Vapor phase-precursor A, inert gas IG, vapor-phase reactant B, and inert gas IG enter channel 210 via inlet 212 and are sequentially pulsed to a surface of porous substrate 260 from outlet 270 of channel 210, located near the center of output face 240 of unit 220.
  • Unit 220 also includes separate inlet 215 for inert gas IG.
  • a sheath of inert gas IG surrounds the flow of gases from delivery channel 210.
  • Optional exhaust system 280 can direct excess gas away from the side of substrate 260 opposite to output face 240. Gas flow is indicated by thin arrows (dotted arrows for IG sheath and solid arrows for flow from channel 210 and for excess gas/exhaust).
  • Substrate 260 can be optionally translated relative to unit 220 as indicated by the heavy arrows.
  • outlets 322 and 342 of two gas delivery channels i.e., channel 320 for vapor-phase precursor A and inert purge gas IG, and channel 340 for vapor- phase reactant B and inert purge gas IG
  • gas delivery unit 380 e.g., at the vertex of an angle, such as a right or acute angle formed by ends of the channels
  • gas delivery unit 380 also includes separate inlet 360 for inert gas IG to provide a flow of inert gas IG to surround outlet 385.
  • Outlet 385 is coplanar with output face 390 of unit 380, but could alternatively be recessed inside unit 380.
  • Optional exhaust system 397 can be positioned to direct the flow of excess gas away from substrate 395. Gas flow is indicated by thin arrows (dotted arrows for IG from inlet 360 and solid arrows for flow from outlet 385 and for excess gas/exhaust). Substrate 395 can be optionally translated relative to unit 380 as indicated by the heavy arrows.
  • Dual delivery channel apparatuses can also be configured so that the outlets of the two channels are near or directly next to one another (e.g., in a plane parallel to or co-planar with the output face).
  • Figure 4 shows dual delivery channel apparatus 400 having channels 410 and 415 with inlets 408 and 413. Each reactive gas (the vapor-phase precursor A and vapor-phase reactant B) is expelled from a separate outlet, 412 or 417, such that the flows from outlets 412 and 417 are delivered in individual flow paths surrounded by inert gas IG.
  • apparatus 400 includes gas delivery unit 405 with two substantially parallel gas delivery channels (i.e., channel 410 forvapor- phase precursor A and channel 415 for vapor-phase reactant B).
  • Partition 420 extends between channels 410 and 415, even extending beyond output face 440 of the delivery unit, which is coplanar with outlets 412 and 417 of channels 410 and 415.
  • Delivery unit 405 includes two separate inputs 430 and 435 for inert gas IG, such that a sheath of inert gas IG can surround the flows of A and B from outlets 412 and 417 of channels 410 and 415.
  • Flows of gases (represented by thin arrows) are directed from unit 405 to porous substrate 460.
  • Optional exhaust system 480 can direct and/or pull excess gas away from substrate 460.
  • Substrate 460 can be optionally translated relative to unit 405 as indicated by the heavy arrows.
  • FIG 5 shows a bottom view of a single delivery channel apparatus 500 having a gas delivery unit 502 with a circular output face.
  • Gas delivery unit 502 comprises a gas delivery channel for reactive gases (cross-hatching) with a circular outlet 506, which has a diameter d and is surrounded by a ring 508 in flow communication with a flow of inert gas IG (stippling) which can enter (arrow) unit 502 via side inlet 504.
  • Figure 6 shows a bottom view of a single delivery channel apparatus 600 having a rectangular output face 602.
  • Outlet 604 of a gas delivery channel for reactive gases can have dimensions I and w and can be surrounded by an outer area 606 in flow communication with a non-reactive gas IG which can enter (arrows) apparatus 600 from a side inlet 608.
  • a substrate sheet (not shown in Figure 6) can be moved past output face 602 at a constant rate to modify several continuous portions of the substrate.
  • Figure 7 shows how movement of apparatus 700 comprising a single point reactor (i.e., comprising single gas delivery unit 710) can provide a patterned film 725 on substrate 720.
  • Single point reactor 710 is placed in proximity to, but not touching, an outer surface of substrate 720.
  • Single point reactor 710 includes a gas delivery channel 712 for sequentially pulsing vapor- phase precursor A, inert gas (inert), vapor-phase reactant B, and inert gas (inert) to a surface of substrate 720, as well as a separate inlet 714 for inert gas (inert).
  • Optional exhaust system 730 can be placed in proximity to an opposing outer surface of substrate 720 from the surface in proximity to reactor 710, e.g., to enhance gas flow and/or remove excess gases (arrow). Between ALD cycles from the sequential pulsing of the gases, reactor 710 can be translated in the x and y directions in a plane over the surface of substrate 720 to create pattern 725 of a deposited film.
  • the apparatus can be moved manually or via an electronically controlled and/or mechanized translation or rastering system (not shown).
  • Arrays (e.g., linear, square, rectangular, circular, or other shaped) of multiple gas delivery units can also be rastered or translated over a surface or surfaces of a substrate to provide a patterned modified substrate.
  • Figure 8 shows an apparatus 800 that includes roller system 820 for moving substrate 840 (e.g., a length of fabric) past array 810.
  • Array 810 includes a linear series of gas delivery units 812 wherein every other gas delivery unit delivers the vapor-phase precursor A and the non-reactive gas I. The remaining gas delivery units deliver the vapor-phase reactant B and the non-reactive gas I.
  • roller system 820 can be used to translate substrate 840 so that portions of the substrate that have been contacted with precursor A are moved into proximity with a flow from a delivery unit that provides reactant B (e.g., to complete formation of an atomic layer of film).
  • Flow of A, B, and I from units 812 is indicated by the thin straight arrows. Movement of roller system 820 is indicated by curved arrows.
  • the vapor flows from the individual delivery units can be directed so that there is overlap between the deposition zones from the precursor and reactant delivery units. If there is overlap between the deposition zones, translation of the substrate is not necessary to complete formation of an atomic layer, but can be performed so that modification of a different portion of the substrate can be performed.
  • the roller system can be used to position the substrate at a particular distance from the array (e.g., 20 mm or less, but not directly in contact) to optimize surface modification.
  • optional exhaust system 860 can be provided in proximity to an opposing outer surface of substrate 840 from the outer surface in proximity to array 810, to direct excess gas away from the substrate (indicated by the thick straight arrow).
  • Figure 9 shows another embodiment of a multiple gas delivery unit apparatus. More particularly, Figure 9 shows an apparatus 900 comprising a linear array 902 of single point reactors 904 (i.e., gas delivery units), wherein each single point reactor 904 includes delivery channels 906 for a vapor-phase reactant R (e.g., H 2 0) and a vapor-phase precursor P (e.g., trimethylaluminum, TMA), and an inlet 908 for a non-reactive (nitrogen, N 2 ) gas IG.
  • R e.g., H 2 0
  • P vapor-phase precursor
  • N 2 non-reactive gas IG
  • one or more of the delivery units of Figure 9 could be a single channel unit that delivers both precursor P and reactant R (e.g., via sequential pulsing through a single delivery channel).
  • outlets 910 and 912 of the two delivery channels 906 are located at (i.e., are co- planar with) output face 914 of a single point reactor.
  • the outlets can be recessed in the body of the reactor (e.g., by about 1 to about 20 mm).
  • a substrate S e.g., a porous substrate
  • which can be movable or fixed, can be positioned in proximity to the output faces (e.g., within about 20 mm or less).
  • a roller system such as that shown in Figure 8 could be added to the apparatus of Figure 9 to facilitate movement of substrate S between material deposition cycles.
  • substrate S can be positioned by a frame or other type of support.
  • gases can be removed from the underside of the substrate (e.g., using an optional exhaust system).
  • each of reactors 904 is a tubular body (e.g., with a largest diameter of about 0.5 to about 1 cm) that tapers toward an end comprising circular output face 914.
  • a tubular body e.g., with a largest diameter of about 0.5 to about 1 cm
  • larger diameter single point reactors can also be used.
  • each of the reactors could have a tubular body that has a largest diameter of between about 0.5 cm and about 4 cm.
  • Gas flow (as shown by arrows) from the outlets 910 and 912 can spread out from output face 914 to provide a conical area over substrate S where gas flows toward substrate S.
  • This area can be referred to as the "deposition zone" DZ and is located over a portion of the substrate where, for example, an atomic layer is deposited by an ALD cycle or cycles to provide a coated substrate CS.
  • the substrate surface area modified by each reactor can be somewhat larger in diameter than the output face of the gas delivery unit.
  • the individual reactors in the array can be positioned such that there is a gap between the deposition zones and a patterned (e.g., dotted) and/or non-homogenous film is provided on the surface of the substrate.
  • the delivery units are provided such that deposition zones DZ touch or overlap to provide a continuous and/or homogenous surface modification on substrate S.
  • linear array 902 shown in Figure 9 a series of adjoining portions of substrate S can be modified to provide coated substrate CS.
  • the shape of deposition zone DZ can vary depending upon the shape of output face 914.
  • the array of multiple single point reactors can be provided as a two dimensional (e.g., square or rectangular) array.
  • FIG. 10 shows apparatus 1000 comprising dual channel single point reactor 1010 with two satellite non-reactive gas delivery units 1090.
  • Single point reactor 1010 has two delivery channels (i.e., 1020 for delivery of vapor- phase precursor (A) and 1030 for delivery of vapor-phase reactant (B)) and side input 1040 for a non-reactive gas (NRG).
  • Outlets 1050 of delivery channels 1020 and 1030 are in the interior of single point reactor 1010, recessed from output face 1060. Gas flow is directed from opening 1070 in output face 1060 to substrate 1080, providing a deposition zone as indicated by the single headed arrows under reactor 1010.
  • Spacers 1075 are extended from the outer sides of output face 1060 toward substrate 1080.
  • Satellite non- reactive gas delivery units 1090 are positioned on either side of single point reactor 1010. Satellite non-reactive gas delivery units can direct a flow of NRG to the surface of the substrate, thereby providing an area over the substrate that is substantially free of reactive gases A and B (see double headed arrows under each of the satellite non-reactive gas units). While satellite non-reactive gas delivery units 1090 as shown in Figure 10 are parallel to single point reactor 1010, either or both could also be inclined at an angle (e.g., at an about 45 degree angle) from the axis of single point reactor 1010. Referring again to Figure 10, exhaust 1095 from the process can exit from openings between spacers 1075 and satellite non-reactive gas delivery units 1090. While Figure 10 shows two satellite non-reactive gas delivery units, additional satellite non- reactive gas delivery units can be provided to completely surround the single point reactor, if desired.
  • the presently disclosed subject matter provides an apparatus for modifying a substrate, wherein the apparatus comprises one or more gas delivery units, each gas delivery unit comprising: a first input for the non-reactive gas; one or more gas delivery channels, wherein a first end of each gas delivery channel is in flow communication with at least an input for receiving the vapor-phase precursor or the vapor-phase reactant, and wherein a second end of each gas delivery channel comprises an outlet for directing a flow of gas to a substrate; and an output face in flow communication with the outlet of each of the one or more gas delivery channels and with the first input for the non-reactive gas, and is adapted for gaseous and/or flow communication with an exterior of the gas delivery unit.
  • the outlet or outlets of the one or more gas delivery channels are coplanarwith the output face. In some embodiments, the outlet or outlets are in an interior space of the gas delivery unit (e.g., recessed by a few millimeters or centimeters from the output face). In some embodiments, the outlet or outlets are recessed by about 1 to about 20 mm (e.g., about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, or about 20 mm) from the output face.
  • the outlet for delivering a flow of the vapor-phase precursor (and/or the vapor-phase reactant) is at or near the center of the output face. In some embodiments, at least the outlet providing the vapor- phase precursor flow is at or near the center of the output face. In some embodiments, when the outlet is recessed in the gas delivery unit, the outlet for delivering a flow of the vapor-phase precursor (and/or the vapor-phase reactant) can be positioned such that gas flow is directed through or near to the center of the output face (e.g., through an opening in the center or near the center of the output face).
  • the output face can have any shape, such as but not limited to, circular, square, rectangular, oval, etc. In some embodiments, the output face is square or rectangular. In some embodiments, the output face is substantially circular. In some embodiments, the output face has a diameter or other dimension (e.g., length or width) that is about 0.5 cm or smaller. However, the output face can also be larger (e.g., be between about 0.5 cm and about 4 cm or larger). In some embodiments, the output face has an opening or a plurality of openings, wherein each opening is smaller in diameter than the output face as a whole, for directing gas flow to the surface of a substrate.
  • a diameter or other dimension e.g., length or width
  • the output face can also be larger (e.g., be between about 0.5 cm and about 4 cm or larger).
  • the output face has an opening or a plurality of openings, wherein each opening is smaller in diameter than the output face as a whole, for directing gas flow to the surface of a substrate.
  • one or more openings in the output face have a diameter between about 0.1 mm and about 0.5 mm (e.g., about 0.1 , 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5 mm).
  • the gas delivery unit comprises a tubular body comprising an input face at a first end of the tubular body adapted to receive one or more input ports and/or one or more gas delivery channels, and wherein the output face is at a second end of the tubular body.
  • the tubular body can be tapered such that the output face has a smaller diameter than the input face.
  • the input face and/or main portion of the tubular body can have a diameter that is between about 0.5 and about 1.0 centimeters (e.g., about 0.5, 0.6, 0.7, 0.8, 0.9 or 1 cm).
  • the input face and/or main portion of the gas delivery unit body is larger than about 1 cm in diameter.
  • the input face and/or main portion of the body is between about 1 cm and about 4 cm in diameter (e.g., about 1 , 1.5, 2, 2.5, 3, 3.5, or 4 cm in diameter).
  • Each gas delivery unit can have one, two, three, four, five, ten, or more gas delivery channels.
  • the gas delivery units can each be single or dual channel gas delivery units (i.e., comprising one or two gas delivery channels, respectively).
  • at least one gas delivery unit comprises a gas delivery channel wherein the first end of the gas delivery channel is in flow communication with one or more input for sequentially receiving the vapor-phase precursor, the non-reactive gas, and the vapor-phase reactant. See e.g., Figures 1 and 2.
  • At least one gas delivery unit comprises at least two gas delivery channels, wherein said at least two gas delivery channels comprise: a first gas delivery channel, wherein said first gas delivery channel has a first end in flow communication with one or more inputs for the vapor-phase precursor or for the vapor-phase precursor and the non-reactive gas, and a second end comprising an outlet for delivering the vapor-phase precursor or for sequentially delivering the vapor-phase precursor and the non-reactive gas; and a second gas delivery channel, wherein said second gas delivery channel has a first end in flow communication with one or more inputs for the vapor-phase reactant or for the vapor-phase reactant and the non-reactive gas, and a second end comprising an outlet for delivering the vapor-phase reactant or for sequentially delivering the vapor-phase reactant and the non-reactive gas.
  • the first and second gas delivery channels are substantially parallel to one another. See e.g., Figure 4.
  • the gas delivery unit can optionally comprise a partition between the first and second gas delivery channels, extending in a direction parallel to said channels, beyond the outlets of said channels toward and/or beyond the outlet face.
  • the gas delivery unit can further comprise a second input for the non-reactive gas such that the first input for the non-reactive gas is located on one side of the partition and the second input for the non-reactive gas is located on the other side of the partition.
  • the flow of gas from both gas delivery channels can be surrounded by sheath of non-reactive gas.
  • the first and second gas delivery channels can join one another near or at their second ends to form a single outlet. See e.g., Figure 3.
  • the single outlet can be formed, for example, at the vertex of a right (i.e., 90°) or acute (i.e., less than 90°) angle formed by portions of the bodies of the first and second gas delivery channels.
  • each gas delivery channel outlet has a diameter of between about 0.1 mm and about 0.5 mm.
  • the outlet or outlets can have a diameter of about 0.1 , 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or about 0.5 mm.
  • the apparatus of the presently disclosed subject matter can comprise a substrate support.
  • the support can aid in keeping the substrate positioned in proximity to, but not in direct contact with, the output face of the gas delivery unit.
  • Suitable supports include, but are not limited to, stationary or adjustable platforms and frames, roller systems, and conveyor belts. Adjustable supports can be manually or mechanically adjustable. In some embodiments, supports can be adjusted via electronic control systems.
  • the support can support the substrate when the substrate is positioned about 20 mm or less from, but not in direct contact with, the output face. In some embodiments, the support can support the substrate positioned about 20, 19, 18, 17, 16, 15, 14, 13, 12, 11 , 10, 9, 8, 7, 6, 5, 4, 3, 2, or about 1 mm from the output face.
  • the support is adapted to hold the substrate stationary.
  • the support is adapted to translate the substrate with respect to an output face.
  • the support can be adapted to translate the substrate in one or more directions in a plane parallel to the output face (between deposition cycles, e.g., to produce a patterned modified substrate) and/or can be adapted to adjust the distance of the substrate from the output face (e.g., to control the rate of deposition or the area size of the deposited film).
  • the apparatus can comprise a roller system for positioning and translating the substrate relative to one or more output faces.
  • one or more gas delivery units of the presently disclosed apparatus can be translated with respect to a length, width, and/or height of a substrate.
  • one or more gas delivery units can be rastered over the substrate to provide a patterned modified substrate.
  • one or more gas delivery units can be provided as an ALD (or other modification process) "gun", which can be handheld or robotically moved relative to a substrate surface.
  • the apparatus comprises an array of gas delivery units.
  • the apparatus comprises a plurality of gas delivery units (e.g., 2, 3. 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 40, 45, 50, 75, 100, 200, 300, 400, 500, 1000 or more gas delivery units).
  • the plurality of gas delivery units can be arranged in a single row to form a linear array of gas delivery units.
  • the array can also be two-dimensional.
  • the plurality of gas delivery units can be arranged in a plurality of rows to form a square or rectangular array of gas delivery units.
  • the apparatus further comprises an exhaust system.
  • the exhaust system can create a pressure differential between the outlet or outlets of the one or more gas delivery channels and the substrate and/or to remove excess vapor-phase precursor, excess vapor-phase reactant, non-reactive gas, and/or any gaseous side products formed during use of the apparatus.
  • the exhaust system can comprise a tube or manifold, a fan, and/or a vacuum.
  • each satellite gas delivery unit comprises a gas delivery channel for delivery of a flow of non-reactive gas to the substrate.
  • Each satellite gas delivery unit can be positioned adjacent to a gas delivery unit that delivers reactive gas to the substrate.
  • a gas delivery unit can be adjacent to one, two, three, or four satellite gas delivery units.
  • the satellite gas delivery units can be used to localize the surface modification to one or more particular positions on the substrate and/or to prevent undesirable gas-phase reactions.
  • the satellite gas delivery unit can have its main axis parallel to that of a gas delivery unit or can be angled (e.g., have its main axis at an about 45 degree angle) relative to the main axis of the gas delivery unit.
  • the apparatus can comprise a roller system and an array of gas delivery units wherein each gas delivery unit delivers either a vapor-phase precursor or a vapor-phase reactant.
  • the apparatus comprises a roller system and an array of vapor- phase precursor delivery units and vapor-phase reactant delivery units, wherein each vapor-phase precursor delivery unit comprises a vapor-phase precursor delivery channel, wherein a first end of the channel is in flow communication with one or more inputs for receiving the vapor-phase precursor or receiving the vapor-phase precursor and a non-reactive gas, and wherein a second end of the channel comprises an outlet for directing a flow of vapor-phase precursor and/or non-reactive gas to a substrate; wherein each vapor-phase reactant delivery unit comprises a vapor-phase reactant delivery channel, wherein a first end of the channel is in flow communication with one or more inputs for receiving the vapor-phase reactant or receiving the vapor-phase reactant and a non-reactive gas, and wherein
  • the apparatus further comprises an exhaust system for creating a pressure differential between the outlets of the delivery channels and the substrate and/or to remove excess vapor-phase precursor, excess vapor-phase reactant, non-reactive gas, and/or any gaseous side products formed during use of the apparatus.
  • the presently disclosed subject matter provides a modified substrate (e.g., a modified porous and/or fiber substrate).
  • the modified substrate is prepared by one of the presently disclosed methods and/or using one of the presently disclosed apparatuses.
  • the modified substrate is modified with a thin film (e.g., of aluminum oxide or another material that can be deposited by ALD or low temperature ALD), wherein the thin film has a thickness of less than 10 microns, less than 1 micron, less than 100 nm, less than 50 nm, less than 10 nm, or less than 1 nm.
  • the modified substrate is patterned with a thin film.
  • the modified substrate can be prepared using a method or apparatus wherein a gas delivery unit or units are rastered or otherwise translated over a surface of the substrate between ALD cycles or wherein a substrate is moved relative to one or more gas delivery units for ALD between ALD cycles.
  • the modified substrate can be prepared wherein a roller or another support system translates the substrate relative to one or more gas delivery units between ALD cycles.
  • the presently disclosed apparatus or method provides a modified fiber or porous substrate wherein the substrate is conformally modified.
  • the presently disclosed subject matter can provide a fiber- based substrate (e.g., a fabric or fiber mat) wherein each fiber in the substrate is modified by a conformal and uniform thin film.
  • the presently disclosed subject matter relates generally to the production of thin films by atomic layer deposition (ALD) process or similar processes at atmospheric pressure and/or in the absence of a closed reaction chamber. Further, in some embodiments, the presently disclosed subject matter more particularly relates to the production of conformal, uniformly thin films with precise thickness and composition control over large scales.
  • the substrate modified using the presently disclosed method or apparatus is a fiber-based substrate.
  • the presently disclosed subject matter can be used to coat and modify low-cost polymer fibers to produce a surface that can be readily functionalized.
  • the modification of the surface energy of the fiber-based substrate can entail atomic layer deposition for surface treatment for fiber-based filters by depositing a material with a strong surface charge, and thereby providing an efficient and durable approach to enable surface functionalization.
  • the substrate can be modified by ALD to provide a high-density amino-group functionalized surface. See U.S. Patent Application Publication No. 2009/0137043, incorporated herein by reference in its entirety.
  • a nonwoven fiber mat comprising a synthetic polymer such as polypropylene, after coating with ALD, can become a low-cost and easy to handle filtration platform to enable a chosen chemical functionality, such as affinity ligands, to be bound to the surface with very high density.
  • a chosen chemical functionality such as affinity ligands
  • Such novel device platform materials can result in a wide variety of new applications, including blood purification, water decontamination, specialty nanoparticle, and nanotube collection, as well as chemical and bio-hazard detection systems.
  • a particular example is the production of precision modified low-cost nonwoven fibers for use in targeted protein filtration and separation devices, such as a blood filtration device. Such devices can be effective at removing transmissible spongiform encephalopathies caused by prion proteins in contaminated blood supplies.
  • the surface energy of the coated fibers can depend on the material used for coating, as well as the thickness of the ALD coating applied.
  • the nonwoven fiber platform is an example of a complex surface topology, where the surface contour and appearance changes as one adjusts the scale of observation.
  • High surface area complex nanostructures are gaining interest in electronic systems. Examples include organic-based photovoltaic structures and novel fuel cell designs where increased surface area enhances the overall device efficiency. (See, for example, U.S. Patent Nos. 3,969,163 and 7,160,424, the disclosures of which are incorporated herein by reference in their entirety.)
  • highly uniform coating techniques such as ALD can allow modification of the surface functionality and composition within the complex nanostructure to broaden the applicability and reduce the fabrication cost of such device systems.
  • manufacturing techniques are of interest that can modify fiber surface functionality, as well as the bulk properties within a woven fabric to protect against mechanical, chemical, biological and thermal exposure, and effectively repel undesirable foreign substances, while maintaining the benefits of lightweight breathable fabrics.
  • Inorganic insulator and metallic coatings on engineered fabrics are capable of meeting at least some of these objectives. Extending reactive systems and components to fabric platforms to produce catalytic mantles is another area of application.
  • methods are provided for reproducibly converting the surface of fiber systems into inorganic material forms to, for example, significantly change the wetting properties of filters and other separation media, or enable template fabrication of hollow nanoscale needles, spheres, or other structures for bio-medical or tissue engineering applications.
  • the wettability of a surface can be affected by the surface topography and roughness. For example a large contact angle observed for coated fibers can be ascribed to an increase in the fiber rigidity by the more incompliant inorganic coating, effectively reducing the total contract area between the fiber and the water droplet. For a super-hydrophobic material, a contact angle of greater than 120° is desired.
  • the ability to conformally modify woven textile materials with near monolayer precision can provide new multifunctional textiles with properties and performance that deviate radically from current structured fabrics.
  • these multifunctional textiles can be used for a number of different tasks, for example in such industries as medical, geotextiles and construction, upholstery, and filtration, to name a few.
  • these modified textile materials can still meet consumer demand in regards to comfort, ease of care, and health issues, and the modified textile materials can protect against mechanical, thermal, chemical, and biological attacks and offer improved durability and performance.
  • methods are provided for surface modification of fiber webs using biocompatible materials such as TiN as a coating for implant materials including, for example, heart valves and orthopedics, due to the superior mechanical properties, corrosion resistance, and low cytotoxicity of TiN.
  • TiN is often used as a hard, wear-resistant surface treatment, and it has been investigated as an antibacterial coating.
  • the self-limiting film growth mechanism that is characteristic of ALD provides a technique to coat a wide range of substrates using conditions more favorable than other methodologies such as physical vapor deposition or plasma immersion ion implantation. Due to the nature of the process, self-limiting reactions allow for high precision of metallic and metal oxide deposition on the nano-scale.
  • ALD atomic layer deposition
  • Atmospheric ALD was performed using nitrogen (N 2 ) as the inert/purge gas, trimethylaluminum (TMA) as the vapor-phase precursor, and water as the vapor-phase reactant, forming a layer of Al 2 0 3 on a substrate.
  • the nitrogen, TMA, and water were provided via a dual channel gas delivery unit which could direct a flow of the precursor, reactant and purge gas to a surface of the substrate.
  • the N 2 flow rate for the water and TMA lines could be varied between about 0.5 and 1.0 slm and the N 2 flow rate for the purge line could be varied between 4 and 0 slm.
  • the effects of providing or not providing a continuous flow of inert gas via the purge line was determined as follows. Substrates were treated to 10 cycles of ALD, each cycle comprising a 1.0 second TMA dose (0.3 slm), a 40 second N 2 purge, a 1.0 second water dose (0.65 slm), and a 40 second N 2 purge. N 2 was provided at a flow rate of 4 slm. Some substrates received a continuous flow of inert gas while other substrates received inert gas only during the 40 second purge steps. The gas delivery unit was heated to 50°C. Without continuous purging, the modified substrate appeared to have particles on its surface. In contrast, the surface of the substrate modified using a continuous inert gas purge appeared to have no particles.
  • the effect of temperature was also studied. Using a gas temperature of either room temperature (about 20°C) or 50°C, substrates were exposed to 10 cycles of ALD using 1 second dosing times for TMA (0.3 slm) and water (0.65 slm). The purge gas flow rate was 4 slm. The modified substrate treated with gases heated to 50°C appeared slightly more homogenous.
  • TMA vapor-phase precursor
  • high gas flow rate e.g., of the inert/purge gas
  • the inert/purge gas can create a low pressure region between the outlet or output face and the substrate.
  • this phenomenon can be explained by Bernoulli's principal. More particularly, it has been observed that a low pressure region can be created when there is a gap size of less than about 5 mm between the reactor output face and the substrate. As a result of the low pressure region, the substrate can be sucked up and become self-positioned relative to the output face without any physical bottom support.
  • the upward force exerted at atmospheric pressure balances with downward force exerted by the high gas flow (e.g., of the carrier gas) out of the reactor.
  • the high gas flow e.g., of the carrier gas
  • This can be attributed mainly to the high gas velocity coming out of the reactor structure (e.g., the tapered structure) at the reactor output face.
  • the gas flow dynamics between the reactor output face and the substrate can resemble that of a confined impinging jet at high velocities and low flow gap relative to orifice diameter.
  • Atmospheric ALD was performed on 12 mm x 12 mm silicon pieces using nitrogen (N 2 ) as the inert/purge gas, trimethylaluminum (TMA) as the vapor-phase precursor, and water as the vapor-phase reactant, thus forming a layer of AI2O3 on a substrate.
  • the nitrogen, TMA, and water were provided via a dual channel gas delivery unit which could direct a flow of the precursor, reactant and purge gas to a surface of the substrate.
  • the N 2 flow rate for the water and TMA lines could be varied between about 0.05 and 0.5 slm and the N 2 flow rate for the purge line could be varied between about 2 and about 20 slm and heated up to about 200°C.
  • Figure 11 shows the growth rate of the Al 2 0 3 film on the surface of the substrate as a function of number of ALD cycles.
  • the film formed after 300 ALD deposition cycles as described above in Example 2 showed a three region (or zone) deposition pattern (e.g., within the deposition zone as a whole). See Figure 12.
  • This deposition pattern is also represented schematically in Figure 13. The pattern is believed to be due to changes in gas velocity along the substrate surface as the carrier (inert) gas exits an ALD point reactor and interacts with a substrate (i.e., a flat, non-porous substrate).
  • a substrate i.e., a flat, non-porous substrate.
  • top view Referring to the top view of Figure 14, gas flow (indicated by arrows) is directed from opening 1410 in output face 1415 of a single point reactor 1400 toward flat substrate 1420.
  • a confined turbulent flow develops outside the central ALD deposition zone (Z1 in Figures 12 and 13), and the turbulent flow shows a small region (see the circular ring labeled Z2 in Figures 12 and 13) of chemical vapor deposition (CVD) Al 2 0 3 outside of the central ALD deposition zone.
  • the ring of Z2 is relatively light in color in Figure 12 and black in Figure 13.
  • the orthogonal jet profile and jet exit velocity is conserved up to the substrate surface. At the impinging point on the surface, the axial velocity is equal to the jet exit velocity and the radial gas velocity is almost zero.
  • SP Stenant point: maximum axial velocity, zero radial velocity, difficult gas purging.
  • Z1 (Zone 1, true ALD deposition zone): accelerating flow with a laminar boundary layer and low radial turbulence intensity.
  • Z2 (Zone 2, transition-small CVD zone): turbulent flow with maximum radial turbulence intensity and velocity. The position and size of this zone depends on the ALD reactor orifice to substrate separation distance, Reynolds number and orifice geometry.
  • Z3 (Zone 3, ALD like deposition zone): Decelerating flow of a likely laminar boundary layer depending on the jet exit velocity and outer surface pressure.
  • the size of the regions/zones can be controlled by decreasing the inert/purge gas flow rate. For example, 300 cycles of ALD deposition was performed on a silicon substrate as described above in Example 2, only changing the inert (N 2 ) gas flow rate from 10 to 7 slm. See Figure 15. When the inert gas flow was reduced, the diameter of Z1 decreased from about 7.5 mm to about 5 mm. Thus, Figure 15 illustrates that the size of Z1, where the laminar flow region exists and true ALD deposition occurs, can be ultimately controlled by changing the impinging flow gas dynamics (e.g. inert gas flow rate, dose times, purge times) and by modifying the reactor deposition head dimensions.
  • impinging flow gas dynamics e.g. inert gas flow rate, dose times, purge times

Abstract

La présente invention concerne la modification de substrats avec un dépôt de couche atomique (ALD) à basse température ou des procédés correspondants, ladite modification étant effectuée à la pression atmosphérique et en présence ou en l'absence d'une chambre de réaction fermée. Le substrat peut être poreux et/ou avoir une surface non-plane. Le procédé peut être réalisé en l'absence de mouvement du substrat. La présente invention concerne également un appareil pour effectuer la modification de substrat en l'absence d'une chambre de réaction fermée et sans qu'aucun mouvement du substrat ou de l'appareil ne soit nécessaire.
PCT/US2013/032203 2012-03-20 2013-03-15 Procédés et appareil pour le dépôt de couche atomique à la pression atmosphérique WO2013142344A1 (fr)

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